Supramolecular synthons in hydrates and solvates of lamotrigine: a tool for cocrystal design

Pavlović, G.; Lekšić, E.; Meštrović, E.

doi:10.1107/S2052520624002567

research papers

STRUCTURAL SCIENCE
CRYSTAL ENGINEERING
MATERIALS

ISSN: 2052-5206

Volume 80| Part 3| June 2024| Pages 193-200

https://doi.org/10.1107/S2052520624002567

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Supramolecular synthons in hydrates and solvates of lamotrigine: a tool for cocrystal design

Gordana Pavlović,^a ^* Edislav Lekšić ^b and Ernest Meštrović ^c

^aDepartment of Applied Chemistry, University of Zagreb Faculty of Textile Technology, Prilaz baruna Filipovića 28a, Zagreb, 10000, Croatia, ^bResearch and Development, PLIVA Croatia Ltd, Prilaz baruna Filipovića 29, Zagreb, 10000, Croatia, and ^cDepartment of General and Inorganic Chemistry, University of Zagreb Faculty of Chemical Engineering and Technology, Trg Marka Marulića 19, Zagreb, 10000, Croatia
^*Correspondence e-mail: gpavlovic@ttf.unizg.hr

Edited by A. Nangia, CSIR–National Chemical Laboratory, India (Received 14 December 2023; accepted 18 March 2024; online 10 May 2024)

The molecule of anti-epileptic drug lamotrigine [LAM; 3,5-diamino-6-(2,3-dichlorophenyl)-1,2,4-triazine] is capable of the formation of multicomponent solids. Such an enhanced tendency is related to the diverse functionalities of the LAM chemical groups able to form hydrogen bonds. Two robust synthons are recognized in the supramolecular structure of LAM itself formed via N—H⋯N hydrogen bond: homosynthon, so-called aminopyridine dimer or synthon 1 [R₂²(8)] and larger homosynthon 2 [R₃²(8)]. The synthetic procedures for a new hydrate and 11 solvates of LAM (in the series: with acetone, ethanol: two polymorphs: form I and form II, 2-propanol, n-butanol, tert-butanol, n-pentanol, benzonitrile, acetonitrile, DMSO and dioxane) were performed. The comparative solid state structural analysis of a new hydrate and 11 solvates of LAM has been undertaken in order to establish robustness of the supramolecular synthons 1 and 2 found in the crystal structure of LAM itself as well as LAM susceptibility to build methodical solid state supramolecular architecture in the given competitive surrounding of potential hydrogen bonds. The aminopyridine dimer homosynthon 1 [R₂²(8)] has been switched from para-para (P-P) topology to ortho-ortho (O-O) topology in all crystal structures, except in LAM:n-pentanol:water solvate where it remains P-P. Homosynthon 2 [R₃²(8)] of the LAM crystal structure imitates in the LAM solvates as a heterosynthon by replacing the triazine nitrogen proton acceptor atoms of LAM with the proton acceptors of solvates molecules.

Keywords: cocrystals; lamotrigine; solvates; crystal engineering; supramolecular synthons.

CCDC references: 1483193; 1483194; 1483195; 1483196; 1483197; 1483198; 1483199; 1483200; 1483201; 1483202; 1483203; 2354026

1. Introduction

Understanding the synthon hierarchy and robustness of the systems susceptible to forming multicomponent solids presents a tool for supramolecular design of materials with desired properties (Almarsson et al., 2012 ; Trask, 2007 ). Solid state chemistry of multicomponent solids has been the focus of pharmaceutical chemistry and industry over the last several decades due to the appearances of various phenomena in such multicomponent solids such as polymorphism (Bernstein, 2007 ), hydrates (Morris, 1999 ; Khankari & Grant, 1995 ), solvates (Griesser, 2006 ) or cocrystals, especially API (active pharmaceutical ingredient) cocrystals (Duggirala et al., 2016 ). Recently, Bolla with coauthors (Bolla et al., 2022 ) published one of the most comprehensive overviews of preparative techniques, design, methodology and crystal engineering of pharmaceutical cocrystals. Such multicomponent solid state forms can modify the physical and chemical properties of pharmaceuticals through the solid state phenomena of mutual molecular recognition and self-assembling via non-covalent interactions. Following the definition of cocrystals given by FDA from February 2018 [US Department of Health and Human Services Food and Drug Administration Center for Drug Evaluation and Research (CDER)] that cocrystals are associated by nonionic and noncovalent bonds/interactions with coformers, one can distinguish among various crystalline solid state forms such as solvates, cocrystals or salts or their subsets such as solvates of cocrystals, solvates of salts or solvates of cocrystals of salts. The classification of cocrystals distinguishes the subset of ionic cocrystals, which are formed from a salt and one or more salts or neutral molecular coformers, from that of molecular cocrystals composed of two or more neutral molecular compounds (Braga et al., 2010 ; Haskins et al., 2022 ).

Anti-epileptic drug lamotrigine (LAM) [3,5-diamino-6-(2,3-dichlorophenyl)-1,2,4-triazine] shows a tendency to form multicomponent solids such as salts, solvates, cocrystals or their subsets such as solvates or hydrates of LAM salts or LAM cocrystals (Sridhar & Ravikumar, 2011 ; Chadha et al., 2011 ). The study of multicomponent forms of LAM such as solvates presents a valuable foundation for the study and design of supramolecular synthons for LAM cocrystals from the crystal engineering perspective (Desiraju, 1995 ; Aakeröy & Salmon, 2005 ; Rodriguez-Hornedo et al., 2007 ).

Analysis of the CSD (version 5.45; November 2023) for a structural fragment of the LAM molecule (with any bonds within both rings) identifies 99 entries of any kind of crystalline form of LAM, all with the single-crystal structure and with 3D coordinates deposited (no filters were applied: rerefined structures, new polymorphs, structures at different temperatures were included). The entries were classified manually into 71 salts and solvates of salts, 13 solvates and 15 cocrystals or their solvates (according to requirement that a coformer is in the solid state form at room temperature following the ΔpKa rule). A detailed list of all multicomponent LAM forms with refcodes is given in Table S1 in supporting information.

In this work, we were particularly focused towards the supramolecular architectures of the crystal structures of 11 solvates (two of them are new polymorphs of LAM ethanol solvate) and a new hydrate polymorph of LAM obtained by single-crystal X-ray diffraction (SCXRD).

The supramolecular architectures of presented LAM multicomponent forms are described based on graph-set analyses of synthons (Etter et al., 1990 ; Etter, 1990 ).

Comparative structural analysis of previously reported crystal structures of the hydrate derivative and three solvates (two of which are mixtures: ethanol/water and n-butanol/water and the third is a 2-propanol derivative with LAM:solvent stoichiometry of 2:2) has been given.

The existence of several stable polymorphic forms contributes to the complexity of the supramolecular architectures of LAM multicomponent crystalline forms.

By applying classifications to crystal forms of active pharmaceutical ingredients, compound LAM tert-butanol solvate (1:2) can be regarded as a cocrystal due to the definition of cocrystals since tert-butanol as a coformer is in the solid state at 20°C.

The majority of chosen solvent molecules contain the oxygen atom functionality (hydrates, alcohols, DMSO, dioxane) acting as a potential proton donor or proton acceptor in the formation of hydrogen bonds, whereas solvates with benzonitrile and acetonitrile molecules involve the –C≡N functionality as the potential proton acceptor in the formation of hydrogen bonds (Fig. 1). In attempts to synthesize cocrystals of LAM with selected coformers in appropriate solvents, we obtained LAM solvates instead of cocrystals [Fig. 1(a)]. Therefore, there is a lot of research to be done in the context of the prediction of the stability of certain crystalline forms of LAM under given preparative conditions.

Figure 1
Overview of syntheses of LAM solvates: (a) solvates prepared from the mixtures of LAM and potential coformer in solvent; (b) solvates prepared from the mixtures of LAM and solvents. For details of synthetic conditions see Section 1 of supporting information.

2. Materials and methods

2.1. Materials

LAM was supplied from in house (PLIVA, Croatia) with purity of 99.9%. Suppliers of solvents and additional substances are listed in supporting information.

2.2. Synthesis of the LAM hydrates and solvates

General observations. Coformer selection methods in the preparation of LAM cocrystals included synthon probability statistics based on analysis of data in the Cambridge Structural Database (CSD; version 5.45, November 2023). In this work, preparation of 12 LAM multicomponent compounds containing molecules of solvents of crystallization is described. Several solvates of LAM crystallized from the mixtures of LAM and potential coformer in chosen solvent as a result of competitiveness between solvent and coformer molecules for more robust synthon formation with the LAM molecule under given preparative conditions. LAM solvates with ethanol, acetone, water, 2-propanol and acetonitrile were isolated in the crystalline form during attempts to synthesize cocrystals of LAM with glycine, EDTA, phthalimide or vanillin (Fig. 1), and do not necessarily represent the most stable form that can be formed in such systems, which are highly dependent on crystallization conditions.

Other LAM solvates were isolated from the mixtures of LAM with dried ethanol, n-butanol, tert-butanol, n-pentanol, benzonitrile, DMSO and dioxane.

Experiments describing procedures for the preparation of single crystals suitable for SCXRD are given in supporting information.

2.3. Single-crystal X-ray diffraction

Single-crystal analyses of all compounds were performed on an Oxford Xcalibur Gemini diffractometer equipped with a Sapphire CCD detector and graphite–monochromated Cu Kα radiation, λ = 1.5418 Å [except for LAM hydrate (1:1): Mo Kα radiation, λ = 0.71073 Å] at 296 (2) K. All diffraction frames were collected using ω scans. General and crystal data for all compounds are listed in Tables S2–S4 in supporting information. CrysAlis CCD and CrysAlis RED (Agilent, 2010 $[Agilent (2010). CrysAlisPro, CrysAlis CCD and CrysAlis RED. Agilent Technologies (now Rigaku Oxford Diffraction), Yarnton, England.]$ ) programs were employed for data collection, cell refinement and data reduction (CrysAlisPro; Agilent, 2010 $[Agilent (2010). CrysAlisPro, CrysAlis CCD and CrysAlis RED. Agilent Technologies (now Rigaku Oxford Diffraction), Yarnton, England.]$ ). The Lorentz–polarization effect was corrected and the diffraction data have been scaled for absorption effects by the multi-scanning method. The structures were solved by direct methods and refined on F² using the weighted full-matrix least-squares method. SHELXS97 (Sheldrick, 2015a ) and SHELXL2014 (Sheldrick, 2015b ), integrated in the WinGX (v. 1.80.05; Farrugia, 2012 ) software package. All non-hydrogen atoms were refined anisotropically. Hydrogen atoms bonded to Csp² and Csp³ carbon atoms were placed in geometrically idealized positions with isotropic displacement parameters fixed at 1.2U_eq [for Csp² carbon atoms] or 1.5U_eq (for methyl groups) of the atoms to which they were attached and they were constrained to ride on their parent atoms. Hydrogen atoms of the LAM amino groups (bonded to N3 and N5 atoms) as well as the hydroxyl alcohol hydrogen atoms were located in difference Fourier maps as small electron densities at the final stages of the refinement procedures. These H-atom coordinates were refined with isotropic displacement parameters set at 1.2U_eq of the corresponding nitrogen or oxygen atoms restraining N—H and O—H distances to 0.86 (2) and 0.82 (2) Å, respectively. In the structure of LAM 2-propanol solvate (1:2), one of the 2-propanol molecules exhibits positional disorder of terminal methyl groups (52:48) with sp³–sp³ distances restrained by the DFIX instruction to 1.51 (1) Å.

Photographs in Fig. S1 show the crystal morphology of the single crystals used for the X-ray diffraction experiment.

The geometries of hydrogen bonds and contacts for all compounds are given in Tables S5–S16.

Molecular geometry calculations (including hydrogen-bonding and non-covalent interactions) were performed using programs PLATON (Spek, 2009 ) and PARST (Nardelli, 1983 , 1995 ) integrated in the WinGX software system. Molecular visualization with ORTEP drawings and packing diagrams were generated using Mercury (Macrae et al., 2008 ) software.

3. Results and discussion

Molecular structures of LAM hydrate and solvates are shown in Fig. 2.

Figure 2
Mercury-rendered ORTEP drawings of asymmetric units of the molecular structures of LAM solvates reported in this work. Atom-numbering schemes are shown for: (a) LAM hydrate (1:1), (b) LAM acetone solvate (1:1), (c) LAM ethanol solvate (1:1) (form I), (d) LAM ethanol solvate (1:1) (form II) (major component denoted as A of EtOH disordered molecule is shown), (e) LAM 2-propanol solvate (1:2) (only major component denoted as A of one 2-PrOH molecule is shown), (f) LAM tert-butanol solvate (1:2) (two tert-butanol molecules are denoted as A and B), (g) LAM n-butanol solvate (2:2) (A and B molecules are denoted), (h) LAM n-pentanol solvate hydrate (1:1:1) (major component A of n-pentanol disordered molecule is shown), (i) LAM benzonitrile solvate (1:2), (j) LAM acetonitrile solvate (1:1), (k) LAM DMSO solvate (1:1) (major component A of disordered DMSO molecule is shown), (l) LAM dioxane solvate (1:1.5). Displacement ellipsoids are drawn at the 50% probability level at 296 (2) K.

A detailed comparative analysis of supramolecular synthons and their relevant geometrical properties in the crystal structures of LAM hydrate and solvates along with the three other solvates (with their CSD refcodes) (Table 1) is given below.

Table 1
Comparative analysis of supramolecular synthons in LAM hydrate and solvates

Crystal and molecular structures of hydrate (No. 1) and solvates (Nos. 3–5, 7, 9, 11–16) are reported in this work and structures 2, 6, 8 and 10 are identified by their CSD refcode.

No.	LAM hydrate/solvate [with LAM/solvate (or hydrate) stoichiometry]	Presence of synthon 1†	Presence of synthon 2†	Supramolecular assembling of synthons (described in Fig. 6)	Geometry of R²₄(16) synthon (synthon 2 – synthon 1 – synthon 2 array)	General supramolecular assembling of R²₄(16) synthon with others†
1	Water (1:1)	Yes	Yes	Discrete dimer	Planar	Extended planar ribbons of synthons R²₄(16) and R⁴₄(10) alternate in the AB fashion
2	Water (1:1) (XUVLOP; Kubicki & Codding, 2001)	No	No	Not formed	Not formed because synthons 1 and 2 are not present	–
3	Acetone (1:1)	Yes	Yes	Extended chains	Planar	Extended planar ribbons of synthons R²₄(16) and R²₂(8) alternate in the AB fashion
4	Ethanol (form I) (1:1)	Yes	Yes	Discrete dimer	Planar	R²₄(16) synthon linked into ribbon motifs via hydrogen bonds
5	Ethanol (form II) (1:1)	Yes	Yes	Extended chains (zigzag)	Planar	Zigzag ribbons of synthons R²₄(16) and R²₂(8) alternate in the AB fashion
6	Ethanol/water (1:1:1) (WUVLOP; Cheney et al., 2010)	Yes	Yes (via H₂O)	Discrete dimer	Planar	3D array of hydrogen bonds
7	2-Propanol (1:2)	Yes	Yes	Extended chains	Planar	Extended planar ribbons of synthons R²₄(16) and R²₂(8) alternate in the AB fashion
8	2-Propanol (2:2) (IJAHOR; Qian et al., 2009 )	Yes	Yes	Extended chains (zigzag)	Planar	Extended non-planar ribbon of alternating R²₄(16) and R²₂(8) synthons
9	n-Butanol (2:2)	Yes	Yes (not centrosymmetric)	Extended chains	Not formed	Extended ribbons of synthons 1 and 2 with another R²₂(8) synthon
10	n-Butanol/water (1:1:1) (OVUNAV; Sridhar & Ravikumar, 2011)	Yes	Yes (via H₂O)	Discrete dimer	Planar	Coplanar dimers layered structure
11	tert-Butanol (1:2)	Yes	Yes	Extended chains	Not planar	Extended planar ribbons of synthons R²₄(16) and R²₂(8) alternate in the AB fashion
12	n-Pentanol/water (1:1:1)	Yes	Yes (via H₂O)	Extended chains	Planar	3D hydrogen-bonded network
13	Benzonitrile (1:2)	Yes	Yes (via N atom of benzonitrile)	Extended chains	Planar	Extended ribbons of alternating R²₄(16) and R²₂(8) synthons
14	Acetonitrile (1:1)	Yes	Yes (via N atom of acetonitrile)	Extended chains	Acetonitrile N atom slightly outside of the synthon 1 plane	Extended non-planar ribbon of alternating R²₄(16) and R²₂(8) synthons
15	DMSO (1:1)	Yes	Yes	Extended chains	Planar	Extended non-planar ribbon of alternating R²₄(16) and R²₂(8) synthons
16	Dioxane (1:1.5)	Yes	Yes	Extended chains	Planar	Extended non-planar ribbon of alternating R²₄(16) and R²₂(8) synthons

†LAM synthons 1 and 2 are formed via N5—H2N5⋯N4 [amino-pyridine synthon 1 or so-called synthon A (Figs. 3

and 6

)] and two hydrogen bonds: N3—H1N3⋯N6 and N5—H1N5⋯N6 (LAM synthon 2, Figs. 3

and 6

). The centrosymmetric synthon, which does not participate in R²₄(16) synthon formation, is of the same topology as synthon 1 (Figs. 3

and 6

), but formed via a different hydrogen bond and it is denoted in this work as synthon B (see Section 3.1.3

3.1. Analysis of supramolecular synthons

Two supramolecular synthons are present in the crystal structure of LAM [Figs. 3(b) and 4]: synthon 1 [R²₂(8)] the so-called aminopyridine centrosymmetrical dimer [involving atoms N3 and N4; para-para (P-P) dimer] and synthon 2 [R²₃(8)] [involving atoms N2, N3 and N5; see Fig. 3(b)]. Synthons 1 and 2 are fused via a N3—H5⋯N4 hydrogen bond which acts as a coupling.

Figure 3
(a) Structural diagram of the LAM molecule with the atom-numbering scheme. (b) Supramolecular synthons 1 and 2 in the crystal structure of the LAM molecule (CSD refcode: EFEMUX01; usually known as motifs 1 and 2, respectively) defined via the N—H⋯N type of hydrogen bond between the N4 atom of 1,2,4-triazine and the amino N3 atom (synthon 1: P-P dimerization) and between the N2 atom of 1,2,4-triazine and the amino N3 and N5 atoms (synthon 2).

Figure 4
Mercury-rendered crystal structures of LAM solvate compounds reported in this work: (a) LAM hydrate (1:1), (b) LAM acetone solvate (1:1), (c) LAM ethanol solvate (1:1) form I, (d) LAM ethanol solvate (1:1) form II, (e) LAM 2-propanol solvate (1:2), (f) LAM n-butanol solvate (2:2), (g) LAM tert-butanol solvate (1:2), (h) LAM n-pentanol solvate hydrate (1:1:1), (i) LAM benzonitrile solvate (1:2), (j) LAM acetonitrile solvate (1:1), (k) LAM DMSO solvate (1:1), (l) LAM dioxane solvate (1:1.5). For description of each crystal structure, see supporting information.

Both synthons 1 and 2 form building units in the form synthon 2–synthon 1–synthon 2 which are recognized as the more complex supramolecular synthon defined as R²₄(16). Synthon R²₄(16) is a robust building block in the crystal engineering of LAM multicomponent solids.

On the basis of the synthon probability statistics, it is well known that the various solvent molecules in the crystal structures of LAM multicomponent solids can participate in the formation of synthon 2 by replacing the N—H⋯N hydrogen bond formed between the amino group and the triazine nitrogen atom of the LAM molecule with N—H⋯O or N—H⋯N hydrogen bonds formed with proton acceptors of the solvent molecules (Figs. 3 and 4).

The investigation is also interesting from the polymorphism (and pseudopolymorphism) viewpoint since some compounds we report here are polymorphs of those previously published (such as the hydrate derivative) (Fig. 1). We also found two new polymorphic forms of the LAM ethanol (1:1) derivative (assigned by us in this work as forms I and II). So far, the crystal structures of two polymorphic forms discovered at 100 (2) K (Hall et al., 2018 ) and 293 (2) K (Évora et al., 2019 ) have been published. All four molecular structures exhibit differences in the LAM molecule conformation defining these forms as conformational polymorphs.

Table 2 and Fig. 5 present the conformational polymorphism of LAM ethanol (1:1) solvates described so far in the literature with polymorphic forms of LAM ethanol (1:1) solvates discovered by us [see Table 1: forms I and II, Figs. 2(c) and 2(d)]. The structures assigned CCDC numbers 1483194 and 1826282 are the same compound but determined at 296 K and 100 K, respectively.

Table 2
Conformational polymorphs of LAM ethanol solvates

CCDC number	Data collection temperature (K)	Space group and unit-cell parameters (Å, °)	Torsion angle† in the LAM molecule	Topology of homosynthon 1	Reference
1826282	100	C2/c, a = 21.2458 (15), b = 10.2320 (8), c = 14.8428 (11), β = 118.808 (4)	−117.6 (7)	O-O (ortho-ortho)	Hall et al. (2018)
1483194 (form II)	296	C2/c, a = 21.268 (9), b = 10.450 (3), c = 19.085 (7), β = 136.662 (3)	−117.4 (3)	O-O	This work
981033	293	C2/c, a = 21.300 (2), b = 10.471 (1), c = 15.024 (1), β = 119.19	117.9 (2)	O-O	Évora et al. (2019)
1483195 (form I)	296	P2₁/n, a = 7.6894 (3), b = 11.3816 (4) c = 15.9147 (5), β = 92.710 (3)	92.9 (2)	O-O	This work

†Describes the spatial orientation around the C—C single bond that connects the 2,3-dichlorophenyl and 1,2,4-triazine rings of the LAM molecule.

Figure 5
Mercury-rendered overlay diagrams exhibiting conformational polymorphism of LAM ethanol (1:1) solvates (see Table 2

). (a) Overlay diagram of the same SCXRD molecular structure at room temperature (CCDC number 1483194 – yellow) and at 100 K (CCDC number 1826282 – red). (b) Overlay diagram of molecular structures with CCDC numbers 981033 (blue), 148195 (green) and 1826282 (red) exhibiting different spatial orientation of 1,2,4-triazine rings of LAM molecules in three structures [see Figs. 4

(d)]; for crystal packing differences in forms I and II, see Section 3.1.3

. The overlays have been quantified via RMSD determination.

3.1.1. Robustness of LAM aminopyridine synthon 1 in LAM solvates: P-P versus O-O topology

Aminopyridine synthon 1 interconnecting LAM molecules was found to be present in all analyzed structures converting from P-P topology to O-O topology in all crystal structures, except in LAM n-pentanol hydrate where it was preserved as the P-P dimer [Fig. 4(h)]. One polymorphic form of hydrate derivative (CSD refcode XUVLOP; Kubicki & Codding, 2001 ) (Table 1) did not retain synthon 1 due to the water molecules participating in the hydrogen bonding between two LAM molecules which disabled the formation of synthon 1, probably due to the size of water molecule along with its potential to form hydrogen bonds. On the other hand, in this work, we report the crystal structure of LAM hydrate, the polymorphic form of the XUVLOP structure, where aminopyridine synthon 1 is preserved. Polymorphic LAM hydrate described here was obtained as a coexisting polymorph in an attempt to synthesize the LAM cocrystal with glycine in boiling water (see Section 1 in supporting information). Moreover, we noticed a crystal mixture of transparent and opaque crystals, the latter being a new polymorphic form, and transparent crystals which are confirmed to be a previously published structure (CSD refcode XUVLOP; Kubicki & Codding, 2001).

3.1.2. Emulation of LAM synthon 2

The functionalities introduced by selected solvent molecules are capable of imitating synthon 2 [R²₃(8)] found in the crystal structure of the LAM molecule itself (Fig. 3) via the formation of N—H⋯O or N—H⋯N hydrogen bonds in the case of solvents with oxygen-containing groups or solvents containing –C≡N functionality, respectively.

Structural analysis of LAM solvate structures with solvents in Table 1 reveals that synthon 2 is not formed only in the structure of the polymorph of LAM hydrate (refcode XUVLOP; Kubicki & Codding, 2001) (ordinal number 2, Table 1).

The competition of solvent molecules to hook up to the LAM molecule by hydrogen bonds in the multicomponent LAM solvates containing a water molecule is particularly challenging from the supramolecular point of view [Fig. 4(a): LAM hydrate (1:1) and Fig. 4(h): LAM n-pentanol hydrate (1:1:1)].

It is established that emulation of the LAM synthon 2 always happens via the N—H⋯O type of hydrogen bond with the water molecule oxygen atom (ordinal numbers 6, 10 and 12 in Table 1), probably due to the size and hydrogen bond capability of the water molecule.

Condensed synthon R²₄(16) was not found in the crystal structures of water (XUVLOP; Kubicki & Codding, 2001) and n-butanol LAM solvates [Nos. 2 and 9, respectively, Table 1; Fig. 4(f): LAM n-butanol solvate (2:2)].

3.1.3. Supramolecular relationship of aminopyridine synthon 1 [R²₂(8)] and topologically identical synthon B

The possible supramolecular arrangements of synthon 1 in the described structures are schematically shown in Fig. 6 showing the assembling of synthon 1 (here, in Fig. 6 assigned as synthon A also) into discrete dimers or into extended chains with the heterosynthon of the same topology R²₂(8) (synthon B) in the alternating AB manner. The extended chains are a more frequent synthon. From Table 1 it can be seen that discrete dimers are found in four structures: hydrate derivative, polymorph I of ethanol derivative, ethanol/water (WUVLOP; Cheney et al., 2010 ) and n-butanol/water (OVUNAV; Sridhar & Ravikumar, 2011) derivatives. In other crystal structures extended chains are present (Table 1).

Figure 6
Possible supramolecular assembling of synthon 1 in the crystal structures of hydrate and solvates with the LAM molecule. Assembling of synthon 1 (`aminopyridine' synthon) into discrete dimers is more rare than assembling into extended zigzag chains alternating with the synthon denoted as B of the same graph-set designation, but of different topology (see Fig. 4

and Table 1

for the frequency of appearance in solvates and hydrates of LAM and crystal structure descriptions in supporting information).

Extended planar ribbons of synthons R²₄(16) (built up of synthons 1 and 2) and synthon B [of R²₂(8) graph-set designation], alternating in the AB fashion, are the most frequent supramolecular architecture of the structures analyzed in this work (Fig. 6; see also crystal structure descriptions in supporting information and Fig. 4).

The additional hydrogen bonds are formed with the solvent molecules with the multifunctional donor–acceptor hydrogen bonds capabilities resulting in the additional supramolecular assembling of molecules. This is particularly emphasized for small solvent molecules such as water or simpler alcohols.

4. Conclusion

In this article an example of a crystal engineering approach as a potential tool for the design of multicomponent solids of LAM [drug lamotrigine: 3,5-diamino-6-(2,3-dichlorophenyl)-1,2,4-triazine], such as cocrystals, is given. The idea was to describe how the understanding of supramolecular arrangement in the crystal structures of hydrates and solvates can be applied to supramolecular cocrystal design in such a way that the crystal supramolecular topology of the hydrates and solvates is maintained in the crystal structures of cocrystals. If it is established that supramolecular synthons in LAM solvates are robust, this will possibly prevent complete supramolecular synthon rearrangement in LAM cocrystals. In this way, LAM solvates can be used as a design tool for LAM cocrystals.

LAM is an excellent tool that gives deep insight into possible supramolecular arrangements of a model molecule in various supramolecular environments in the crystalline state exhibiting hierarchy of molecular recognition. We previously successfully applied this approach in the preparation of LAM cocrystals (Lekšić et al., 2010 ; Lekšić, 2013 ).

Supramolecular analysis of a new hydrate and 11 new solvates [with acetone, ethanol with two polymorphs (form I and form II), 2-propanol, n-butanol, tert-butanol, n-pentanol, benzonitrile, acetonitrile, DMSO and dioxane] of LAM resulted in the observation of robustness of three synthons in the supramolecularly competitive surroundings: synthon 1 of R²₂(8) topology, synthon 2 of R²₃(8) topology and their combination, supramolecular synthon R²₄(16). LAM synthon 1 persists in all solvates except in the hydrate, while synthon 2 of R²₃(8) topology is a place for the mutual molecular recognition of LAM with the functional groups of solvent molecules in order to maintain synthon 2 topology.

It is shown that the formation of LAM solvates is highly dependent on crystallization conditions, size of the solvent molecule and its ability to form hydrogen bonds.

Since the LAM molecule itself has a great abundance of hydrogen-bond donors/acceptors as well as molecules of various solvents along with the phenomenon of polymorphism, there is a need for further development and investigations of the crystalline multicomponent forms of the LAM molecule as a fast growing field, particularly from the pharmaceutical point of view.

Supporting information

CCDC references: 1483193; 1483194; 1483195; 1483196; 1483197; 1483198; 1483199; 1483200; 1483201; 1483202; 1483203; 2354026

Crystal structure: contains datablocks global, LAM_hydrate, LAM_ethanol_form_I, LAM_ethanol_form_II, LAM_acetone_solvate, LAM_2-propanol_solvate, LAM_n-butanol_solvate, LAM_tert-butanol_solvate, LAM_n-pentanol_solvate, LAM_benzonitrile_solvate, LAM_acetonitrile_solvate, LAM_DMSO_solvate, LAM_dioxane_solvate. DOI: https://doi.org/10.1107/S2052520624002567/aw5084sup1.cif

Structure factors: contains datablock LAM_hydrate. DOI: https://doi.org/10.1107/S2052520624002567/aw5084LAM_hydratesup2.hkl

Structure factors: contains datablock LAM_ethanol_form_I. DOI: https://doi.org/10.1107/S2052520624002567/aw5084LAM_ethanol_form_Isup3.hkl

Structure factors: contains datablock LAM_ethanol_form_II. DOI: https://doi.org/10.1107/S2052520624002567/aw5084LAM_ethanol_form_IIsup4.hkl

Structure factors: contains datablock LAM_acetone_solvate. DOI: https://doi.org/10.1107/S2052520624002567/aw5084LAM_acetone_solvatesup5.hkl

Structure factors: contains datablock LAM_2-propanol_solvate. DOI: https://doi.org/10.1107/S2052520624002567/aw5084LAM_2-propanol_solvatesup6.hkl

Structure factors: contains datablock LAM_n-butanol_solvate. DOI: https://doi.org/10.1107/S2052520624002567/aw5084LAM_n-butanol_solvatesup7.hkl

Structure factors: contains datablock LAM_tert-butanol_solvate. DOI: https://doi.org/10.1107/S2052520624002567/aw5084LAM_tert-butanol_solvatesup8.hkl

Structure factors: contains datablock LAM_n-pentanol_solvate. DOI: https://doi.org/10.1107/S2052520624002567/aw5084LAM_n-pentanol_solvatesup9.hkl

Structure factors: contains datablock LAM_benzonitrile_solvate. DOI: https://doi.org/10.1107/S2052520624002567/aw5084LAM_benzonitrile_solvatesup10.hkl

Structure factors: contains datablock LAM_acetonitrile_solvate. DOI: https://doi.org/10.1107/S2052520624002567/aw5084LAM_acetonitrile_solvatesup11.hkl

Structure factors: contains datablock LAM_DMSO_solvate. DOI: https://doi.org/10.1107/S2052520624002567/aw5084LAM_DMSO_solvatesup12.hkl

Structure factors: contains datablock LAM_dioxane_solvate. DOI: https://doi.org/10.1107/S2052520624002567/aw5084LAM_dioxane_solvatesup13.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2052520624002567/aw5084sup14.pdf

Computing details top

(LAM_hydrate) top

Crystal data top

C₉H₇Cl₂N₅·H₂O	F(000) = 560
M_r = 274.11	D_x = 1.567 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 9.3283 (3) Å	Cell parameters from 4207 reflections
b = 9.8379 (3) Å	θ = 3.5–31.9°
c = 12.9148 (3) Å	µ = 0.55 mm⁻¹
β = 101.405 (3)°	T = 296 K
V = 1161.80 (6) Å³	Prism, colourless
Z = 4	0.20 × 0.10 × 0.10 mm

Data collection top

Oxford Xcalibur Gemini Sapphire CCD detector diffractometer	1835 reflections with I > 2σ(I)
Radiation source: Enhance (Mo) X-ray Source	R_int = 0.031
ω–scans	θ_max = 27.0°, θ_min = 3.6°
Absorption correction: multi-scan CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.32.18. Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −10→11
T_min = 0.479, T_max = 1.000	k = −12→12
7485 measured reflections	l = −16→15
2501 independent reflections

Refinement top

Refinement on F²	6 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.041	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.115	w = 1/[σ²(F_o²) + (0.0754P)²] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max = 0.001
2501 reflections	Δρ_max = 0.28 e Å⁻³
172 parameters	Δρ_min = −0.27 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	1.02473 (6)	0.45682 (6)	0.37439 (4)	0.05256 (19)
Cl2	1.03429 (7)	0.54000 (6)	0.14203 (4)	0.0558 (2)
O1	0.9575 (2)	−0.06140 (17)	0.66411 (12)	0.0569 (4)
H1OA	1.015 (2)	−0.088 (3)	0.6290 (17)	0.068*
H1OB	0.920 (3)	0.0056 (18)	0.6323 (19)	0.068*
N1	0.83512 (18)	0.19940 (17)	0.45980 (11)	0.0411 (4)
N2	0.81946 (18)	0.18129 (17)	0.56081 (11)	0.0428 (4)
N3	0.7199 (2)	0.25217 (19)	0.69970 (12)	0.0487 (5)
H1N3	0.665 (2)	0.307 (2)	0.7277 (16)	0.058*
H2N3	0.773 (2)	0.1915 (18)	0.7362 (16)	0.058*
N4	0.64316 (19)	0.36016 (16)	0.54106 (11)	0.0419 (4)
N5	0.5724 (3)	0.4634 (2)	0.38009 (14)	0.0651 (6)
H1N5	0.577 (3)	0.476 (3)	0.3146 (9)	0.078*
H2N5	0.508 (3)	0.509 (3)	0.409 (2)	0.078*
C1	0.7821 (2)	0.31367 (19)	0.29063 (13)	0.0366 (4)
C2	0.8948 (2)	0.39478 (19)	0.27027 (13)	0.0376 (4)
C3	0.9034 (2)	0.4275 (2)	0.16769 (14)	0.0420 (5)
C4	0.8039 (2)	0.3733 (2)	0.08390 (14)	0.0491 (5)
H4	0.8108	0.3940	0.0148	0.059*
C5	0.6951 (2)	0.2890 (2)	0.10333 (15)	0.0518 (5)
H5	0.6299	0.2501	0.0473	0.062*
C6	0.6825 (2)	0.2617 (2)	0.20610 (14)	0.0447 (5)
H6	0.6059	0.2077	0.2186	0.054*
C7	0.7601 (2)	0.29209 (19)	0.40100 (13)	0.0357 (4)
C8	0.7276 (2)	0.26514 (18)	0.59686 (13)	0.0375 (4)
C9	0.6563 (2)	0.37407 (19)	0.44044 (13)	0.0403 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0616 (4)	0.0609 (4)	0.0338 (3)	−0.0132 (3)	0.0060 (2)	−0.0009 (2)
Cl2	0.0668 (4)	0.0611 (4)	0.0470 (3)	−0.0111 (3)	0.0292 (3)	0.0028 (2)
O1	0.0783 (12)	0.0561 (10)	0.0396 (8)	0.0196 (8)	0.0198 (7)	0.0060 (6)
N1	0.0473 (10)	0.0456 (9)	0.0334 (7)	0.0050 (8)	0.0155 (7)	0.0031 (7)
N2	0.0508 (10)	0.0471 (10)	0.0329 (7)	0.0065 (8)	0.0143 (7)	0.0068 (7)
N3	0.0656 (12)	0.0534 (12)	0.0303 (8)	0.0066 (9)	0.0170 (8)	0.0056 (7)
N4	0.0536 (10)	0.0452 (10)	0.0310 (7)	0.0082 (8)	0.0183 (7)	0.0033 (6)
N5	0.0901 (16)	0.0756 (15)	0.0375 (9)	0.0452 (12)	0.0316 (10)	0.0175 (9)
C1	0.0453 (10)	0.0376 (10)	0.0299 (8)	0.0065 (8)	0.0153 (7)	−0.0003 (7)
C2	0.0460 (11)	0.0393 (10)	0.0291 (8)	0.0019 (9)	0.0115 (7)	−0.0021 (7)
C3	0.0497 (12)	0.0476 (11)	0.0336 (9)	0.0010 (9)	0.0199 (8)	0.0018 (8)
C4	0.0580 (13)	0.0646 (14)	0.0275 (8)	0.0020 (11)	0.0153 (8)	0.0005 (8)
C5	0.0560 (13)	0.0679 (14)	0.0314 (9)	−0.0050 (11)	0.0088 (8)	−0.0073 (9)
C6	0.0486 (12)	0.0508 (12)	0.0381 (10)	−0.0042 (9)	0.0167 (8)	−0.0016 (8)
C7	0.0427 (10)	0.0374 (10)	0.0296 (8)	0.0009 (8)	0.0133 (7)	0.0008 (7)
C8	0.0449 (11)	0.0393 (10)	0.0306 (8)	−0.0035 (8)	0.0134 (7)	0.0021 (7)
C9	0.0520 (12)	0.0420 (11)	0.0307 (8)	0.0069 (9)	0.0172 (8)	0.0035 (7)

Geometric parameters (Å, º) top

Cl1—C2	1.7336 (18)	N5—H1N5	0.862 (7)
Cl2—C3	1.728 (2)	N5—H2N5	0.89 (3)
O1—H1OA	0.813 (10)	C1—C6	1.384 (3)
O1—H1OB	0.816 (10)	C1—C2	1.386 (3)
N1—C7	1.299 (2)	C1—C7	1.495 (2)
N1—N2	1.3529 (19)	C2—C3	1.381 (2)
N2—C8	1.337 (2)	C3—C4	1.385 (3)
N3—C8	1.350 (2)	C4—C5	1.371 (3)
N3—H1N3	0.868 (10)	C4—H4	0.9300
N3—H2N3	0.855 (10)	C5—C6	1.382 (3)
N4—C9	1.336 (2)	C5—H5	0.9300
N4—C8	1.338 (2)	C6—H6	0.9300
N5—C9	1.323 (3)	C7—C9	1.429 (3)

H1OA—O1—H1OB	104 (3)	C5—C4—C3	119.69 (17)
C7—N1—N2	120.51 (15)	C5—C4—H4	120.2
C8—N2—N1	116.95 (15)	C3—C4—H4	120.2
C8—N3—H1N3	120.1 (16)	C4—C5—C6	119.99 (18)
C8—N3—H2N3	118.0 (16)	C4—C5—H5	120.0
H1N3—N3—H2N3	122 (2)	C6—C5—H5	120.0
C9—N4—C8	115.98 (16)	C5—C6—C1	120.98 (19)
C9—N5—H1N5	122.1 (19)	C5—C6—H6	119.5
C9—N5—H2N5	117.2 (18)	C1—C6—H6	119.5
H1N5—N5—H2N5	121 (2)	N1—C7—C9	120.83 (15)
C6—C1—C2	118.62 (16)	N1—C7—C1	119.84 (16)
C6—C1—C7	120.18 (17)	C9—C7—C1	119.33 (16)
C2—C1—C7	120.99 (16)	N2—C8—N4	126.37 (15)
C3—C2—C1	120.41 (17)	N2—C8—N3	116.53 (17)
C3—C2—Cl1	119.87 (15)	N4—C8—N3	117.10 (17)
C1—C2—Cl1	119.72 (13)	N5—C9—N4	118.94 (17)
C2—C3—C4	120.19 (19)	N5—C9—C7	121.89 (16)
C2—C3—Cl2	120.68 (15)	N4—C9—C7	119.18 (16)
C4—C3—Cl2	119.10 (15)

C7—N1—N2—C8	−1.9 (3)	N2—N1—C7—C1	178.12 (16)
C6—C1—C2—C3	2.7 (3)	C6—C1—C7—N1	101.7 (2)
C7—C1—C2—C3	−172.03 (17)	C2—C1—C7—N1	−83.6 (2)
C6—C1—C2—Cl1	−177.90 (15)	C6—C1—C7—C9	−78.3 (2)
C7—C1—C2—Cl1	7.3 (3)	C2—C1—C7—C9	96.4 (2)
C1—C2—C3—C4	−3.6 (3)	N1—N2—C8—N4	4.2 (3)
Cl1—C2—C3—C4	177.05 (16)	N1—N2—C8—N3	−175.82 (17)
C1—C2—C3—Cl2	174.49 (15)	C9—N4—C8—N2	−2.1 (3)
Cl1—C2—C3—Cl2	−4.9 (2)	C9—N4—C8—N3	177.89 (18)
C2—C3—C4—C5	1.2 (3)	C8—N4—C9—N5	177.9 (2)
Cl2—C3—C4—C5	−176.91 (17)	C8—N4—C9—C7	−2.0 (3)
C3—C4—C5—C6	2.0 (3)	N1—C7—C9—N5	−175.9 (2)
C4—C5—C6—C1	−2.8 (3)	C1—C7—C9—N5	4.0 (3)
C2—C1—C6—C5	0.5 (3)	N1—C7—C9—N4	4.0 (3)
C7—C1—C6—C5	175.26 (18)	C1—C7—C9—N4	−176.03 (16)
N2—N1—C7—C9	−1.9 (3)

(LAM_ethanol_form_I) top

Crystal data top

C₉H₇Cl₂N₅·C₂H₆O	F(000) = 624
M_r = 302.16	D_x = 1.443 Mg m⁻³
Monoclinic, P2₁/n	Cu Kα radiation, λ = 1.54184 Å
a = 7.6894 (3) Å	Cell parameters from 4792 reflections
b = 11.3816 (4) Å	θ = 3.9–72.6°
c = 15.9147 (5) Å	µ = 4.21 mm⁻¹
β = 92.710 (3)°	T = 296 K
V = 1391.26 (9) Å³	Prism, colourless
Z = 4	0.50 × 0.50 × 0.30 mm

Data collection top

Xcalibur, Sapphire3, Gemini diffractometer	2412 reflections with I > 2σ(I)
Radiation source: Enhance (Cu) X-ray Source	R_int = 0.029
ω scans	θ_max = 70.0°, θ_min = 4.8°
Absorption correction: multi-scan CrysAlisPro, Agilent Technologies, Version 1.171.36.21. Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −9→9
T_min = 0.550, T_max = 1.000	k = −13→9
12626 measured reflections	l = −19→19
2638 independent reflections

Refinement top

Refinement on F²	5 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.039	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.110	w = 1/[σ²(F_o²) + (0.0601P)² + 0.4355P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.001
2638 reflections	Δρ_max = 0.27 e Å⁻³
187 parameters	Δρ_min = −0.45 e Å⁻³

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	−0.03838 (6)	0.50665 (5)	0.17951 (3)	0.05642 (17)
Cl2	0.25084 (8)	0.57327 (5)	0.05412 (3)	0.0689 (2)
O1	0.4277 (2)	0.61783 (16)	0.35409 (11)	0.0723 (5)
H1O1	0.445 (5)	0.655 (3)	0.3112 (14)	0.109*
N1	−0.0212 (2)	0.23614 (14)	0.29808 (10)	0.0471 (4)
N2	−0.1458 (2)	0.20046 (14)	0.34940 (11)	0.0511 (4)
N3	−0.2958 (3)	0.23307 (17)	0.46746 (12)	0.0606 (5)
H1N3	−0.313 (3)	0.265 (2)	0.5152 (10)	0.073*
H2N3	−0.345 (3)	0.1683 (14)	0.4540 (16)	0.073*
N4	−0.0815 (2)	0.36565 (13)	0.43869 (9)	0.0437 (3)
N5	0.1310 (3)	0.49581 (15)	0.40440 (12)	0.0587 (5)
H1N5	0.212 (3)	0.516 (2)	0.3722 (14)	0.070*
H2N5	0.111 (3)	0.532 (2)	0.4502 (10)	0.070*
C1	0.2039 (2)	0.36481 (15)	0.25463 (10)	0.0399 (4)
C2	0.1673 (2)	0.44488 (15)	0.18999 (10)	0.0404 (4)
C3	0.2957 (3)	0.47549 (17)	0.13589 (11)	0.0474 (4)
C4	0.4606 (3)	0.4290 (2)	0.14575 (14)	0.0614 (6)
H4	0.5461	0.4503	0.1092	0.074*
C5	0.4981 (3)	0.3507 (2)	0.21018 (15)	0.0660 (6)
H5	0.6096	0.3195	0.2174	0.079*
C6	0.3709 (3)	0.31832 (19)	0.26401 (13)	0.0547 (5)
H6	0.3972	0.2649	0.3070	0.066*
C7	0.0689 (2)	0.33129 (14)	0.31362 (10)	0.0383 (4)
C8	−0.1694 (2)	0.26724 (15)	0.41658 (11)	0.0426 (4)
C9	0.0391 (2)	0.39963 (15)	0.38721 (10)	0.0410 (4)
C10	0.5951 (4)	0.5790 (3)	0.3828 (2)	0.0820 (8)
H10A	0.6548	0.5460	0.3359	0.098*
H10B	0.5828	0.5174	0.4242	0.098*
C11	0.6990 (4)	0.6728 (4)	0.4198 (3)	0.1063 (11)
H11A	0.8110	0.6428	0.4384	0.159*
H11B	0.7135	0.7334	0.3787	0.159*
H11C	0.6416	0.7048	0.4670	0.159*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0477 (3)	0.0644 (3)	0.0573 (3)	0.0077 (2)	0.0038 (2)	0.0135 (2)
Cl2	0.0865 (4)	0.0744 (4)	0.0471 (3)	−0.0008 (3)	0.0155 (3)	0.0179 (2)
O1	0.0537 (8)	0.0858 (11)	0.0775 (11)	−0.0127 (8)	0.0029 (8)	0.0391 (9)
N1	0.0526 (9)	0.0448 (8)	0.0441 (8)	−0.0047 (7)	0.0067 (7)	−0.0096 (6)
N2	0.0549 (9)	0.0462 (8)	0.0530 (9)	−0.0129 (7)	0.0088 (7)	−0.0088 (7)
N3	0.0665 (11)	0.0592 (10)	0.0578 (10)	−0.0248 (9)	0.0213 (9)	−0.0073 (8)
N4	0.0510 (8)	0.0446 (8)	0.0362 (7)	−0.0098 (6)	0.0114 (6)	−0.0051 (6)
N5	0.0734 (12)	0.0565 (10)	0.0489 (9)	−0.0279 (8)	0.0295 (8)	−0.0196 (7)
C1	0.0468 (9)	0.0393 (8)	0.0338 (8)	0.0006 (7)	0.0061 (7)	−0.0057 (6)
C2	0.0449 (9)	0.0407 (8)	0.0357 (8)	0.0011 (7)	0.0040 (7)	−0.0054 (7)
C3	0.0590 (11)	0.0489 (10)	0.0352 (9)	−0.0019 (8)	0.0110 (8)	−0.0005 (7)
C4	0.0571 (12)	0.0741 (14)	0.0551 (12)	0.0030 (10)	0.0254 (10)	−0.0003 (10)
C5	0.0514 (11)	0.0812 (15)	0.0667 (13)	0.0189 (11)	0.0176 (10)	0.0047 (12)
C6	0.0567 (11)	0.0585 (11)	0.0495 (10)	0.0155 (9)	0.0098 (9)	0.0062 (9)
C7	0.0447 (9)	0.0367 (8)	0.0337 (8)	0.0021 (6)	0.0036 (6)	−0.0007 (6)
C8	0.0438 (9)	0.0412 (9)	0.0429 (9)	−0.0047 (7)	0.0031 (7)	0.0020 (7)
C9	0.0482 (9)	0.0389 (8)	0.0363 (8)	−0.0049 (7)	0.0074 (7)	−0.0029 (7)
C10	0.0804 (17)	0.0743 (16)	0.0897 (19)	0.0052 (13)	−0.0134 (14)	0.0161 (14)
C11	0.0803 (19)	0.118 (3)	0.118 (3)	−0.0163 (18)	−0.0202 (19)	0.018 (2)

Geometric parameters (Å, º) top

Cl1—C2	1.7318 (18)	C1—C2	1.393 (2)
Cl2—C3	1.7345 (19)	C1—C7	1.482 (2)
O1—C10	1.416 (3)	C2—C3	1.385 (3)
O1—H1O1	0.820 (10)	C3—C4	1.376 (3)
N1—C7	1.303 (2)	C4—C5	1.379 (3)
N1—N2	1.351 (2)	C4—H4	0.9300
N2—C8	1.331 (2)	C5—C6	1.380 (3)
N3—C8	1.351 (2)	C5—H5	0.9300
N3—H1N3	0.857 (10)	C6—H6	0.9300
N3—H2N3	0.851 (10)	C7—C9	1.433 (2)
N4—C9	1.324 (2)	C10—C11	1.442 (5)
N4—C8	1.346 (2)	C10—H10A	0.9700
N5—C9	1.324 (2)	C10—H10B	0.9700
N5—H1N5	0.857 (10)	C11—H11A	0.9600
N5—H2N5	0.859 (10)	C11—H11B	0.9600
C1—C6	1.390 (3)	C11—H11C	0.9600

C10—O1—H1O1	105 (3)	C5—C6—C1	120.65 (19)
C7—N1—N2	121.41 (15)	C5—C6—H6	119.7
C8—N2—N1	116.20 (15)	C1—C6—H6	119.7
C8—N3—H1N3	123.6 (19)	N1—C7—C9	120.14 (16)
C8—N3—H2N3	114.9 (18)	N1—C7—C1	118.41 (15)
H1N3—N3—H2N3	120 (3)	C9—C7—C1	121.43 (15)
C9—N4—C8	116.04 (15)	N2—C8—N4	126.82 (16)
C9—N5—H1N5	119.7 (18)	N2—C8—N3	116.49 (16)
C9—N5—H2N5	117.2 (18)	N4—C8—N3	116.69 (17)
H1N5—N5—H2N5	123 (3)	N4—C9—N5	119.76 (16)
C6—C1—C2	118.79 (16)	N4—C9—C7	119.38 (15)
C6—C1—C7	120.34 (16)	N5—C9—C7	120.86 (16)
C2—C1—C7	120.86 (15)	O1—C10—C11	112.2 (3)
C3—C2—C1	119.92 (16)	O1—C10—H10A	109.2
C3—C2—Cl1	120.84 (14)	C11—C10—H10A	109.2
C1—C2—Cl1	119.24 (13)	O1—C10—H10B	109.2
C4—C3—C2	120.83 (18)	C11—C10—H10B	109.2
C4—C3—Cl2	118.79 (15)	H10A—C10—H10B	107.9
C2—C3—Cl2	120.38 (15)	C10—C11—H11A	109.5
C3—C4—C5	119.53 (19)	C10—C11—H11B	109.5
C3—C4—H4	120.2	H11A—C11—H11B	109.5
C5—C4—H4	120.2	C10—C11—H11C	109.5
C4—C5—C6	120.3 (2)	H11A—C11—H11C	109.5
C4—C5—H5	119.9	H11B—C11—H11C	109.5
C6—C5—H5	119.9

C7—N1—N2—C8	−0.6 (3)	N2—N1—C7—C1	179.81 (16)
C6—C1—C2—C3	0.9 (3)	C6—C1—C7—N1	−85.8 (2)
C7—C1—C2—C3	179.62 (16)	C2—C1—C7—N1	95.5 (2)
C6—C1—C2—Cl1	−178.15 (14)	C6—C1—C7—C9	92.9 (2)
C7—C1—C2—Cl1	0.6 (2)	C2—C1—C7—C9	−85.8 (2)
C1—C2—C3—C4	−0.9 (3)	N1—N2—C8—N4	−0.4 (3)
Cl1—C2—C3—C4	178.08 (16)	N1—N2—C8—N3	178.98 (17)
C1—C2—C3—Cl2	178.96 (13)	C9—N4—C8—N2	0.9 (3)
Cl1—C2—C3—Cl2	−2.0 (2)	C9—N4—C8—N3	−178.48 (18)
C2—C3—C4—C5	0.2 (3)	C8—N4—C9—N5	179.81 (19)
Cl2—C3—C4—C5	−179.65 (19)	C8—N4—C9—C7	−0.4 (2)
C3—C4—C5—C6	0.5 (4)	N1—C7—C9—N4	−0.5 (3)
C4—C5—C6—C1	−0.6 (4)	C1—C7—C9—N4	−179.23 (16)
C2—C1—C6—C5	−0.1 (3)	N1—C7—C9—N5	179.22 (19)
C7—C1—C6—C5	−178.9 (2)	C1—C7—C9—N5	0.5 (3)
N2—N1—C7—C9	1.1 (3)

(LAM_ethanol_form_II) top

Crystal data top

C₁₁H₁₃Cl₂N₅O	F(000) = 1248
M_r = 302.16	D_x = 1.379 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 21.268 (9) Å	Cell parameters from 1132 reflections
b = 10.450 (3) Å	θ = 3.1–31.9°
c = 19.085 (7) Å	µ = 0.45 mm⁻¹
β = 136.662 (3)°	T = 296 K
V = 2911.1 (18) Å³	Prism, colourless
Z = 8	0.50 × 0.50 × 0.30 mm

Data collection top

Oxford Xcalibur Gemini diffractometer	θ_max = 27.0°, θ_min = 3.1°
9035 measured reflections	h = −27→24
3173 independent reflections	k = −12→13
1575 reflections with I > 2σ(I)	l = −24→24
R_int = 0.038

Refinement top

Refinement on F²	7 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.041	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.103	w = 1/[σ²(F_o²) + (0.0558P)²] where P = (F_o² + 2F_c²)/3
S = 0.82	(Δ/σ)_max = 0.001
3173 reflections	Δρ_max = 0.35 e Å⁻³
205 parameters	Δρ_min = −0.31 e Å⁻³

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cl1	0.19605 (4)	0.33114 (7)	0.10695 (5)	0.0775 (2)
Cl2	0.39425 (4)	0.37241 (8)	0.21226 (6)	0.0925 (3)
O1	0.25203 (11)	0.44687 (19)	0.41223 (13)	0.0734 (5)
H1O1	0.2301 (19)	0.3801 (18)	0.379 (2)	0.110*
N1	0.16208 (11)	0.23345 (18)	0.27716 (12)	0.0534 (5)
N2	0.08001 (11)	0.22087 (19)	0.24142 (13)	0.0545 (5)
N3	−0.06696 (12)	0.1501 (2)	0.11602 (14)	0.0653 (6)
H1N3	−0.1115 (12)	0.114 (2)	0.0586 (11)	0.078*
H2N3	−0.0748 (16)	0.186 (2)	0.1499 (16)	0.078*
N4	0.02721 (10)	0.09866 (17)	0.10082 (12)	0.0463 (4)
N5	0.12636 (11)	0.0424 (2)	0.09519 (14)	0.0559 (5)
H1N5	0.1779 (9)	0.046 (2)	0.1167 (16)	0.067*
H2N5	0.0828 (11)	0.002 (2)	0.0399 (11)	0.067*
C1	0.27255 (12)	0.2035 (2)	0.27667 (15)	0.0476 (5)
C2	0.28729 (13)	0.2690 (2)	0.22666 (15)	0.0508 (6)
C3	0.37514 (14)	0.2892 (2)	0.27323 (18)	0.0600 (6)
C4	0.44892 (15)	0.2445 (3)	0.3699 (2)	0.0750 (8)
H4	0.5079	0.2573	0.4006	0.090*
C5	0.43613 (15)	0.1815 (3)	0.42078 (19)	0.0779 (8)
H5	0.4864	0.1517	0.4866	0.093*
C6	0.34843 (14)	0.1613 (2)	0.37507 (16)	0.0636 (7)
H6	0.3404	0.1189	0.4109	0.076*
C7	0.17874 (12)	0.1820 (2)	0.22937 (14)	0.0447 (5)
C8	0.01549 (13)	0.1563 (2)	0.15342 (15)	0.0489 (5)
C9	0.11068 (12)	0.1063 (2)	0.14076 (14)	0.0428 (5)
C10A	0.2115 (3)	0.4730 (11)	0.4462 (6)	0.097 (2)	0.57
H10A	0.2472	0.5382	0.4988	0.116*	0.57
H10B	0.2136	0.3960	0.4762	0.116*	0.57
C11A	0.1162 (6)	0.5163 (9)	0.3632 (6)	0.118 (3)	0.57
H11A	0.0921	0.5325	0.3896	0.177*	0.57
H11B	0.1139	0.5935	0.3341	0.177*	0.57
H11C	0.0803	0.4513	0.3115	0.177*	0.57
C10B	0.1869 (7)	0.5266 (9)	0.3920 (9)	0.087 (3)	0.43
H10C	0.1373	0.5445	0.3194	0.104*	0.43
H10D	0.2152	0.6072	0.4279	0.104*	0.43
C11B	0.1506 (15)	0.4635 (13)	0.4253 (14)	0.145 (5)	0.43
H11D	0.1062	0.5182	0.4114	0.217*	0.43
H11E	0.1220	0.3843	0.3891	0.217*	0.43
H11F	0.1997	0.4468	0.4973	0.217*	0.43

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0594 (3)	0.0873 (5)	0.0701 (4)	−0.0030 (3)	0.0421 (3)	0.0179 (4)
Cl2	0.0866 (5)	0.1127 (7)	0.1106 (6)	−0.0347 (4)	0.0822 (5)	−0.0216 (5)
O1	0.0617 (10)	0.0862 (15)	0.0832 (12)	−0.0223 (9)	0.0563 (10)	−0.0299 (10)
N1	0.0523 (10)	0.0630 (13)	0.0542 (10)	−0.0137 (9)	0.0418 (9)	−0.0149 (9)
N2	0.0522 (10)	0.0705 (14)	0.0545 (11)	−0.0145 (9)	0.0432 (9)	−0.0183 (10)
N3	0.0468 (10)	0.1005 (19)	0.0593 (12)	−0.0120 (10)	0.0420 (9)	−0.0224 (12)
N4	0.0436 (9)	0.0574 (12)	0.0466 (9)	−0.0083 (8)	0.0356 (8)	−0.0105 (9)
N5	0.0449 (10)	0.0726 (15)	0.0594 (11)	−0.0161 (9)	0.0410 (10)	−0.0257 (10)
C1	0.0419 (11)	0.0500 (15)	0.0471 (12)	−0.0075 (9)	0.0312 (10)	−0.0100 (10)
C2	0.0429 (11)	0.0522 (15)	0.0558 (13)	−0.0093 (10)	0.0354 (10)	−0.0103 (11)
C3	0.0528 (13)	0.0655 (17)	0.0683 (15)	−0.0139 (11)	0.0461 (13)	−0.0166 (13)
C4	0.0439 (13)	0.089 (2)	0.0794 (19)	−0.0091 (13)	0.0408 (14)	−0.0138 (16)
C5	0.0435 (13)	0.087 (2)	0.0544 (15)	0.0023 (13)	0.0198 (12)	−0.0049 (15)
C6	0.0519 (13)	0.0722 (18)	0.0493 (13)	−0.0069 (12)	0.0312 (11)	−0.0049 (12)
C7	0.0431 (11)	0.0517 (14)	0.0439 (11)	−0.0056 (9)	0.0331 (10)	−0.0056 (10)
C8	0.0509 (12)	0.0550 (15)	0.0513 (12)	−0.0053 (10)	0.0405 (11)	−0.0050 (11)
C9	0.0423 (11)	0.0486 (13)	0.0429 (11)	−0.0052 (9)	0.0328 (10)	−0.0047 (10)
C10A	0.068 (4)	0.151 (8)	0.080 (4)	−0.008 (4)	0.057 (4)	−0.025 (4)
C11A	0.117 (6)	0.098 (7)	0.172 (8)	0.015 (4)	0.116 (6)	0.002 (5)
C10B	0.082 (6)	0.087 (6)	0.104 (7)	0.012 (4)	0.071 (5)	0.025 (5)
C11B	0.226 (14)	0.109 (11)	0.226 (15)	−0.078 (11)	0.205 (14)	−0.081 (10)

Geometric parameters (Å, º) top

Cl1—C2	1.720 (2)	C3—C4	1.368 (3)
Cl2—C3	1.721 (2)	C4—C5	1.355 (4)
O1—C10B	1.409 (9)	C4—H4	0.9300
O1—C10A	1.431 (7)	C5—C6	1.385 (3)
O1—H1O1	0.819 (10)	C5—H5	0.9300
N1—C7	1.310 (2)	C6—H6	0.9300
N1—N2	1.341 (2)	C7—C9	1.421 (3)
N2—C8	1.344 (3)	C10A—C11A	1.467 (7)
N3—C8	1.330 (3)	C10A—H10A	0.9700
N3—H1N3	0.857 (10)	C10A—H10B	0.9700
N3—H2N3	0.860 (10)	C11A—H11A	0.9600
N4—C9	1.331 (2)	C11A—H11B	0.9600
N4—C8	1.340 (2)	C11A—H11C	0.9600
N5—C9	1.317 (2)	C10B—C11B	1.466 (8)
N5—H1N5	0.847 (9)	C10B—H10C	0.9700
N5—H2N5	0.854 (9)	C10B—H10D	0.9700
C1—C2	1.383 (3)	C11B—H11D	0.9600
C1—C6	1.385 (3)	C11B—H11E	0.9600
C1—C7	1.492 (3)	C11B—H11F	0.9600
C2—C3	1.382 (3)

C10B—O1—H1O1	113 (2)	C9—C7—C1	124.07 (18)
C10A—O1—H1O1	108 (2)	N3—C8—N4	117.85 (19)
C7—N1—N2	121.13 (17)	N3—C8—N2	116.38 (19)
N1—N2—C8	116.94 (17)	N4—C8—N2	125.77 (18)
C8—N3—H1N3	120.5 (16)	N5—C9—N4	117.67 (17)
C8—N3—H2N3	118.4 (16)	N5—C9—C7	122.67 (17)
H1N3—N3—H2N3	121 (2)	N4—C9—C7	119.66 (18)
C9—N4—C8	116.19 (16)	O1—C10A—C11A	112.5 (9)
C9—N5—H1N5	121.3 (15)	O1—C10A—H10A	109.1
C9—N5—H2N5	119.9 (15)	C11A—C10A—H10A	109.1
H1N5—N5—H2N5	119 (2)	O1—C10A—H10B	109.1
C2—C1—C6	117.91 (19)	C11A—C10A—H10B	109.1
C2—C1—C7	122.10 (18)	H10A—C10A—H10B	107.8
C6—C1—C7	119.9 (2)	C10A—C11A—H11A	109.5
C3—C2—C1	120.7 (2)	C10A—C11A—H11B	109.5
C3—C2—Cl1	119.22 (18)	H11A—C11A—H11B	109.5
C1—C2—Cl1	120.03 (15)	C10A—C11A—H11C	109.5
C4—C3—C2	120.2 (2)	H11A—C11A—H11C	109.5
C4—C3—Cl2	118.72 (18)	H11B—C11A—H11C	109.5
C2—C3—Cl2	121.05 (19)	O1—C10B—C11B	109.8 (12)
C5—C4—C3	120.1 (2)	O1—C10B—H10C	109.7
C5—C4—H4	120.0	C11B—C10B—H10C	109.7
C3—C4—H4	120.0	O1—C10B—H10D	109.7
C4—C5—C6	120.2 (2)	C11B—C10B—H10D	109.7
C4—C5—H5	119.9	H10C—C10B—H10D	108.2
C6—C5—H5	119.9	C10B—C11B—H11D	109.5
C1—C6—C5	120.9 (2)	C10B—C11B—H11E	109.5
C1—C6—H6	119.6	H11D—C11B—H11E	109.5
C5—C6—H6	119.6	C10B—C11B—H11F	109.5
N1—C7—C9	119.97 (17)	H11D—C11B—H11F	109.5
N1—C7—C1	115.89 (17)	H11E—C11B—H11F	109.5

C7—N1—N2—C8	−1.7 (3)	N2—N1—C7—C1	179.70 (19)
C6—C1—C2—C3	1.2 (3)	C2—C1—C7—N1	−118.0 (2)
C7—C1—C2—C3	178.9 (2)	C6—C1—C7—N1	59.7 (3)
C6—C1—C2—Cl1	−176.57 (17)	C2—C1—C7—C9	64.9 (3)
C7—C1—C2—Cl1	1.2 (3)	C6—C1—C7—C9	−117.4 (2)
C1—C2—C3—C4	−0.1 (3)	C9—N4—C8—N3	−179.7 (2)
Cl1—C2—C3—C4	177.7 (2)	C9—N4—C8—N2	0.5 (3)
C1—C2—C3—Cl2	−179.14 (17)	N1—N2—C8—N3	−176.6 (2)
Cl1—C2—C3—Cl2	−1.3 (3)	N1—N2—C8—N4	3.2 (3)
C2—C3—C4—C5	−0.8 (4)	C8—N4—C9—N5	174.9 (2)
Cl2—C3—C4—C5	178.3 (2)	C8—N4—C9—C7	−5.3 (3)
C3—C4—C5—C6	0.4 (4)	N1—C7—C9—N5	−173.4 (2)
C2—C1—C6—C5	−1.5 (3)	C1—C7—C9—N5	3.6 (3)
C7—C1—C6—C5	−179.3 (2)	N1—C7—C9—N4	6.8 (3)
C4—C5—C6—C1	0.7 (4)	C1—C7—C9—N4	−176.19 (19)
N2—N1—C7—C9	−3.0 (3)

(LAM_acetone_solvate) top

Crystal data top

C₉H₇Cl₂N₅·C₃H₆O	Z = 2
M_r = 314.17	F(000) = 324
Triclinic, P1	D_x = 1.356 Mg m⁻³
a = 7.1227 (6) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.6434 (10) Å	Cell parameters from 1624 reflections
c = 10.9101 (13) Å	θ = 4.2–60.9°
α = 94.031 (9)°	µ = 0.42 mm⁻¹
β = 100.823 (9)°	T = 296 K
γ = 107.105 (8)°	Stick, colourless
V = 769.47 (14) Å³	0.60 × 0.20 × 0.20 mm

Data collection top

Xcalibur, Sapphire3, Gemini diffractometer	1721 reflections with I > 2σ(I)
Radiation source: Enhance (Cu) X-ray Source	R_int = 0.029
ω scans	θ_max = 23.8°, θ_min = 1.9°
Absorption correction: multi-scan	h = −7→7
T_min = 0.716, T_max = 1.000	k = −6→12
3812 measured reflections	l = −11→12
2283 independent reflections

Refinement top

Refinement on F²	4 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.041	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.122	w = 1/[σ²(F_o²) + (0.0689P)²] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max = 0.001
2283 reflections	Δρ_max = 0.21 e Å⁻³
193 parameters	Δρ_min = −0.24 e Å⁻³

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	0.85131 (10)	0.18644 (9)	0.90144 (7)	0.0861 (3)
Cl2	1.26101 (13)	0.21477 (11)	1.08348 (8)	0.1091 (4)
O1	0.0098 (3)	−0.0938 (2)	0.6908 (2)	0.0947 (7)
N1	0.8507 (3)	0.42002 (19)	0.63750 (19)	0.0591 (5)
N2	0.6829 (3)	0.42271 (19)	0.5584 (2)	0.0604 (6)
N3	0.3808 (3)	0.3123 (2)	0.4285 (2)	0.0683 (6)
H1N3	0.277 (3)	0.2430 (18)	0.399 (3)	0.082*
H2N3	0.364 (4)	0.3888 (15)	0.421 (3)	0.082*
N4	0.5691 (3)	0.18587 (18)	0.51721 (18)	0.0563 (5)
N5	0.7720 (4)	0.0692 (2)	0.5992 (2)	0.0710 (7)
H1N5	0.884 (2)	0.064 (3)	0.640 (2)	0.085*
H2N5	0.678 (3)	−0.0017 (18)	0.561 (2)	0.085*
C1	1.0724 (3)	0.3169 (2)	0.7464 (2)	0.0511 (6)
C2	1.0759 (3)	0.2648 (2)	0.8603 (2)	0.0558 (6)
C3	1.2562 (4)	0.2790 (3)	0.9427 (2)	0.0641 (7)
C4	1.4353 (4)	0.3467 (3)	0.9136 (3)	0.0732 (8)
H4	1.5566	0.3558	0.9687	0.088*
C5	1.4348 (4)	0.4009 (3)	0.8031 (3)	0.0771 (8)
H5	1.5558	0.4475	0.7837	0.092*
C6	1.2550 (4)	0.3861 (3)	0.7207 (3)	0.0657 (7)
H6	1.2564	0.4236	0.6462	0.079*
C7	0.8813 (3)	0.3068 (2)	0.6574 (2)	0.0499 (6)
C8	0.5477 (4)	0.3065 (2)	0.5045 (2)	0.0538 (6)
C9	0.7403 (3)	0.1853 (2)	0.5915 (2)	0.0528 (6)
C10	0.1575 (4)	−0.1214 (3)	0.7326 (3)	0.0655 (7)
C11	0.3514 (5)	−0.0167 (3)	0.7858 (4)	0.1119 (13)
H11A	0.4530	−0.0569	0.8148	0.168*
H11B	0.3902	0.0370	0.7221	0.168*
H11C	0.3369	0.0378	0.8551	0.168*
C12	0.1536 (5)	−0.2606 (3)	0.7360 (3)	0.0906 (10)
H12A	0.2859	−0.2629	0.7727	0.136*
H12B	0.0611	−0.3024	0.7857	0.136*
H12C	0.1113	−0.3069	0.6519	0.136*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0561 (4)	0.1130 (7)	0.0789 (5)	0.0085 (4)	0.0108 (3)	0.0352 (4)
Cl2	0.0927 (6)	0.1551 (9)	0.0780 (6)	0.0438 (6)	−0.0038 (4)	0.0464 (6)
O1	0.0683 (13)	0.0759 (14)	0.1295 (18)	0.0265 (11)	−0.0135 (12)	0.0235 (12)
N1	0.0577 (12)	0.0458 (12)	0.0673 (13)	0.0152 (9)	−0.0005 (10)	0.0079 (10)
N2	0.0569 (12)	0.0445 (12)	0.0712 (13)	0.0162 (10)	−0.0076 (10)	0.0075 (10)
N3	0.0669 (14)	0.0488 (13)	0.0784 (15)	0.0221 (11)	−0.0158 (12)	0.0059 (12)
N4	0.0599 (12)	0.0429 (12)	0.0583 (12)	0.0183 (9)	−0.0083 (10)	0.0045 (9)
N5	0.0670 (14)	0.0463 (13)	0.0867 (17)	0.0225 (11)	−0.0188 (12)	0.0002 (11)
C1	0.0486 (13)	0.0436 (13)	0.0566 (14)	0.0137 (11)	0.0031 (11)	0.0031 (11)
C2	0.0479 (13)	0.0536 (14)	0.0617 (15)	0.0146 (11)	0.0054 (11)	0.0052 (12)
C3	0.0582 (16)	0.0732 (17)	0.0585 (15)	0.0260 (14)	−0.0012 (12)	0.0070 (13)
C4	0.0491 (16)	0.085 (2)	0.0778 (19)	0.0238 (14)	−0.0031 (13)	−0.0034 (16)
C5	0.0479 (15)	0.089 (2)	0.084 (2)	0.0085 (14)	0.0131 (14)	0.0040 (17)
C6	0.0576 (16)	0.0684 (17)	0.0654 (16)	0.0124 (13)	0.0117 (13)	0.0082 (13)
C7	0.0506 (13)	0.0423 (13)	0.0537 (13)	0.0146 (10)	0.0033 (10)	0.0072 (10)
C8	0.0585 (14)	0.0464 (14)	0.0539 (14)	0.0198 (11)	0.0002 (11)	0.0077 (11)
C9	0.0557 (14)	0.0426 (14)	0.0565 (14)	0.0184 (11)	−0.0008 (11)	0.0057 (11)
C10	0.0550 (15)	0.0621 (17)	0.0739 (17)	0.0169 (13)	0.0036 (13)	0.0081 (14)
C11	0.067 (2)	0.078 (2)	0.166 (4)	0.0043 (17)	0.004 (2)	−0.008 (2)
C12	0.083 (2)	0.070 (2)	0.117 (3)	0.0308 (17)	0.0091 (19)	0.0152 (18)

Geometric parameters (Å, º) top

Cl1—C2	1.730 (2)	C2—C3	1.383 (3)
Cl2—C3	1.723 (3)	C3—C4	1.375 (4)
O1—C10	1.193 (3)	C4—C5	1.373 (4)
N1—C7	1.312 (3)	C4—H4	0.9300
N1—N2	1.346 (3)	C5—C6	1.379 (4)
N2—C8	1.337 (3)	C5—H5	0.9300
N3—C8	1.336 (3)	C6—H6	0.9300
N3—H1N3	0.865 (10)	C7—C9	1.425 (3)
N3—H2N3	0.864 (10)	C10—C12	1.476 (4)
N4—C9	1.333 (3)	C10—C11	1.480 (4)
N4—C8	1.350 (3)	C11—H11A	0.9600
N5—C9	1.326 (3)	C11—H11B	0.9600
N5—H1N5	0.859 (10)	C11—H11C	0.9600
N5—H2N5	0.862 (10)	C12—H12A	0.9600
C1—C6	1.384 (3)	C12—H12B	0.9600
C1—C2	1.395 (3)	C12—H12C	0.9600
C1—C7	1.486 (3)

C7—N1—N2	120.55 (19)	C1—C6—H6	119.3
C8—N2—N1	117.65 (18)	N1—C7—C9	120.14 (19)
C8—N3—H1N3	122.8 (19)	N1—C7—C1	115.5 (2)
C8—N3—H2N3	118.8 (19)	C9—C7—C1	124.34 (19)
H1N3—N3—H2N3	117 (3)	N3—C8—N2	116.3 (2)
C9—N4—C8	115.83 (19)	N3—C8—N4	118.0 (2)
C9—N5—H1N5	121 (2)	N2—C8—N4	125.7 (2)
C9—N5—H2N5	119 (2)	N5—C9—N4	117.3 (2)
H1N5—N5—H2N5	120 (3)	N5—C9—C7	122.8 (2)
C6—C1—C2	117.7 (2)	N4—C9—C7	119.93 (19)
C6—C1—C7	119.9 (2)	O1—C10—C12	121.6 (3)
C2—C1—C7	122.3 (2)	O1—C10—C11	121.0 (3)
C3—C2—C1	120.9 (2)	C12—C10—C11	117.4 (3)
C3—C2—Cl1	119.6 (2)	C10—C11—H11A	109.5
C1—C2—Cl1	119.45 (17)	C10—C11—H11B	109.5
C4—C3—C2	120.0 (2)	H11A—C11—H11B	109.5
C4—C3—Cl2	118.95 (19)	C10—C11—H11C	109.5
C2—C3—Cl2	121.0 (2)	H11A—C11—H11C	109.5
C5—C4—C3	119.9 (2)	H11B—C11—H11C	109.5
C5—C4—H4	120.0	C10—C12—H12A	109.5
C3—C4—H4	120.0	C10—C12—H12B	109.5
C4—C5—C6	120.0 (3)	H12A—C12—H12B	109.5
C4—C5—H5	120.0	C10—C12—H12C	109.5
C6—C5—H5	120.0	H12A—C12—H12C	109.5
C5—C6—C1	121.4 (3)	H12B—C12—H12C	109.5
C5—C6—H6	119.3

C7—N1—N2—C8	1.9 (3)	N2—N1—C7—C1	179.9 (2)
C6—C1—C2—C3	−1.8 (3)	C6—C1—C7—N1	−59.6 (3)
C7—C1—C2—C3	−178.2 (2)	C2—C1—C7—N1	116.8 (3)
C6—C1—C2—Cl1	175.96 (18)	C6—C1—C7—C9	117.7 (3)
C7—C1—C2—Cl1	−0.5 (3)	C2—C1—C7—C9	−65.9 (3)
C1—C2—C3—C4	0.9 (4)	N1—N2—C8—N3	178.7 (2)
Cl1—C2—C3—C4	−176.9 (2)	N1—N2—C8—N4	−3.6 (4)
C1—C2—C3—Cl2	179.97 (18)	C9—N4—C8—N3	178.4 (2)
Cl1—C2—C3—Cl2	2.2 (3)	C9—N4—C8—N2	0.7 (4)
C2—C3—C4—C5	0.4 (4)	C8—N4—C9—N5	−175.6 (2)
Cl2—C3—C4—C5	−178.7 (2)	C8—N4—C9—C7	3.7 (3)
C3—C4—C5—C6	−0.7 (4)	N1—C7—C9—N5	173.8 (2)
C4—C5—C6—C1	−0.2 (4)	C1—C7—C9—N5	−3.4 (4)
C2—C1—C6—C5	1.5 (4)	N1—C7—C9—N4	−5.4 (4)
C7—C1—C6—C5	178.0 (2)	C1—C7—C9—N4	177.4 (2)
N2—N1—C7—C9	2.4 (4)

(LAM_2-propanol_solvate) top

Crystal data top

C₉H₇Cl₂N₅·2(C₃H₈O)	F(000) = 792
M_r = 376.28	D_x = 1.228 Mg m⁻³
Monoclinic, P2₁/n	Cu Kα radiation, λ = 1.54184 Å
a = 10.5757 (10) Å	Cell parameters from 1076 reflections
b = 12.8768 (19) Å	θ = 3.0–72.4°
c = 15.0121 (17) Å	µ = 3.01 mm⁻¹
β = 95.258 (8)°	T = 296 K
V = 2035.8 (4) Å³	Prism, colourless
Z = 4	0.60 × 0.38 × 0.24 mm

Data collection top

Xcalibur, Sapphire3, Gemini diffractometer	1794 reflections with I > 2σ(I)
Radiation source: Enhance (Cu) X-ray Source	R_int = 0.109
ω scans	θ_max = 67.5°, θ_min = 4.5°
Absorption correction: multi-scan CrysAlisPro, Agilent Technologies, Version 1.171.36.21. Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −10→12
T_min = 0.397, T_max = 1.000	k = −15→15
20445 measured reflections	l = −17→17
3668 independent reflections

Refinement top

Refinement on F²	10 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.080	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.272	w = 1/[σ²(F_o²) + (0.1359P)²] where P = (F_o² + 2F_c²)/3
S = 0.97	(Δ/σ)_max < 0.001
3668 reflections	Δρ_max = 0.27 e Å⁻³
256 parameters	Δρ_min = −0.33 e Å⁻³

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cl1	0.06053 (17)	0.49851 (11)	0.19269 (10)	0.1088 (6)
Cl2	−0.0667 (2)	0.36294 (18)	0.03533 (11)	0.1466 (9)
O1	0.0146 (4)	0.1620 (6)	0.7384 (3)	0.151 (2)
H11O	−0.041 (6)	0.184 (7)	0.768 (5)	0.181*
O2	0.2331 (4)	0.6938 (4)	0.6910 (3)	0.1110 (13)
H12O	0.299 (4)	0.686 (5)	0.725 (4)	0.133*
N1	0.3187 (3)	0.3837 (3)	0.3625 (2)	0.0649 (9)
N2	0.3727 (3)	0.4364 (3)	0.4344 (2)	0.0632 (9)
N3	0.3479 (3)	0.5382 (4)	0.5559 (3)	0.0751 (11)
N4	0.1665 (3)	0.4786 (3)	0.4767 (2)	0.0674 (9)
N5	−0.0113 (4)	0.4158 (4)	0.3959 (3)	0.0838 (12)
C1	0.1427 (4)	0.3178 (4)	0.2673 (3)	0.0662 (11)
C2	0.0753 (4)	0.3659 (4)	0.1945 (3)	0.0733 (12)
C3	0.0228 (5)	0.3060 (5)	0.1238 (3)	0.0888 (15)
C4	0.0403 (6)	0.2015 (5)	0.1232 (4)	0.1062 (19)
H4	0.0048	0.1620	0.0753	0.127*
C5	0.1099 (7)	0.1544 (5)	0.1929 (5)	0.119 (2)
H5	0.1237	0.0831	0.1917	0.142*
C6	0.1602 (5)	0.2121 (4)	0.2655 (4)	0.0947 (16)
H6	0.2060	0.1792	0.3133	0.114*
C7	0.1947 (4)	0.3784 (3)	0.3462 (3)	0.0609 (10)
C8	0.2938 (4)	0.4831 (3)	0.4865 (3)	0.0618 (10)
C9	0.1151 (4)	0.4252 (3)	0.4064 (3)	0.0644 (11)
C10	−0.0376 (8)	0.1601 (9)	0.6473 (5)	0.135 (3)
H10A	−0.1080	0.2098	0.6403	0.162*	0.52 (3)
H10B	−0.1242	0.1329	0.6470	0.162*	0.48 (3)
C11A	−0.087 (2)	0.0571 (12)	0.6249 (11)	0.144 (8)	0.52 (3)
H11A	−0.1224	0.0561	0.5636	0.216*	0.52 (3)
H11B	−0.0200	0.0070	0.6333	0.216*	0.52 (3)
H11C	−0.1525	0.0401	0.6630	0.216*	0.52 (3)
C11B	0.032 (5)	0.089 (4)	0.593 (3)	0.40 (5)	0.48 (3)
H11D	−0.0058	0.0896	0.5326	0.596*	0.48 (3)
H11E	0.1189	0.1105	0.5948	0.596*	0.48 (3)
H11F	0.0280	0.0198	0.6170	0.596*	0.48 (3)
C12A	0.060 (3)	0.193 (3)	0.5894 (13)	0.21 (2)	0.52 (3)
H12A	0.0251	0.1918	0.5281	0.321*	0.52 (3)
H12B	0.0874	0.2622	0.6052	0.321*	0.52 (3)
H12C	0.1311	0.1465	0.5971	0.321*	0.52 (3)
C12B	−0.049 (4)	0.2711 (15)	0.623 (2)	0.216 (18)	0.48 (3)
H12D	−0.0837	0.2774	0.5619	0.324*	0.48 (3)
H12E	−0.1037	0.3052	0.6613	0.324*	0.48 (3)
H12F	0.0336	0.3028	0.6300	0.324*	0.48 (3)
C13	0.2862 (12)	0.8237 (8)	0.5907 (7)	0.201 (5)
H13A	0.3762	0.8224	0.6065	0.302*
H13B	0.2617	0.8913	0.5682	0.302*
H13C	0.2643	0.7726	0.5453	0.302*
C14	0.2219 (9)	0.8015 (7)	0.6672 (6)	0.141 (3)
H14	0.1320	0.8098	0.6462	0.170*
C15	0.2406 (8)	0.8731 (6)	0.7457 (6)	0.162 (4)
H15A	0.1827	0.8549	0.7887	0.243*
H15B	0.2250	0.9433	0.7261	0.243*
H15C	0.3263	0.8671	0.7725	0.243*
H2N3	0.4289 (14)	0.546 (6)	0.561 (6)	0.194*
H1N5	−0.058 (6)	0.447 (6)	0.432 (4)	0.194*
H1N3	0.309 (7)	0.571 (6)	0.595 (4)	0.194*
H2N5	−0.041 (8)	0.369 (5)	0.359 (4)	0.194*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.1308 (14)	0.0950 (11)	0.0965 (10)	0.0158 (8)	−0.0125 (9)	0.0012 (7)
Cl2	0.1386 (17)	0.209 (2)	0.0844 (10)	0.0109 (14)	−0.0308 (10)	−0.0181 (11)
O1	0.078 (3)	0.269 (7)	0.105 (4)	−0.016 (4)	0.010 (2)	0.040 (4)
O2	0.089 (3)	0.121 (3)	0.119 (3)	−0.014 (2)	−0.010 (2)	−0.020 (3)
N1	0.055 (2)	0.076 (2)	0.064 (2)	0.0036 (16)	0.0053 (15)	−0.0070 (16)
N2	0.0465 (18)	0.077 (2)	0.065 (2)	0.0038 (15)	0.0024 (14)	−0.0044 (16)
N3	0.051 (2)	0.104 (3)	0.070 (2)	−0.001 (2)	0.0011 (17)	−0.023 (2)
N4	0.0458 (18)	0.089 (3)	0.067 (2)	−0.0007 (16)	0.0032 (14)	−0.0168 (18)
N5	0.044 (2)	0.119 (4)	0.089 (3)	−0.002 (2)	0.0042 (17)	−0.035 (2)
C1	0.052 (2)	0.079 (3)	0.068 (2)	0.002 (2)	0.0086 (18)	−0.013 (2)
C2	0.060 (3)	0.087 (3)	0.073 (3)	0.001 (2)	0.007 (2)	−0.014 (2)
C3	0.073 (3)	0.125 (5)	0.067 (3)	−0.001 (3)	−0.001 (2)	−0.024 (3)
C4	0.099 (4)	0.116 (5)	0.103 (4)	−0.022 (4)	0.008 (3)	−0.049 (4)
C5	0.151 (6)	0.092 (4)	0.111 (5)	−0.001 (4)	0.001 (4)	−0.039 (4)
C6	0.099 (4)	0.084 (4)	0.099 (4)	0.009 (3)	−0.002 (3)	−0.023 (3)
C7	0.053 (2)	0.069 (2)	0.060 (2)	0.0001 (19)	0.0027 (17)	−0.0059 (18)
C8	0.052 (2)	0.071 (3)	0.063 (2)	0.0023 (18)	0.0021 (17)	0.0004 (19)
C9	0.045 (2)	0.080 (3)	0.068 (2)	0.0015 (19)	0.0023 (17)	−0.012 (2)
C10	0.124 (6)	0.179 (9)	0.102 (5)	−0.007 (5)	0.011 (4)	0.026 (5)
C11A	0.19 (2)	0.123 (14)	0.127 (12)	0.025 (12)	0.029 (11)	−0.007 (10)
C11B	0.39 (9)	0.48 (8)	0.31 (5)	0.30 (8)	0.00 (5)	−0.10 (6)
C12A	0.24 (3)	0.31 (5)	0.106 (12)	−0.09 (3)	0.069 (15)	0.025 (19)
C12B	0.31 (4)	0.15 (2)	0.18 (2)	−0.01 (2)	−0.06 (3)	0.065 (17)
C13	0.281 (14)	0.171 (9)	0.156 (9)	−0.042 (9)	0.040 (9)	0.010 (7)
C14	0.143 (7)	0.122 (6)	0.157 (8)	−0.010 (5)	0.004 (6)	−0.013 (6)
C15	0.152 (8)	0.137 (6)	0.201 (9)	−0.018 (5)	0.041 (6)	−0.075 (6)

Geometric parameters (Å, º) top

Cl1—C2	1.714 (5)	C10—C11A	1.455 (14)
Cl2—C3	1.723 (6)	C10—C11B	1.466 (17)
O1—C10	1.427 (8)	C10—C12A	1.471 (14)
O1—H11O	0.82 (2)	C10—C12B	1.478 (14)
O2—C14	1.435 (9)	C10—H10A	0.9800
O2—H12O	0.83 (2)	C10—H10B	0.9800
N1—C7	1.313 (5)	C11A—H11A	0.9600
N1—N2	1.356 (4)	C11A—H11B	0.9600
N2—C8	1.337 (5)	C11A—H11C	0.9600
N3—C8	1.344 (5)	C11B—H11D	0.9600
N3—H2N3	0.859 (10)	C11B—H11E	0.9600
N3—H1N3	0.861 (10)	C11B—H11F	0.9600
N4—C9	1.332 (5)	C12A—H12A	0.9600
N4—C8	1.342 (5)	C12A—H12B	0.9600
N5—C9	1.336 (5)	C12A—H12C	0.9600
N5—H1N5	0.862 (10)	C12B—H12D	0.9600
N5—H2N5	0.861 (10)	C12B—H12E	0.9600
C1—C6	1.374 (6)	C12B—H12F	0.9600
C1—C2	1.395 (6)	C13—C14	1.418 (11)
C1—C7	1.482 (5)	C13—H13A	0.9600
C2—C3	1.386 (6)	C13—H13B	0.9600
C3—C4	1.358 (8)	C13—H13C	0.9600
C4—C5	1.366 (9)	C14—C15	1.494 (9)
C4—H4	0.9300	C14—H14	0.9800
C5—C6	1.384 (7)	C15—H15A	0.9600
C5—H5	0.9300	C15—H15B	0.9600
C6—H6	0.9300	C15—H15C	0.9600
C7—C9	1.424 (5)

C10—O1—H11O	107 (6)	C12A—C10—H10A	108.4
C14—O2—H12O	108 (5)	O1—C10—H10B	106.9
C7—N1—N2	120.9 (3)	C11B—C10—H10B	106.9
C8—N2—N1	116.8 (3)	C12B—C10—H10B	106.9
C8—N3—H2N3	119 (6)	C10—C11A—H11A	109.5
C8—N3—H1N3	127 (6)	C10—C11A—H11B	109.5
H2N3—N3—H1N3	114 (7)	H11A—C11A—H11B	109.5
C9—N4—C8	116.2 (3)	C10—C11A—H11C	109.5
C9—N5—H1N5	121 (6)	H11A—C11A—H11C	109.5
C9—N5—H2N5	116 (6)	H11B—C11A—H11C	109.5
H1N5—N5—H2N5	122 (8)	C10—C11B—H11D	109.5
C6—C1—C2	119.0 (4)	C10—C11B—H11E	109.5
C6—C1—C7	119.8 (4)	H11D—C11B—H11E	109.5
C2—C1—C7	121.3 (4)	C10—C11B—H11F	109.5
C3—C2—C1	119.5 (5)	H11D—C11B—H11F	109.5
C3—C2—Cl1	120.9 (4)	H11E—C11B—H11F	109.5
C1—C2—Cl1	119.6 (3)	C10—C12A—H12A	109.5
C4—C3—C2	120.8 (5)	C10—C12A—H12B	109.5
C4—C3—Cl2	118.8 (4)	H12A—C12A—H12B	109.5
C2—C3—Cl2	120.4 (5)	C10—C12A—H12C	109.5
C3—C4—C5	119.9 (5)	H12A—C12A—H12C	109.5
C3—C4—H4	120.1	H12B—C12A—H12C	109.5
C5—C4—H4	120.1	C10—C12B—H12D	109.5
C4—C5—C6	120.4 (6)	C10—C12B—H12E	109.5
C4—C5—H5	119.8	H12D—C12B—H12E	109.5
C6—C5—H5	119.8	C10—C12B—H12F	109.5
C1—C6—C5	120.3 (6)	H12D—C12B—H12F	109.5
C1—C6—H6	119.8	H12E—C12B—H12F	109.5
C5—C6—H6	119.8	C14—C13—H13A	109.5
N1—C7—C9	119.9 (4)	C14—C13—H13B	109.5
N1—C7—C1	117.8 (4)	H13A—C13—H13B	109.5
C9—C7—C1	122.2 (4)	C14—C13—H13C	109.5
N2—C8—N4	126.1 (4)	H13A—C13—H13C	109.5
N2—C8—N3	116.5 (4)	H13B—C13—H13C	109.5
N4—C8—N3	117.3 (4)	C13—C14—O2	111.3 (8)
N4—C9—N5	118.1 (4)	C13—C14—C15	118.4 (8)
N4—C9—C7	119.8 (4)	O2—C14—C15	113.5 (7)
N5—C9—C7	122.0 (4)	C13—C14—H14	103.9
O1—C10—C11A	109.7 (10)	O2—C14—H14	103.9
O1—C10—C11B	111.8 (18)	C15—C14—H14	103.9
O1—C10—C12A	109.3 (11)	C14—C15—H15A	109.5
C11A—C10—C12A	112.6 (15)	C14—C15—H15B	109.5
O1—C10—C12B	103.6 (12)	H15A—C15—H15B	109.5
C11B—C10—C12B	120 (2)	C14—C15—H15C	109.5
O1—C10—H10A	108.4	H15A—C15—H15C	109.5
C11A—C10—H10A	108.4	H15B—C15—H15C	109.5

C7—N1—N2—C8	−0.8 (6)	N2—N1—C7—C1	−178.9 (4)
C6—C1—C2—C3	2.7 (7)	C6—C1—C7—N1	66.2 (6)
C7—C1—C2—C3	−176.8 (4)	C2—C1—C7—N1	−114.2 (5)
C6—C1—C2—Cl1	−176.2 (4)	C6—C1—C7—C9	−110.3 (5)
C7—C1—C2—Cl1	4.2 (6)	C2—C1—C7—C9	69.3 (6)
C1—C2—C3—C4	−2.4 (8)	N1—N2—C8—N4	3.4 (6)
Cl1—C2—C3—C4	176.5 (4)	N1—N2—C8—N3	−177.8 (4)
C1—C2—C3—Cl2	177.2 (4)	C9—N4—C8—N2	−2.4 (6)
Cl1—C2—C3—Cl2	−3.9 (6)	C9—N4—C8—N3	178.8 (4)
C2—C3—C4—C5	0.2 (9)	C8—N4—C9—N5	177.8 (4)
Cl2—C3—C4—C5	−179.4 (5)	C8—N4—C9—C7	−1.0 (6)
C3—C4—C5—C6	1.7 (11)	N1—C7—C9—N4	3.3 (6)
C2—C1—C6—C5	−0.9 (8)	C1—C7—C9—N4	179.7 (4)
C7—C1—C6—C5	178.7 (5)	N1—C7—C9—N5	−175.4 (5)
C4—C5—C6—C1	−1.4 (10)	C1—C7—C9—N5	1.0 (7)
N2—N1—C7—C9	−2.4 (6)

(LAM_n-butanol_solvate) top

Crystal data top

C₁₃H₁₇Cl₂N₅O	Z = 4
M_r = 330.21	F(000) = 688
Triclinic, P1	D_x = 1.325 Mg m⁻³
a = 10.8596 (9) Å	Cu Kα radiation, λ = 1.54184 Å
b = 11.4487 (13) Å	Cell parameters from 1904 reflections
c = 15.5823 (14) Å	θ = 3.0–72.5°
α = 98.562 (8)°	µ = 3.58 mm⁻¹
β = 101.242 (7)°	T = 296 K
γ = 115.425 (10)°	Stick, colourless
V = 1655.9 (3) Å³	0.68 × 0.38 × 0.25 mm

Data collection top

Xcalibur, Sapphire3, Gemini diffractometer	3774 reflections with I > 2σ(I)
Radiation source: Enhance (Cu) X-ray Source	R_int = 0.052
ω scans	θ_max = 68.0°, θ_min = 3.0°
Absorption correction: multi-scan	h = −13→11
T_min = 0.527, T_max = 1.000	k = −12→13
16409 measured reflections	l = −18→18
6028 independent reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.072	w = 1/[σ²(F_o²) + (0.1272P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.249	(Δ/σ)_max = 0.001
S = 1.04	Δρ_max = 0.39 e Å⁻³
6028 reflections	Δρ_min = −0.30 e Å⁻³
391 parameters	Extinction correction: SHELXL-2019/2 (Sheldrick 2019), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
10 restraints	Extinction coefficient: 0.0027 (6)

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cl1A	0.8736 (2)	0.52001 (17)	0.87200 (10)	0.1382 (6)
Cl1B	−0.24521 (9)	0.18746 (10)	0.23534 (7)	0.0852 (3)
Cl2A	1.1096 (3)	0.7627 (3)	1.03321 (11)	0.1905 (10)
Cl2B	−0.47628 (15)	−0.08172 (16)	0.09918 (9)	0.1353 (6)
O1A	0.5304 (4)	0.7420 (5)	0.7670 (2)	0.1349 (14)
H1A	0.560936	0.693362	0.746083	0.202*
O1B	0.4772 (3)	0.1073 (4)	0.3504 (3)	0.1227 (12)
H1B	0.448066	0.139931	0.313087	0.184*
N1A	0.6296 (3)	0.5752 (3)	0.6904 (2)	0.0764 (8)
N1B	0.0501 (3)	0.1760 (3)	0.4282 (2)	0.0735 (7)
N2A	0.5233 (3)	0.4763 (3)	0.6220 (2)	0.0799 (8)
N2B	0.1601 (3)	0.2808 (3)	0.49119 (19)	0.0750 (7)
N3A	0.4500 (3)	0.2955 (3)	0.5052 (2)	0.0859 (9)
H3A1	0.364729	0.284284	0.498008	0.103*
H3A2	0.465712	0.241268	0.470176	0.103*
N3B	0.2426 (3)	0.4718 (3)	0.6027 (2)	0.0831 (9)
H3B1	0.230309	0.530422	0.636182	0.100*
H3B2	0.326340	0.478999	0.610204	0.100*
N4A	0.6894 (3)	0.4101 (3)	0.58071 (19)	0.0704 (7)
N4B	0.0025 (3)	0.3615 (3)	0.52932 (18)	0.0701 (7)
N5A	0.9268 (3)	0.5315 (3)	0.6589 (2)	0.0808 (8)
H5A1	0.945522	0.480916	0.622858	0.097*
H5A2	0.994550	0.596403	0.702423	0.097*
N5B	−0.2351 (3)	0.2455 (3)	0.4537 (2)	0.0895 (10)
H5B1	−0.248834	0.302078	0.488025	0.107*
H5B2	−0.305813	0.179828	0.412120	0.107*
C1A	0.8702 (4)	0.7053 (4)	0.7848 (2)	0.0722 (8)
C1B	−0.1933 (3)	0.0394 (4)	0.3446 (2)	0.0713 (8)
C2A	0.9304 (4)	0.6817 (4)	0.8643 (3)	0.0864 (10)
C2B	−0.2738 (3)	0.0393 (3)	0.2624 (2)	0.0725 (8)
C3A	1.0326 (5)	0.7889 (6)	0.9362 (3)	0.1055 (14)
C3B	−0.3769 (4)	−0.0807 (4)	0.2010 (3)	0.0921 (12)
C4B	−0.4008 (5)	−0.2019 (5)	0.2209 (4)	0.1132 (16)
H4B	−0.469918	−0.282225	0.179704	0.136*
C4A	1.0737 (5)	0.9187 (6)	0.9302 (4)	0.1152 (17)
H4A	1.141385	0.990272	0.978713	0.138*
C5A	1.0156 (5)	0.9423 (5)	0.8537 (4)	0.1112 (15)
H5A	1.044227	1.030084	0.850199	0.133*
C5B	−0.3225 (6)	−0.2033 (5)	0.3016 (4)	0.1156 (16)
H5B	−0.338991	−0.284325	0.314983	0.139*
C6A	0.9141 (4)	0.8370 (4)	0.7807 (3)	0.0873 (10)
H6A	0.875222	0.854743	0.728761	0.105*
C6B	−0.2198 (5)	−0.0841 (4)	0.3622 (3)	0.0921 (11)
H6B	−0.166763	−0.085830	0.416152	0.111*
C7A	0.7609 (3)	0.5937 (4)	0.7072 (2)	0.0690 (8)
C7B	−0.0793 (3)	0.1628 (3)	0.4117 (2)	0.0653 (7)
C8A	0.5569 (3)	0.3962 (4)	0.5702 (2)	0.0717 (8)
C8B	0.1318 (3)	0.3699 (4)	0.5393 (2)	0.0678 (8)
C9A	0.7923 (3)	0.5091 (3)	0.6471 (2)	0.0693 (8)
C9B	−0.1050 (3)	0.2594 (4)	0.4648 (2)	0.0681 (8)
C10A	0.5708 (8)	0.7697 (9)	0.8628 (4)	0.150 (3)
H10A	0.539386	0.831898	0.886600	0.180*
H10B	0.673952	0.814065	0.884932	0.180*
C10B	0.3845 (9)	−0.0332 (10)	0.3277 (9)	0.250 (6)
H10C	0.386150	−0.069107	0.267715	0.300*
H10D	0.429997	−0.068268	0.368870	0.300*
C11A	0.5132 (15)	0.6501 (14)	0.8997 (6)	0.217 (5)
H11A	0.559615	0.674033	0.964199	0.260*
H11B	0.529255	0.579716	0.869500	0.260*
C11B	0.1474 (14)	−0.1900 (16)	0.3043 (10)	0.301 (9)
H11C	0.155027	−0.231848	0.353413	0.361*
H11D	0.151927	−0.245304	0.252640	0.361*
C12A	0.353 (2)	0.6026 (18)	0.8821 (11)	0.237 (7)	0.83
H12A	0.336935	0.675261	0.908526	0.285*	0.83
H12B	0.305663	0.572892	0.817416	0.285*	0.83
C12C	0.401 (5)	0.530 (3)	0.873 (3)	0.111 (10)	0.17
H12C	0.435674	0.464992	0.870692	0.134*	0.17
H12D	0.350233	0.518897	0.811230	0.134*	0.17
C12B	0.2607 (19)	−0.0843 (13)	0.3264 (13)	0.402 (13)
H12E	0.229616	−0.028871	0.296743	0.482*
H12F	0.270097	−0.052869	0.389834	0.482*
C13A	0.2977 (16)	0.494 (2)	0.9230 (10)	0.311 (9)
H13A	0.340865	0.525672	0.987445	0.466*
H13B	0.319067	0.424767	0.898897	0.466*
H13C	0.196382	0.458098	0.910020	0.466*
C13B	0.0182 (12)	−0.2094 (16)	0.2836 (10)	0.291 (9)
H13D	0.004210	−0.161659	0.333676	0.437*
H13E	−0.046064	−0.303469	0.270444	0.437*
H13F	0.000214	−0.177663	0.231338	0.437*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1A	0.1918 (16)	0.1237 (11)	0.1065 (9)	0.0817 (11)	0.0344 (10)	0.0399 (8)
Cl1B	0.0768 (5)	0.0884 (6)	0.0870 (6)	0.0436 (5)	0.0111 (4)	0.0161 (5)
Cl2A	0.212 (2)	0.231 (2)	0.0947 (10)	0.1147 (18)	−0.0253 (11)	0.0104 (11)
Cl2B	0.1159 (9)	0.1353 (12)	0.1056 (9)	0.0555 (8)	−0.0211 (7)	−0.0223 (7)
O1A	0.151 (3)	0.181 (4)	0.111 (2)	0.127 (3)	0.029 (2)	0.004 (2)
O1B	0.0789 (18)	0.118 (3)	0.137 (3)	0.0365 (18)	0.0151 (18)	−0.007 (2)
N1A	0.0673 (15)	0.0868 (19)	0.0793 (17)	0.0442 (15)	0.0235 (13)	0.0059 (14)
N1B	0.0698 (15)	0.0818 (18)	0.0802 (16)	0.0489 (14)	0.0213 (13)	0.0119 (14)
N2A	0.0649 (15)	0.092 (2)	0.0857 (18)	0.0473 (15)	0.0199 (13)	0.0014 (15)
N2B	0.0662 (14)	0.0853 (18)	0.0808 (17)	0.0492 (14)	0.0176 (13)	0.0042 (14)
N3A	0.0619 (15)	0.102 (2)	0.0873 (19)	0.0446 (16)	0.0163 (14)	−0.0030 (17)
N3B	0.0619 (15)	0.094 (2)	0.0893 (19)	0.0444 (15)	0.0139 (13)	0.0000 (16)
N4A	0.0582 (13)	0.0785 (17)	0.0784 (16)	0.0387 (13)	0.0228 (12)	0.0077 (13)
N4B	0.0621 (14)	0.0828 (18)	0.0719 (15)	0.0450 (13)	0.0184 (12)	0.0058 (13)
N5A	0.0603 (14)	0.086 (2)	0.0900 (19)	0.0391 (14)	0.0192 (13)	−0.0045 (15)
N5B	0.0649 (15)	0.101 (2)	0.093 (2)	0.0487 (16)	0.0111 (14)	−0.0144 (17)
C1A	0.0699 (17)	0.079 (2)	0.0734 (18)	0.0420 (16)	0.0253 (15)	0.0072 (15)
C1B	0.0694 (17)	0.0711 (19)	0.0819 (19)	0.0423 (15)	0.0244 (15)	0.0113 (15)
C2A	0.094 (2)	0.094 (3)	0.077 (2)	0.051 (2)	0.0259 (18)	0.0142 (19)
C2B	0.0638 (16)	0.0682 (19)	0.082 (2)	0.0341 (15)	0.0190 (15)	0.0032 (15)
C3A	0.101 (3)	0.129 (4)	0.078 (2)	0.060 (3)	0.012 (2)	0.003 (3)
C3B	0.074 (2)	0.088 (3)	0.096 (3)	0.0383 (19)	0.0106 (18)	−0.007 (2)
C4B	0.097 (3)	0.076 (3)	0.136 (4)	0.032 (2)	0.022 (3)	−0.013 (3)
C4A	0.096 (3)	0.118 (4)	0.099 (3)	0.043 (3)	0.015 (2)	−0.021 (3)
C5A	0.111 (3)	0.087 (3)	0.120 (4)	0.044 (3)	0.033 (3)	−0.007 (3)
C5B	0.128 (4)	0.070 (3)	0.137 (4)	0.042 (3)	0.038 (3)	0.012 (3)
C6A	0.095 (2)	0.084 (3)	0.092 (2)	0.053 (2)	0.032 (2)	0.011 (2)
C6B	0.100 (3)	0.079 (2)	0.105 (3)	0.051 (2)	0.031 (2)	0.020 (2)
C7A	0.0631 (16)	0.078 (2)	0.0724 (18)	0.0400 (15)	0.0226 (14)	0.0133 (15)
C7B	0.0661 (16)	0.0685 (18)	0.0694 (17)	0.0403 (14)	0.0204 (13)	0.0123 (14)
C8A	0.0619 (16)	0.082 (2)	0.0755 (19)	0.0392 (16)	0.0246 (14)	0.0108 (16)
C8B	0.0625 (16)	0.080 (2)	0.0695 (17)	0.0431 (15)	0.0178 (13)	0.0139 (15)
C9A	0.0610 (16)	0.075 (2)	0.0786 (19)	0.0387 (15)	0.0246 (14)	0.0126 (16)
C9B	0.0632 (16)	0.082 (2)	0.0690 (17)	0.0447 (16)	0.0199 (14)	0.0125 (15)
C10A	0.173 (6)	0.193 (7)	0.104 (4)	0.135 (6)	0.006 (4)	−0.015 (4)
C10B	0.137 (6)	0.156 (8)	0.330 (15)	−0.012 (6)	0.089 (8)	−0.056 (8)
C11A	0.307 (15)	0.279 (16)	0.108 (5)	0.195 (14)	0.035 (7)	0.025 (7)
C11B	0.184 (11)	0.328 (19)	0.302 (17)	0.020 (13)	0.063 (12)	0.163 (16)
C12A	0.267 (19)	0.219 (15)	0.192 (13)	0.117 (14)	−0.016 (12)	0.066 (12)
C12C	0.14 (3)	0.056 (13)	0.11 (2)	0.042 (16)	0.024 (19)	0.000 (13)
C12B	0.297 (18)	0.179 (12)	0.55 (3)	−0.059 (12)	0.17 (2)	0.069 (15)
C13A	0.317 (19)	0.41 (3)	0.241 (15)	0.185 (19)	0.110 (14)	0.118 (17)
C13B	0.182 (10)	0.39 (2)	0.39 (2)	0.156 (14)	0.118 (13)	0.234 (19)

Geometric parameters (Å, º) top

Cl1A—C2A	1.714 (5)	C4B—C5B	1.380 (7)
Cl1B—C2B	1.722 (4)	C4B—H4B	0.9300
Cl2A—C3A	1.712 (5)	C4A—C5A	1.356 (8)
Cl2B—C3B	1.732 (5)	C4A—H4A	0.9300
O1A—C10A	1.416 (7)	C5A—C6A	1.387 (6)
O1A—H1A	0.8200	C5A—H5A	0.9300
O1B—C10B	1.423 (9)	C5B—C6B	1.377 (7)
O1B—H1B	0.8200	C5B—H5B	0.9300
N1A—C7A	1.313 (4)	C6A—H6A	0.9300
N1A—N2A	1.338 (4)	C6B—H6B	0.9300
N1B—C7B	1.314 (4)	C7A—C9A	1.438 (4)
N1B—N2B	1.338 (4)	C7B—C9B	1.439 (4)
N2A—C8A	1.344 (4)	C10A—C11A	1.495 (13)
N2B—C8B	1.352 (4)	C10A—H10A	0.9700
N3A—C8A	1.321 (5)	C10A—H10B	0.9700
N3A—H3A1	0.8600	C10B—C12B	1.209 (16)
N3A—H3A2	0.8600	C10B—H10C	0.9700
N3B—C8B	1.331 (4)	C10B—H10D	0.9700
N3B—H3B1	0.8600	C11A—C12C	1.32 (3)
N3B—H3B2	0.8600	C11A—C12A	1.536 (19)
N4A—C9A	1.310 (4)	C11A—H11A	0.9700
N4A—C8A	1.351 (4)	C11A—H11B	0.9700
N4B—C9B	1.328 (4)	C11B—C12B	1.237 (15)
N4B—C8B	1.341 (4)	C11B—C13B	1.287 (13)
N5A—C9A	1.339 (4)	C11B—H11C	0.9700
N5A—H5A1	0.8600	C11B—H11D	0.9700
N5A—H5A2	0.8600	C12A—C13A	1.436 (18)
N5B—C9B	1.324 (4)	C12A—H12A	0.9700
N5B—H5B1	0.8600	C12A—H12B	0.9700
N5B—H5B2	0.8600	C12C—C13A	1.44 (4)
C1A—C6A	1.388 (5)	C12C—H12C	0.9700
C1A—C2A	1.404 (5)	C12C—H12D	0.9700
C1A—C7A	1.477 (5)	C12B—H12E	0.9700
C1B—C6B	1.399 (5)	C12B—H12F	0.9700
C1B—C2B	1.402 (5)	C13A—H13A	0.9600
C1B—C7B	1.474 (5)	C13A—H13B	0.9600
C2A—C3A	1.389 (6)	C13A—H13C	0.9600
C2B—C3B	1.388 (5)	C13B—H13D	0.9600
C3A—C4A	1.381 (8)	C13B—H13E	0.9600
C3B—C4B	1.392 (7)	C13B—H13F	0.9600

C10A—O1A—H1A	109.5	N3B—C8B—N4B	118.5 (3)
C10B—O1B—H1B	109.5	N3B—C8B—N2B	116.1 (3)
C7A—N1A—N2A	122.1 (3)	N4B—C8B—N2B	125.3 (3)
C7B—N1B—N2B	121.4 (3)	N4A—C9A—N5A	119.9 (3)
N1A—N2A—C8A	116.9 (3)	N4A—C9A—C7A	120.1 (3)
N1B—N2B—C8B	117.2 (2)	N5A—C9A—C7A	120.1 (3)
C8A—N3A—H3A1	120.0	N5B—C9B—N4B	119.0 (3)
C8A—N3A—H3A2	120.0	N5B—C9B—C7B	121.4 (3)
H3A1—N3A—H3A2	120.0	N4B—C9B—C7B	119.5 (3)
C8B—N3B—H3B1	120.0	O1A—C10A—C11A	115.3 (7)
C8B—N3B—H3B2	120.0	O1A—C10A—H10A	108.5
H3B1—N3B—H3B2	120.0	C11A—C10A—H10A	108.5
C9A—N4A—C8A	117.0 (3)	O1A—C10A—H10B	108.5
C9B—N4B—C8B	116.8 (3)	C11A—C10A—H10B	108.5
C9A—N5A—H5A1	120.0	H10A—C10A—H10B	107.5
C9A—N5A—H5A2	120.0	C12B—C10B—O1B	125.1 (12)
H5A1—N5A—H5A2	120.0	C12B—C10B—H10C	106.1
C9B—N5B—H5B1	120.0	O1B—C10B—H10C	106.1
C9B—N5B—H5B2	120.0	C12B—C10B—H10D	106.1
H5B1—N5B—H5B2	120.0	O1B—C10B—H10D	106.1
C6A—C1A—C2A	118.5 (4)	H10C—C10B—H10D	106.3
C6A—C1A—C7A	120.1 (3)	C12C—C11A—C10A	137 (2)
C2A—C1A—C7A	121.4 (3)	C10A—C11A—C12A	106.7 (11)
C6B—C1B—C2B	118.1 (3)	C10A—C11A—H11A	110.4
C6B—C1B—C7B	118.5 (3)	C12A—C11A—H11A	110.4
C2B—C1B—C7B	123.3 (3)	C10A—C11A—H11B	110.4
C3A—C2A—C1A	120.0 (4)	C12A—C11A—H11B	110.4
C3A—C2A—Cl1A	120.8 (4)	H11A—C11A—H11B	108.6
C1A—C2A—Cl1A	119.2 (3)	C12B—C11B—C13B	130 (2)
C3B—C2B—C1B	120.4 (4)	C12B—C11B—H11C	104.8
C3B—C2B—Cl1B	118.9 (3)	C13B—C11B—H11C	104.8
C1B—C2B—Cl1B	120.7 (3)	C12B—C11B—H11D	104.8
C4A—C3A—C2A	120.1 (5)	C13B—C11B—H11D	104.8
C4A—C3A—Cl2A	119.0 (4)	H11C—C11B—H11D	105.8
C2A—C3A—Cl2A	120.9 (5)	C13A—C12A—C11A	107.4 (13)
C2B—C3B—C4B	120.0 (4)	C13A—C12A—H12A	110.2
C2B—C3B—Cl2B	120.7 (4)	C11A—C12A—H12A	110.2
C4B—C3B—Cl2B	119.4 (3)	C13A—C12A—H12B	110.2
C5B—C4B—C3B	120.3 (4)	C11A—C12A—H12B	110.2
C5B—C4B—H4B	119.9	H12A—C12A—H12B	108.5
C3B—C4B—H4B	119.9	C11A—C12C—C13A	121 (2)
C5A—C4A—C3A	120.2 (5)	C11A—C12C—H12C	107.2
C5A—C4A—H4A	119.9	C13A—C12C—H12C	107.2
C3A—C4A—H4A	119.9	C11A—C12C—H12D	107.2
C4A—C5A—C6A	120.8 (5)	C13A—C12C—H12D	107.2
C4A—C5A—H5A	119.6	H12C—C12C—H12D	106.8
C6A—C5A—H5A	119.6	C10B—C12B—C11B	146 (2)
C6B—C5B—C4B	119.6 (5)	C10B—C12B—H12C	100.5
C6B—C5B—H5B	120.2	C11B—C12B—H12C	100.5
C4B—C5B—H5B	120.2	C10B—C12B—H12D	100.5
C5A—C6A—C1A	120.4 (4)	C11B—C12B—H12D	100.5
C5A—C6A—H6A	119.8	H12C—C12B—H12D	104.3
C1A—C6A—H6A	119.8	C12A—C13A—H13A	109.5
C5B—C6B—C1B	121.6 (4)	C12A—C13A—H13B	109.5
C5B—C6B—H6B	119.2	H13A—C13A—H13B	109.5
C1B—C6B—H6B	119.2	C12A—C13A—H13C	109.5
N1A—C7A—C9A	118.7 (3)	H13A—C13A—H13C	109.5
N1A—C7A—C1A	117.8 (3)	H13B—C13A—H13C	109.5
C9A—C7A—C1A	123.4 (3)	C11B—C13B—H13D	109.5
N1B—C7B—C9B	119.6 (3)	C11B—C13B—H13E	109.5
N1B—C7B—C1B	116.5 (3)	H13D—C13B—H13E	109.5
C9B—C7B—C1B	123.6 (3)	C11B—C13B—H13F	109.5
N3A—C8A—N2A	116.3 (3)	H13D—C13B—H13F	109.5
N3A—C8A—N4A	118.7 (3)	H13E—C13B—H13F	109.5
N2A—C8A—N4A	125.1 (3)

C7A—N1A—N2A—C8A	−0.4 (5)	C6A—C1A—C7A—C9A	106.8 (4)
C7B—N1B—N2B—C8B	2.3 (5)	C2A—C1A—C7A—C9A	−74.1 (5)
C6A—C1A—C2A—C3A	−0.7 (5)	N2B—N1B—C7B—C9B	−2.7 (5)
C7A—C1A—C2A—C3A	−179.8 (3)	N2B—N1B—C7B—C1B	−176.6 (3)
C6A—C1A—C2A—Cl1A	178.0 (3)	C6B—C1B—C7B—N1B	60.9 (4)
C7A—C1A—C2A—Cl1A	−1.1 (5)	C2B—C1B—C7B—N1B	−117.0 (4)
C6B—C1B—C2B—C3B	0.3 (5)	C6B—C1B—C7B—C9B	−112.7 (4)
C7B—C1B—C2B—C3B	178.1 (3)	C2B—C1B—C7B—C9B	69.5 (5)
C6B—C1B—C2B—Cl1B	−179.0 (3)	N1A—N2A—C8A—N3A	177.3 (3)
C7B—C1B—C2B—Cl1B	−1.2 (4)	N1A—N2A—C8A—N4A	−1.7 (6)
C1A—C2A—C3A—C4A	0.9 (7)	C9A—N4A—C8A—N3A	−178.4 (3)
Cl1A—C2A—C3A—C4A	−177.8 (4)	C9A—N4A—C8A—N2A	0.6 (6)
C1A—C2A—C3A—Cl2A	−179.0 (3)	C9B—N4B—C8B—N3B	179.3 (3)
Cl1A—C2A—C3A—Cl2A	2.3 (6)	C9B—N4B—C8B—N2B	−2.3 (5)
C1B—C2B—C3B—C4B	0.0 (6)	N1B—N2B—C8B—N3B	178.7 (3)
Cl1B—C2B—C3B—C4B	179.3 (3)	N1B—N2B—C8B—N4B	0.3 (5)
C1B—C2B—C3B—Cl2B	−179.8 (3)	C8A—N4A—C9A—N5A	−177.4 (3)
Cl1B—C2B—C3B—Cl2B	−0.5 (4)	C8A—N4A—C9A—C7A	2.5 (5)
C2B—C3B—C4B—C5B	0.1 (7)	N1A—C7A—C9A—N4A	−4.5 (5)
Cl2B—C3B—C4B—C5B	179.8 (4)	C1A—C7A—C9A—N4A	178.6 (3)
C2A—C3A—C4A—C5A	−0.7 (8)	N1A—C7A—C9A—N5A	175.4 (3)
Cl2A—C3A—C4A—C5A	179.2 (4)	C1A—C7A—C9A—N5A	−1.5 (5)
C3A—C4A—C5A—C6A	0.2 (8)	C8B—N4B—C9B—N5B	178.6 (3)
C3B—C4B—C5B—C6B	−0.4 (8)	C8B—N4B—C9B—C7B	1.8 (5)
C4A—C5A—C6A—C1A	0.0 (7)	N1B—C7B—C9B—N5B	−176.1 (3)
C2A—C1A—C6A—C5A	0.3 (5)	C1B—C7B—C9B—N5B	−2.7 (5)
C7A—C1A—C6A—C5A	179.4 (3)	N1B—C7B—C9B—N4B	0.6 (5)
C4B—C5B—C6B—C1B	0.6 (8)	C1B—C7B—C9B—N4B	174.0 (3)
C2B—C1B—C6B—C5B	−0.6 (6)	O1A—C10A—C11A—C12C	−27 (3)
C7B—C1B—C6B—C5B	−178.5 (4)	O1A—C10A—C11A—C12A	−71.2 (11)
N2A—N1A—C7A—C9A	3.3 (5)	C10A—C11A—C12A—C13A	−175.9 (13)
N2A—N1A—C7A—C1A	−179.5 (3)	C10A—C11A—C12C—C13A	−117 (3)
C6A—C1A—C7A—N1A	−70.2 (4)	O1B—C10B—C12B—C11B	170 (3)
C2A—C1A—C7A—N1A	108.9 (4)	C13B—C11B—C12B—C10B	−153 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1A—H1A···N1A	0.82	1.98	2.797 (4)	178
O1B—H1B···O1Aⁱ	0.82	1.94	2.708 (6)	155
N3A—H3A2···O1B	0.86	2.29	3.135 (4)	167
N3A—H3A1···N2B	0.86	2.19	3.042 (4)	173
N3B—H3B2···N2A	0.86	2.13	2.983 (4)	174
N5A—H5A1···N4Bⁱⁱ	0.86	2.20	3.064 (4)	177
N5B—H5B2···O1Bⁱⁱⁱ	0.86	2.09	2.809 (4)	141
N5B—H5B1···N4Aⁱⁱⁱ	0.86	2.15	2.999 (4)	169

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x+1, y, z; (iii) x−1, y, z.

(LAM_tert-butanol_solvate) top

Crystal data top

C₁₇H₂₇Cl₂N₅O₂	Z = 2
M_r = 404.33	F(000) = 428
Triclinic, P1	D_x = 1.207 Mg m⁻³
a = 7.437 (3) Å	Cu Kα radiation, λ = 1.54184 Å
b = 10.302 (3) Å	Cell parameters from 2105 reflections
c = 14.811 (3) Å	θ = 2.9–72.3°
α = 79.70 (2)°	µ = 2.79 mm⁻¹
β = 85.34 (3)°	T = 296 K
γ = 88.71 (3)°	Needle, colourless
V = 1112.8 (6) Å³	0.60 × 0.50 × 0.05 mm

Data collection top

Xcalibur, Sapphire3, Gemini diffractometer	R_int = 0.198
Radiation source: Enhance (Cu) X-ray Source	θ_max = 70.0°, θ_min = 3.0°
ω scans	h = −8→9
9317 measured reflections	k = −12→12
4182 independent reflections	l = −17→18
878 reflections with I > 2σ(I)

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.125	w = 1/[σ²(F_o²) + (0.0986P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.353	(Δ/σ)_max < 0.001
S = 0.83	Δρ_max = 0.47 e Å⁻³
4182 reflections	Δρ_min = −0.28 e Å⁻³
242 parameters	Extinction correction: SHELXL-2014/7 (Sheldrick 2014, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
2 restraints	Extinction coefficient: 0.0018 (8)

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	0.5741 (4)	0.3478 (3)	0.33282 (19)	0.1002 (11)
Cl2	0.8763 (5)	0.3606 (3)	0.4662 (2)	0.1274 (14)
O1A	0.8546 (10)	0.6684 (7)	0.1735 (5)	0.086 (2)
O2B	0.7140 (14)	0.8594 (7)	0.2657 (6)	0.117 (3)
N1	0.6685 (11)	0.1162 (7)	0.1467 (5)	0.076 (2)
N2	0.5559 (12)	0.0894 (8)	0.0853 (6)	0.089 (3)
N3	0.3619 (12)	0.1652 (8)	−0.0233 (6)	0.108 (4)
H3A	0.3070	0.2273	−0.0575	0.129*
H3B	0.3469	0.0843	−0.0283	0.129*
N4	0.4914 (10)	0.3225 (7)	0.0441 (5)	0.076 (2)
N5	0.6369 (10)	0.4686 (7)	0.1081 (5)	0.078 (2)
H5A	0.5835	0.5292	0.0719	0.093*
H5B	0.7091	0.4897	0.1456	0.093*
C1	0.8318 (14)	0.2508 (9)	0.2230 (7)	0.079 (3)
C2	0.7942 (12)	0.2977 (9)	0.3037 (7)	0.073 (3)
C3	0.9224 (16)	0.3031 (11)	0.3652 (7)	0.091 (3)
C4	1.0972 (16)	0.2586 (12)	0.3429 (8)	0.104 (4)
H4	1.1866	0.2625	0.3827	0.124*
C5	1.1380 (14)	0.2105 (12)	0.2653 (8)	0.104 (4)
H5	1.2541	0.1792	0.2532	0.125*
C6	1.0093 (14)	0.2068 (10)	0.2027 (8)	0.093 (3)
H6	1.0398	0.1757	0.1482	0.111*
C7	0.6954 (12)	0.2365 (9)	0.1590 (6)	0.068 (2)
C8	0.4707 (14)	0.1944 (10)	0.0379 (7)	0.082 (3)
C9	0.6076 (13)	0.3405 (10)	0.1062 (6)	0.072 (3)
C10A	1.0510 (15)	0.6828 (12)	0.1615 (8)	0.090 (3)
C10B	0.6289 (19)	0.8536 (13)	0.3551 (8)	0.102 (4)
C11A	1.1158 (17)	0.5811 (13)	0.1048 (10)	0.142 (5)
H11A	1.2448	0.5851	0.0942	0.214*
H11B	1.0815	0.4949	0.1371	0.214*
H11C	1.0626	0.5985	0.0469	0.214*
C11B	0.6264 (19)	0.7076 (12)	0.3941 (9)	0.138 (5)
H11D	0.5702	0.6937	0.4557	0.207*
H11E	0.5597	0.6624	0.3565	0.207*
H11F	0.7479	0.6741	0.3950	0.207*
C12A	1.1246 (16)	0.6508 (14)	0.2583 (9)	0.140 (6)
H12A	1.2534	0.6596	0.2523	0.211*
H12B	1.0724	0.7110	0.2958	0.211*
H12C	1.0933	0.5621	0.2866	0.211*
C12B	0.458 (2)	0.9188 (15)	0.3544 (10)	0.168 (7)
H12D	0.4053	0.9124	0.4164	0.253*
H12E	0.4734	1.0100	0.3271	0.253*
H12F	0.3800	0.8780	0.3193	0.253*
C13A	1.0920 (17)	0.8230 (12)	0.1161 (10)	0.136 (5)
H13A	1.2203	0.8349	0.1075	0.204*
H13B	1.0417	0.8412	0.0575	0.204*
H13C	1.0402	0.8822	0.1545	0.204*
C13B	0.763 (2)	0.9206 (13)	0.4105 (10)	0.168 (7)
H13D	0.7112	0.9192	0.4722	0.251*
H13E	0.8755	0.8729	0.4123	0.251*
H13F	0.7838	1.0103	0.3807	0.251*
H2BO	0.72 (2)	0.936 (6)	0.238 (10)	0.201*
H1AO	0.806 (19)	0.728 (11)	0.197 (10)	0.201*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.095 (2)	0.123 (3)	0.0884 (18)	0.0047 (17)	−0.0194 (14)	−0.0290 (17)
Cl2	0.147 (3)	0.148 (3)	0.098 (2)	−0.009 (2)	−0.046 (2)	−0.035 (2)
O1A	0.086 (5)	0.089 (5)	0.092 (5)	0.009 (4)	−0.018 (4)	−0.032 (4)
O2B	0.173 (8)	0.075 (5)	0.097 (6)	0.043 (6)	−0.010 (6)	−0.004 (5)
N1	0.102 (6)	0.054 (5)	0.073 (5)	0.009 (4)	−0.019 (4)	−0.006 (4)
N2	0.107 (7)	0.079 (6)	0.090 (6)	0.011 (5)	−0.047 (5)	−0.025 (5)
N3	0.148 (8)	0.062 (6)	0.124 (8)	0.010 (5)	−0.081 (7)	−0.017 (5)
N4	0.084 (6)	0.064 (5)	0.087 (5)	0.009 (4)	−0.037 (4)	−0.019 (4)
N5	0.094 (6)	0.063 (5)	0.081 (5)	0.015 (4)	−0.032 (4)	−0.015 (4)
C1	0.086 (7)	0.062 (6)	0.094 (7)	0.007 (5)	−0.032 (6)	−0.020 (5)
C2	0.069 (6)	0.067 (6)	0.086 (6)	0.002 (5)	−0.028 (5)	−0.014 (5)
C3	0.107 (9)	0.086 (8)	0.080 (7)	−0.001 (7)	−0.035 (6)	−0.006 (6)
C4	0.089 (8)	0.120 (10)	0.104 (9)	−0.004 (7)	−0.036 (7)	−0.012 (8)
C5	0.068 (7)	0.147 (11)	0.096 (8)	0.020 (7)	−0.031 (6)	−0.011 (8)
C6	0.080 (7)	0.098 (8)	0.102 (8)	0.035 (6)	−0.032 (6)	−0.017 (7)
C7	0.082 (7)	0.046 (5)	0.074 (6)	0.008 (5)	−0.024 (5)	0.001 (4)
C8	0.097 (8)	0.067 (7)	0.091 (7)	0.017 (6)	−0.043 (6)	−0.027 (6)
C9	0.078 (6)	0.063 (7)	0.079 (6)	0.014 (5)	−0.017 (5)	−0.022 (5)
C10A	0.083 (8)	0.090 (9)	0.104 (8)	0.009 (7)	−0.024 (6)	−0.028 (7)
C10B	0.133 (11)	0.086 (9)	0.078 (7)	0.028 (8)	0.005 (7)	0.001 (6)
C11A	0.101 (10)	0.132 (12)	0.203 (16)	−0.009 (9)	0.009 (10)	−0.061 (11)
C11B	0.165 (14)	0.109 (11)	0.132 (12)	0.010 (9)	0.027 (10)	−0.016 (9)
C12A	0.098 (9)	0.193 (15)	0.123 (11)	−0.005 (9)	−0.051 (8)	0.014 (10)
C12B	0.175 (16)	0.165 (15)	0.151 (15)	0.072 (13)	−0.012 (12)	0.001 (12)
C13A	0.121 (11)	0.094 (10)	0.188 (15)	−0.021 (8)	−0.018 (10)	−0.011 (9)
C13B	0.24 (2)	0.125 (13)	0.149 (14)	−0.021 (12)	−0.047 (14)	−0.028 (10)

Geometric parameters (Å, º) top

Cl1—C2	1.748 (10)	C6—H6	0.9300
Cl2—C3	1.712 (11)	C7—C9	1.392 (11)
O1A—C10A	1.464 (13)	C10A—C11A	1.504 (15)
O1A—H1AO	0.82 (2)	C10A—C13A	1.507 (14)
O2B—C10B	1.412 (14)	C10A—C12A	1.554 (13)
O2B—H2BO	0.82 (2)	C10B—C12B	1.424 (16)
N1—C7	1.306 (10)	C10B—C11B	1.511 (15)
N1—N2	1.353 (9)	C10B—C13B	1.585 (17)
N2—C8	1.355 (10)	C11A—H11A	0.9600
N3—C8	1.340 (10)	C11A—H11B	0.9600
N3—H3A	0.8600	C11A—H11C	0.9600
N3—H3B	0.8600	C11B—H11D	0.9600
N4—C9	1.351 (10)	C11B—H11E	0.9600
N4—C8	1.352 (11)	C11B—H11F	0.9600
N5—C9	1.348 (10)	C12A—H12A	0.9600
N5—H5A	0.8600	C12A—H12B	0.9600
N5—H5B	0.8600	C12A—H12C	0.9600
C1—C2	1.375 (13)	C12B—H12D	0.9600
C1—C6	1.413 (13)	C12B—H12E	0.9600
C1—C7	1.469 (11)	C12B—H12F	0.9600
C2—C3	1.380 (11)	C13A—H13A	0.9600
C3—C4	1.402 (15)	C13A—H13B	0.9600
C4—C5	1.340 (15)	C13A—H13C	0.9600
C4—H4	0.9300	C13B—H13D	0.9600
C5—C6	1.391 (12)	C13B—H13E	0.9600
C5—H5	0.9300	C13B—H13F	0.9600

C10A—O1A—H1AO	111 (10)	C13A—C10A—C12A	111.1 (10)
C10B—O2B—H2BO	111 (10)	O2B—C10B—C12B	112.4 (11)
C7—N1—N2	122.1 (8)	O2B—C10B—C11B	103.4 (10)
N1—N2—C8	116.1 (8)	C12B—C10B—C11B	115.8 (13)
C8—N3—H3A	120.0	O2B—C10B—C13B	106.1 (12)
C8—N3—H3B	120.0	C12B—C10B—C13B	110.9 (13)
H3A—N3—H3B	120.0	C11B—C10B—C13B	107.5 (10)
C9—N4—C8	113.4 (8)	C10A—C11A—H11A	109.5
C9—N5—H5A	120.0	C10A—C11A—H11B	109.5
C9—N5—H5B	120.0	H11A—C11A—H11B	109.5
H5A—N5—H5B	120.0	C10A—C11A—H11C	109.5
C2—C1—C6	118.2 (9)	H11A—C11A—H11C	109.5
C2—C1—C7	123.7 (9)	H11B—C11A—H11C	109.5
C6—C1—C7	118.0 (9)	C10B—C11B—H11D	109.5
C1—C2—C3	122.6 (10)	C10B—C11B—H11E	109.5
C1—C2—Cl1	119.4 (7)	H11D—C11B—H11E	109.5
C3—C2—Cl1	118.0 (9)	C10B—C11B—H11F	109.5
C2—C3—C4	117.6 (11)	H11D—C11B—H11F	109.5
C2—C3—Cl2	122.9 (10)	H11E—C11B—H11F	109.5
C4—C3—Cl2	119.5 (9)	C10A—C12A—H12A	109.5
C5—C4—C3	121.4 (10)	C10A—C12A—H12B	109.5
C5—C4—H4	119.3	H12A—C12A—H12B	109.5
C3—C4—H4	119.3	C10A—C12A—H12C	109.5
C4—C5—C6	121.0 (11)	H12A—C12A—H12C	109.5
C4—C5—H5	119.5	H12B—C12A—H12C	109.5
C6—C5—H5	119.5	C10B—C12B—H12D	109.5
C5—C6—C1	119.2 (11)	C10B—C12B—H12E	109.5
C5—C6—H6	120.4	H12D—C12B—H12E	109.5
C1—C6—H6	120.4	C10B—C12B—H12F	109.5
N1—C7—C9	118.9 (8)	H12D—C12B—H12F	109.5
N1—C7—C1	115.7 (8)	H12E—C12B—H12F	109.5
C9—C7—C1	125.1 (8)	C10A—C13A—H13A	109.5
N3—C8—N4	118.6 (9)	C10A—C13A—H13B	109.5
N3—C8—N2	114.8 (9)	H13A—C13A—H13B	109.5
N4—C8—N2	126.5 (8)	C10A—C13A—H13C	109.5
N5—C9—N4	113.3 (8)	H13A—C13A—H13C	109.5
N5—C9—C7	123.7 (8)	H13B—C13A—H13C	109.5
N4—C9—C7	122.9 (9)	C10B—C13B—H13D	109.5
O1A—C10A—C11A	105.0 (9)	C10B—C13B—H13E	109.5
O1A—C10A—C13A	107.9 (9)	H13D—C13B—H13E	109.5
C11A—C10A—C13A	114.2 (12)	C10B—C13B—H13F	109.5
O1A—C10A—C12A	107.8 (10)	H13D—C13B—H13F	109.5
C11A—C10A—C12A	110.3 (11)	H13E—C13B—H13F	109.5

C7—N1—N2—C8	−0.8 (15)	N2—N1—C7—C1	−175.5 (9)
C6—C1—C2—C3	−0.1 (16)	C2—C1—C7—N1	−117.4 (11)
C7—C1—C2—C3	176.1 (9)	C6—C1—C7—N1	58.8 (14)
C6—C1—C2—Cl1	−177.9 (7)	C2—C1—C7—C9	68.5 (15)
C7—C1—C2—Cl1	−1.6 (14)	C6—C1—C7—C9	−115.3 (11)
C1—C2—C3—C4	0.1 (16)	C9—N4—C8—N3	−178.4 (10)
Cl1—C2—C3—C4	177.9 (8)	C9—N4—C8—N2	−1.4 (16)
C1—C2—C3—Cl2	−179.7 (8)	N1—N2—C8—N3	179.2 (10)
Cl1—C2—C3—Cl2	−1.9 (13)	N1—N2—C8—N4	2.1 (17)
C2—C3—C4—C5	−1.0 (19)	C8—N4—C9—N5	176.0 (9)
Cl2—C3—C4—C5	178.8 (10)	C8—N4—C9—C7	−0.6 (15)
C3—C4—C5—C6	2 (2)	N1—C7—C9—N5	−174.4 (10)
C4—C5—C6—C1	−1.9 (18)	C1—C7—C9—N5	−0.5 (16)
C2—C1—C6—C5	1.0 (16)	N1—C7—C9—N4	1.8 (16)
C7—C1—C6—C5	−175.5 (10)	C1—C7—C9—N4	175.7 (10)
N2—N1—C7—C9	−1.0 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1A—H1AO···O2B	0.82 (2)	1.91 (3)	2.733 (11)	172 (15)
N3—H3B···N2ⁱ	0.86	2.20	2.965 (12)	149
N3—H3A···O1Aⁱⁱ	0.86	2.27	3.094 (10)	160
N5—H5A···N4ⁱⁱ	0.86	2.19	3.025 (10)	165
N5—H5B···O1A	0.86	2.27	2.986 (10)	140
O2B—H2BO···N1ⁱⁱⁱ	0.82 (2)	2.15 (6)	2.935 (10)	160 (15)
N3—H3A···O1Aⁱⁱ	0.86	2.27	3.094 (10)	160
N3—H3B···N2ⁱ	0.86	2.20	2.965 (12)	149
N5—H5A···N4ⁱⁱ	0.86	2.19	3.025 (10)	165
N5—H5B···O1A	0.86	2.27	2.986 (10)	140
O1A—H1AO···O2B	0.82 (2)	1.91 (3)	2.733 (11)	172 (15)

Symmetry codes: (i) −x+1, −y, −z; (ii) −x+1, −y+1, −z; (iii) x, y+1, z.

(LAM_n-pentanol_solvate) top

Crystal data top

C₉H₇Cl₂N₅·C₅H₁₂O·H₂O	Z = 2
M_r = 362.26	F(000) = 380
Triclinic, P1	D_x = 1.323 Mg m⁻³
a = 7.6284 (8) Å	Cu Kα radiation, λ = 1.54184 Å
b = 8.5181 (9) Å	Cell parameters from 2686 reflections
c = 14.5190 (13) Å	θ = 3.2–72.8°
α = 84.043 (8)°	µ = 3.35 mm⁻¹
β = 75.989 (8)°	T = 296 K
γ = 85.943 (9)°	Prism, colourless
V = 909.41 (16) Å³	0.55 × 0.55 × 0.15 mm

Data collection top

Xcalibur, Sapphire3, Gemini diffractometer	2735 reflections with I > 2σ(I)
Radiation source: Enhance (Cu) X-ray Source	R_int = 0.035
ω scans	θ_max = 70.0°, θ_min = 3.2°
Absorption correction: multi-scan CrysAlisPro, Agilent Technologies, Version 1.171.36.21. Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −9→8
T_min = 0.305, T_max = 1.000	k = −10→10
9619 measured reflections	l = −17→17
3448 independent reflections

Refinement top

Refinement on F²	55 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.062	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.204	w = 1/[σ²(F_o²) + (0.116P)² + 0.1605P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
3448 reflections	Δρ_max = 0.31 e Å⁻³
238 parameters	Δρ_min = −0.31 e Å⁻³

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cl1	0.27370 (10)	0.13131 (15)	0.14817 (7)	0.1069 (4)
Cl2	0.01605 (15)	0.23352 (17)	0.01237 (6)	0.1211 (5)
O1	0.2661 (3)	0.4404 (2)	0.48819 (16)	0.0716 (5)
H1O	0.191 (4)	0.449 (5)	0.5388 (17)	0.107*
H2O	0.251 (6)	0.530 (2)	0.463 (3)	0.107*
O2	0.9522 (3)	0.5374 (3)	0.32149 (18)	0.0841 (6)
H1O2	0.997 (6)	0.612 (4)	0.336 (3)	0.126*
N1	0.1284 (3)	−0.1878 (2)	0.35341 (15)	0.0581 (5)
N2	0.2387 (3)	−0.2494 (2)	0.40928 (15)	0.0597 (5)
N3	0.4362 (3)	−0.2087 (2)	0.49918 (18)	0.0682 (6)
H1N3	0.485 (4)	−0.3039 (18)	0.501 (2)	0.082*
H2N3	0.510 (4)	−0.151 (4)	0.518 (2)	0.082*
N4	0.2907 (3)	0.0107 (2)	0.44159 (14)	0.0529 (5)
N5	0.1348 (4)	0.2235 (2)	0.38520 (19)	0.0702 (6)
H1N5	0.064 (4)	0.267 (4)	0.351 (2)	0.084*
H2N5	0.190 (4)	0.285 (3)	0.412 (2)	0.084*
C1	−0.0216 (3)	0.0203 (3)	0.27542 (17)	0.0541 (5)
C2	0.0460 (3)	0.0957 (3)	0.18461 (19)	0.0636 (6)
C3	−0.0665 (4)	0.1397 (4)	0.1240 (2)	0.0727 (7)
C4	−0.2471 (4)	0.1087 (5)	0.1523 (2)	0.0843 (9)
H4	−0.3231	0.1383	0.1115	0.101*
C5	−0.3146 (4)	0.0344 (5)	0.2406 (2)	0.0877 (10)
H5	−0.4365	0.0127	0.2593	0.105*
C6	−0.2042 (4)	−0.0085 (4)	0.3018 (2)	0.0713 (7)
H6	−0.2528	−0.0577	0.3620	0.086*
C7	0.0987 (3)	−0.0359 (3)	0.34013 (17)	0.0521 (5)
C8	0.3188 (3)	−0.1473 (3)	0.44805 (17)	0.0526 (5)
C9	0.1762 (3)	0.0687 (3)	0.38919 (17)	0.0522 (5)
C10	0.8711 (6)	0.5668 (5)	0.2422 (3)	0.1071 (12)
H10A	0.9444	0.5141	0.1888	0.128*
H10B	0.8678	0.6793	0.2232	0.128*
C11	0.6899 (7)	0.5117 (8)	0.2642 (4)	0.1371 (19)
H11A	0.6162	0.5682	0.3158	0.165*
H11B	0.6934	0.4005	0.2867	0.165*
C12	0.6011 (9)	0.5326 (9)	0.1811 (4)	0.175 (3)
H12A	0.6951	0.5177	0.1239	0.209*	0.61
H12B	0.5198	0.4471	0.1891	0.209*	0.61
H12C	0.6516	0.6255	0.1420	0.209*	0.39
H12D	0.6450	0.4434	0.1441	0.209*	0.39
C13A	0.5030 (12)	0.6739 (11)	0.1637 (6)	0.136 (3)	0.61
H13A	0.5860	0.7545	0.1317	0.163*	0.61
H13B	0.4349	0.7105	0.2237	0.163*	0.61
C13B	0.4112 (13)	0.548 (2)	0.1885 (8)	0.140 (5)	0.39
H13C	0.3523	0.5988	0.2455	0.168*	0.39
H13D	0.3634	0.4442	0.1937	0.168*	0.39
C14	0.3704 (10)	0.6473 (11)	0.1002 (5)	0.194 (3)
H14A	0.3043	0.7447	0.0888	0.291*	0.61
H14B	0.4382	0.6125	0.0405	0.291*	0.61
H14C	0.2873	0.5686	0.1324	0.291*	0.61
H14D	0.2420	0.6567	0.1063	0.291*	0.39
H14E	0.4163	0.7506	0.0957	0.291*	0.39
H14F	0.4274	0.5964	0.0439	0.291*	0.39

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0566 (5)	0.1677 (10)	0.0906 (6)	−0.0246 (5)	−0.0224 (4)	0.0400 (6)
Cl2	0.0991 (7)	0.1816 (12)	0.0766 (6)	−0.0128 (7)	−0.0324 (5)	0.0483 (6)
O1	0.0870 (14)	0.0428 (9)	0.0889 (13)	0.0058 (8)	−0.0341 (11)	0.0018 (8)
O2	0.0957 (16)	0.0699 (12)	0.0971 (15)	−0.0094 (11)	−0.0476 (13)	0.0075 (11)
N1	0.0634 (12)	0.0486 (10)	0.0667 (12)	−0.0006 (8)	−0.0276 (9)	0.0015 (8)
N2	0.0706 (13)	0.0414 (9)	0.0731 (12)	0.0015 (8)	−0.0331 (10)	0.0029 (8)
N3	0.0803 (15)	0.0430 (10)	0.0924 (16)	0.0086 (9)	−0.0486 (13)	0.0014 (10)
N4	0.0570 (11)	0.0410 (9)	0.0652 (11)	0.0036 (7)	−0.0270 (9)	0.0002 (8)
N5	0.0855 (16)	0.0444 (11)	0.0939 (16)	0.0124 (10)	−0.0516 (13)	−0.0048 (10)
C1	0.0520 (12)	0.0517 (12)	0.0610 (13)	0.0016 (9)	−0.0207 (10)	−0.0014 (9)
C2	0.0494 (13)	0.0737 (16)	0.0678 (14)	−0.0016 (11)	−0.0197 (11)	0.0056 (12)
C3	0.0688 (17)	0.0879 (19)	0.0624 (14)	0.0020 (14)	−0.0253 (12)	0.0091 (13)
C4	0.0612 (17)	0.119 (3)	0.0786 (18)	0.0079 (16)	−0.0355 (14)	0.0020 (17)
C5	0.0476 (15)	0.131 (3)	0.086 (2)	−0.0049 (16)	−0.0237 (14)	0.0018 (19)
C6	0.0566 (15)	0.0892 (19)	0.0664 (15)	−0.0017 (13)	−0.0166 (12)	0.0038 (13)
C7	0.0513 (12)	0.0457 (11)	0.0610 (12)	0.0013 (9)	−0.0198 (10)	0.0002 (9)
C8	0.0551 (12)	0.0430 (11)	0.0605 (12)	0.0010 (9)	−0.0196 (10)	0.0040 (9)
C9	0.0522 (12)	0.0438 (11)	0.0614 (12)	0.0028 (8)	−0.0198 (10)	0.0026 (9)
C10	0.122 (3)	0.107 (3)	0.105 (3)	−0.016 (2)	−0.056 (2)	0.008 (2)
C11	0.116 (4)	0.192 (5)	0.119 (4)	−0.016 (3)	−0.060 (3)	−0.003 (3)
C12	0.146 (5)	0.262 (8)	0.143 (5)	0.053 (5)	−0.091 (4)	−0.051 (5)
C13A	0.116 (6)	0.187 (9)	0.118 (6)	0.031 (6)	−0.054 (5)	−0.040 (6)
C13B	0.105 (8)	0.200 (13)	0.130 (9)	−0.024 (8)	−0.049 (7)	−0.024 (9)
C14	0.149 (5)	0.297 (10)	0.154 (5)	0.058 (6)	−0.089 (5)	−0.026 (6)

Geometric parameters (Å, º) top

Cl1—C2	1.728 (3)	C6—H6	0.9300
Cl2—C3	1.723 (3)	C7—C9	1.435 (3)
O1—H1O	0.823 (10)	C10—C11	1.441 (5)
O1—H2O	0.823 (10)	C10—H10A	0.9700
O2—C10	1.427 (4)	C10—H10B	0.9700
O2—H1O2	0.813 (10)	C11—C12	1.510 (5)
N1—C7	1.300 (3)	C11—H11A	0.9700
N1—N2	1.349 (3)	C11—H11B	0.9700
N2—C8	1.338 (3)	C12—C13A	1.405 (8)
N3—C8	1.342 (3)	C12—C13B	1.424 (8)
N3—H1N3	0.869 (10)	C12—H12A	0.9700
N3—H2N3	0.875 (10)	C12—H12B	0.9700
N4—C9	1.329 (3)	C12—H12C	0.9700
N4—C8	1.345 (3)	C12—H12D	0.9700
N5—C9	1.333 (3)	C13A—C14	1.565 (7)
N5—H1N5	0.864 (10)	C13A—H13A	0.9700
N5—H2N5	0.870 (10)	C13A—H13B	0.9700
C1—C6	1.385 (4)	C13B—C14	1.544 (9)
C1—C2	1.400 (4)	C13B—H13C	0.9700
C1—C7	1.489 (3)	C13B—H13D	0.9700
C2—C3	1.380 (4)	C14—H14A	0.9600
C3—C4	1.375 (4)	C14—H14B	0.9600
C4—C5	1.366 (5)	C14—H14C	0.9600
C4—H4	0.9300	C14—H14D	0.9600
C5—C6	1.373 (4)	C14—H14E	0.9600
C5—H5	0.9300	C14—H14F	0.9600

H1O—O1—H2O	97 (4)	H10A—C10—H10B	107.9
C10—O2—H1O2	116 (3)	C10—C11—C12	114.1 (5)
C7—N1—N2	121.04 (19)	C10—C11—H11A	108.7
C8—N2—N1	117.05 (18)	C12—C11—H11A	108.7
C8—N3—H1N3	128 (2)	C10—C11—H11B	108.7
C8—N3—H2N3	123 (2)	C12—C11—H11B	108.7
H1N3—N3—H2N3	105 (3)	H11A—C11—H11B	107.6
C9—N4—C8	115.91 (19)	C13A—C12—C11	120.1 (6)
C9—N5—H1N5	122 (2)	C13B—C12—C11	125.3 (7)
C9—N5—H2N5	120 (2)	C13A—C12—H12A	107.3
H1N5—N5—H2N5	118 (3)	C11—C12—H12A	107.3
C6—C1—C2	117.8 (2)	C13A—C12—H12B	107.3
C6—C1—C7	120.4 (2)	C11—C12—H12B	107.3
C2—C1—C7	121.7 (2)	H12A—C12—H12B	106.9
C3—C2—C1	120.7 (2)	C13B—C12—H12C	106.0
C3—C2—Cl1	120.0 (2)	C11—C12—H12C	106.0
C1—C2—Cl1	119.26 (19)	C13B—C12—H12D	106.0
C4—C3—C2	120.0 (3)	C11—C12—H12D	106.0
C4—C3—Cl2	119.1 (2)	H12C—C12—H12D	106.3
C2—C3—Cl2	120.9 (2)	C12—C13A—C14	110.3 (6)
C5—C4—C3	119.8 (3)	C12—C13A—H13A	109.6
C5—C4—H4	120.1	C14—C13A—H13A	109.6
C3—C4—H4	120.1	C12—C13A—H13B	109.6
C4—C5—C6	120.7 (3)	C14—C13A—H13B	109.6
C4—C5—H5	119.7	H13A—C13A—H13B	108.1
C6—C5—H5	119.7	C12—C13B—C14	110.5 (7)
C5—C6—C1	121.0 (3)	C12—C13B—H13C	109.5
C5—C6—H6	119.5	C14—C13B—H13C	109.5
C1—C6—H6	119.5	C12—C13B—H13D	109.5
N1—C7—C9	120.0 (2)	C14—C13B—H13D	109.5
N1—C7—C1	116.9 (2)	H13C—C13B—H13D	108.1
C9—C7—C1	123.13 (19)	C13A—C14—H14A	109.5
N2—C8—N3	116.85 (19)	C13A—C14—H14B	109.5
N2—C8—N4	126.0 (2)	H14A—C14—H14B	109.5
N3—C8—N4	117.1 (2)	C13A—C14—H14C	109.5
N4—C9—N5	118.4 (2)	H14A—C14—H14C	109.5
N4—C9—C7	119.71 (19)	H14B—C14—H14C	109.5
N5—C9—C7	121.9 (2)	C13B—C14—H14D	109.5
O2—C10—C11	111.9 (4)	C13B—C14—H14E	109.5
O2—C10—H10A	109.2	H14D—C14—H14E	109.5
C11—C10—H10A	109.2	C13B—C14—H14F	109.5
O2—C10—H10B	109.2	H14D—C14—H14F	109.5
C11—C10—H10B	109.2	H14E—C14—H14F	109.5

C7—N1—N2—C8	−1.6 (4)	C2—C1—C7—N1	−108.2 (3)
C6—C1—C2—C3	0.1 (4)	C6—C1—C7—C9	−109.7 (3)
C7—C1—C2—C3	176.7 (2)	C2—C1—C7—C9	73.8 (3)
C6—C1—C2—Cl1	−179.1 (2)	N1—N2—C8—N3	−176.4 (2)
C7—C1—C2—Cl1	−2.5 (3)	N1—N2—C8—N4	4.6 (4)
C1—C2—C3—C4	−0.4 (5)	C9—N4—C8—N2	−2.1 (4)
Cl1—C2—C3—C4	178.8 (3)	C9—N4—C8—N3	178.9 (2)
C1—C2—C3—Cl2	179.6 (2)	C8—N4—C9—N5	175.9 (2)
Cl1—C2—C3—Cl2	−1.2 (4)	C8—N4—C9—C7	−3.0 (3)
C2—C3—C4—C5	0.0 (5)	N1—C7—C9—N4	5.8 (4)
Cl2—C3—C4—C5	180.0 (3)	C1—C7—C9—N4	−176.2 (2)
C3—C4—C5—C6	0.6 (6)	N1—C7—C9—N5	−173.1 (3)
C4—C5—C6—C1	−0.9 (5)	C1—C7—C9—N5	4.9 (4)
C2—C1—C6—C5	0.5 (4)	O2—C10—C11—C12	−177.1 (5)
C7—C1—C6—C5	−176.1 (3)	C10—C11—C12—C13A	−88.6 (9)
N2—N1—C7—C9	−3.3 (4)	C10—C11—C12—C13B	−154.1 (10)
N2—N1—C7—C1	178.6 (2)	C11—C12—C13A—C14	−159.9 (6)
C6—C1—C7—N1	68.3 (3)	C11—C12—C13B—C14	151.2 (9)

(LAM_benzonitrile_solvate) top

Crystal data top

C₉H₇Cl₂N₅·2(C₇H₅N)	Z = 2
M_r = 462.34	F(000) = 476
Triclinic, P1	D_x = 1.330 Mg m⁻³
a = 10.3096 (8) Å	Cu Kα radiation, λ = 1.54184 Å
b = 10.6257 (6) Å	Cell parameters from 3971 reflections
c = 12.0489 (11) Å	θ = 3.9–67.2°
α = 74.280 (6)°	µ = 2.73 mm⁻¹
β = 75.318 (7)°	T = 296 K
γ = 67.161 (6)°	Prism, colourless
V = 1154.46 (17) Å³	0.55 × 0.35 × 0.25 mm

Data collection top

Goniometer Xcalibur, detector: Sapphire3 (Gemini Cu) diffractometer	3095 reflections with I > 2σ(I)
Radiation source: Enhance (Cu) X-ray Source	R_int = 0.031
ω scans	θ_max = 67.3°, θ_min = 3.9°
Absorption correction: multi-scan CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.33.34d. Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −12→12
T_min = 0.697, T_max = 1.000	k = −12→7
10040 measured reflections	l = −14→14
4117 independent reflections

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.043	w = 1/[σ²(F_o²) + (0.0821P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.120	(Δ/σ)_max < 0.001
S = 0.93	Δρ_max = 0.19 e Å⁻³
4117 reflections	Δρ_min = −0.20 e Å⁻³
302 parameters	Extinction correction: SHELXL-2014/7 (Sheldrick 2014, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
4 restraints	Extinction coefficient: 0.0055 (7)

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	0.14641 (5)	0.22313 (6)	0.36178 (4)	0.07545 (19)
Cl2	0.39049 (8)	0.19536 (7)	0.48741 (5)	0.0961 (2)
N1	0.23463 (15)	0.05239 (14)	0.09448 (13)	0.0564 (4)
N2	0.13168 (17)	0.06030 (14)	0.03966 (14)	0.0604 (4)
N3	−0.0689 (2)	0.19269 (16)	−0.04074 (18)	0.0764 (5)
H1N3	−0.1370 (19)	0.2705 (16)	−0.056 (2)	0.092*
H2N3	−0.077 (3)	0.1184 (17)	−0.049 (2)	0.092*
N4	0.03749 (15)	0.30734 (13)	0.02270 (13)	0.0559 (4)
N5	0.15069 (18)	0.41571 (14)	0.08498 (16)	0.0649 (4)
H1N5	0.093 (2)	0.4959 (14)	0.0546 (18)	0.078*
H2N5	0.2253 (16)	0.411 (2)	0.1072 (19)	0.078*
N6A	1.0965 (3)	−0.0913 (4)	0.7094 (3)	0.1308 (10)
N6B	0.6494 (3)	0.4551 (3)	0.8832 (3)	0.1294 (10)
C1	0.35319 (18)	0.15171 (15)	0.17683 (15)	0.0506 (4)
C2	0.32150 (18)	0.17803 (16)	0.29007 (15)	0.0539 (4)
C3	0.4294 (2)	0.16664 (18)	0.34551 (17)	0.0623 (4)
C4	0.5680 (2)	0.1308 (2)	0.2899 (2)	0.0718 (5)
H4	0.6397	0.1235	0.3275	0.086*
C5	0.6013 (2)	0.1056 (2)	0.1780 (2)	0.0729 (5)
H5	0.6955	0.0821	0.1399	0.087*
C6	0.49533 (19)	0.11497 (18)	0.12244 (17)	0.0617 (4)
H6	0.5193	0.0964	0.0473	0.074*
C7	0.23953 (17)	0.16526 (16)	0.11505 (14)	0.0502 (4)
C9	0.14097 (18)	0.29907 (16)	0.07353 (15)	0.0513 (4)
C8	0.03580 (19)	0.18599 (17)	0.00970 (16)	0.0556 (4)
C10A	0.9217 (3)	0.1513 (3)	0.6370 (2)	0.0904 (7)
C11A	0.9394 (5)	0.2669 (5)	0.6469 (3)	0.1335 (13)
H11A	1.0134	0.2595	0.6819	0.160*
C12A	0.8455 (7)	0.3983 (5)	0.6040 (4)	0.159 (2)
H12A	0.8561	0.4788	0.6109	0.191*
C13A	0.7388 (6)	0.4069 (4)	0.5521 (4)	0.1545 (18)
H13A	0.6768	0.4939	0.5232	0.185*
C14A	0.7216 (5)	0.2919 (4)	0.5420 (3)	0.1416 (13)
H14A	0.6484	0.2988	0.5062	0.170*
C15A	0.8134 (4)	0.1636 (3)	0.5854 (3)	0.1113 (9)
H15A	0.8011	0.0837	0.5793	0.134*
C16A	1.0186 (3)	0.0153 (4)	0.6786 (3)	0.0993 (8)
C10B	0.4455 (2)	0.4229 (2)	0.82049 (18)	0.0687 (5)
C11B	0.3246 (2)	0.5355 (2)	0.7988 (2)	0.0804 (6)
H11B	0.3163	0.6227	0.8079	0.096*
C12B	0.2167 (3)	0.5193 (3)	0.7640 (2)	0.0980 (8)
H12B	0.1354	0.5956	0.7485	0.118*
C13B	0.2281 (4)	0.3930 (4)	0.7520 (3)	0.1090 (9)
H13B	0.1539	0.3827	0.7288	0.131*
C14B	0.3468 (4)	0.2800 (3)	0.7735 (2)	0.1059 (9)
H14B	0.3526	0.1933	0.7652	0.127*
C15B	0.4588 (3)	0.2934 (2)	0.8075 (2)	0.0848 (6)
H15B	0.5407	0.2170	0.8213	0.102*
C16B	0.5587 (3)	0.4413 (3)	0.8558 (2)	0.0902 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0621 (3)	0.0903 (4)	0.0702 (3)	−0.0219 (2)	0.0005 (2)	−0.0268 (2)
Cl2	0.1155 (5)	0.1015 (4)	0.0767 (4)	−0.0210 (4)	−0.0381 (3)	−0.0297 (3)
N1	0.0541 (8)	0.0461 (7)	0.0699 (9)	−0.0101 (6)	−0.0157 (7)	−0.0186 (6)
N2	0.0617 (9)	0.0471 (7)	0.0789 (10)	−0.0125 (7)	−0.0222 (7)	−0.0217 (7)
N3	0.0831 (12)	0.0509 (8)	0.1113 (14)	−0.0178 (8)	−0.0518 (11)	−0.0159 (9)
N4	0.0587 (8)	0.0424 (7)	0.0709 (9)	−0.0151 (6)	−0.0232 (7)	−0.0100 (6)
N5	0.0677 (10)	0.0422 (7)	0.0944 (12)	−0.0163 (7)	−0.0399 (9)	−0.0075 (7)
N6A	0.0768 (16)	0.160 (3)	0.146 (3)	−0.0329 (17)	−0.0240 (16)	−0.022 (2)
N6B	0.0863 (16)	0.169 (3)	0.167 (3)	−0.0493 (17)	−0.0300 (17)	−0.071 (2)
C1	0.0505 (9)	0.0401 (7)	0.0599 (9)	−0.0111 (7)	−0.0132 (7)	−0.0102 (6)
C2	0.0539 (10)	0.0460 (8)	0.0602 (10)	−0.0132 (7)	−0.0121 (8)	−0.0111 (7)
C3	0.0683 (12)	0.0521 (9)	0.0671 (11)	−0.0131 (8)	−0.0242 (9)	−0.0116 (8)
C4	0.0627 (12)	0.0654 (11)	0.0934 (15)	−0.0162 (9)	−0.0352 (11)	−0.0131 (10)
C5	0.0463 (10)	0.0713 (11)	0.0942 (15)	−0.0109 (9)	−0.0143 (10)	−0.0167 (10)
C6	0.0535 (10)	0.0576 (9)	0.0686 (11)	−0.0099 (8)	−0.0093 (8)	−0.0183 (8)
C7	0.0492 (9)	0.0440 (8)	0.0560 (9)	−0.0117 (7)	−0.0093 (7)	−0.0135 (6)
C9	0.0514 (9)	0.0439 (8)	0.0604 (9)	−0.0144 (7)	−0.0140 (7)	−0.0114 (7)
C8	0.0604 (10)	0.0481 (9)	0.0632 (10)	−0.0184 (8)	−0.0157 (8)	−0.0140 (7)
C10A	0.0945 (18)	0.1105 (19)	0.0731 (14)	−0.0500 (16)	0.0062 (13)	−0.0255 (13)
C11A	0.167 (4)	0.147 (3)	0.119 (3)	−0.089 (3)	0.005 (2)	−0.050 (2)
C12A	0.245 (6)	0.126 (3)	0.132 (3)	−0.103 (4)	0.023 (3)	−0.055 (3)
C13A	0.216 (5)	0.102 (3)	0.109 (3)	−0.043 (3)	0.013 (3)	−0.017 (2)
C14A	0.166 (4)	0.117 (3)	0.133 (3)	−0.040 (3)	−0.049 (3)	−0.001 (2)
C15A	0.122 (2)	0.0953 (19)	0.123 (2)	−0.0413 (17)	−0.0359 (19)	−0.0117 (16)
C16A	0.0736 (16)	0.131 (2)	0.0984 (19)	−0.0435 (17)	−0.0052 (14)	−0.0268 (17)
C10B	0.0647 (12)	0.0756 (12)	0.0711 (12)	−0.0268 (10)	−0.0102 (9)	−0.0198 (9)
C11B	0.0741 (14)	0.0779 (13)	0.0913 (15)	−0.0245 (11)	−0.0150 (11)	−0.0211 (11)
C12B	0.0726 (15)	0.121 (2)	0.0935 (18)	−0.0253 (15)	−0.0228 (13)	−0.0133 (15)
C13B	0.116 (2)	0.149 (3)	0.0961 (19)	−0.078 (2)	−0.0349 (17)	−0.0134 (18)
C14B	0.160 (3)	0.1021 (19)	0.0898 (17)	−0.079 (2)	−0.0271 (18)	−0.0156 (14)
C15B	0.1027 (18)	0.0730 (13)	0.0783 (14)	−0.0249 (12)	−0.0237 (13)	−0.0140 (10)
C16B	0.0704 (14)	0.1103 (18)	0.1020 (18)	−0.0315 (13)	−0.0146 (13)	−0.0390 (14)

Geometric parameters (Å, º) top

Cl1—C2	1.7311 (18)	C7—C9	1.434 (2)
Cl2—C3	1.737 (2)	C10A—C11A	1.350 (5)
N1—C7	1.310 (2)	C10A—C15A	1.358 (4)
N1—N2	1.351 (2)	C10A—C16A	1.442 (5)
N2—C8	1.336 (2)	C11A—C12A	1.403 (7)
N3—C8	1.338 (2)	C11A—H11A	0.9300
N3—H1N3	0.862 (10)	C12A—C13A	1.359 (7)
N3—H2N3	0.858 (10)	C12A—H12A	0.9300
N4—C9	1.323 (2)	C13A—C14A	1.341 (6)
N4—C8	1.348 (2)	C13A—H13A	0.9300
N5—C9	1.327 (2)	C14A—C15A	1.375 (5)
N5—H1N5	0.873 (10)	C14A—H14A	0.9300
N5—H2N5	0.854 (10)	C15A—H15A	0.9300
N6A—C16A	1.133 (4)	C10B—C11B	1.375 (3)
N6B—C16B	1.138 (3)	C10B—C15B	1.378 (3)
C1—C6	1.392 (2)	C10B—C16B	1.433 (3)
C1—C2	1.399 (2)	C11B—C12B	1.367 (4)
C1—C7	1.484 (2)	C11B—H11B	0.9300
C2—C3	1.388 (3)	C12B—C13B	1.345 (4)
C3—C4	1.366 (3)	C12B—H12B	0.9300
C4—C5	1.377 (3)	C13B—C14B	1.363 (5)
C4—H4	0.9300	C13B—H13B	0.9300
C5—C6	1.379 (3)	C14B—C15B	1.387 (4)
C5—H5	0.9300	C14B—H14B	0.9300
C6—H6	0.9300	C15B—H15B	0.9300

C7—N1—N2	120.29 (13)	C11A—C10A—C16A	120.4 (3)
C8—N2—N1	117.46 (13)	C15A—C10A—C16A	120.0 (3)
C8—N3—H1N3	120.5 (17)	C10A—C11A—C12A	119.5 (4)
C8—N3—H2N3	120.8 (17)	C10A—C11A—H11A	120.2
H1N3—N3—H2N3	118 (2)	C12A—C11A—H11A	120.2
C9—N4—C8	116.30 (14)	C13A—C12A—C11A	119.3 (4)
C9—N5—H1N5	119.5 (15)	C13A—C12A—H12A	120.3
C9—N5—H2N5	118.2 (16)	C11A—C12A—H12A	120.3
H1N5—N5—H2N5	121 (2)	C14A—C13A—C12A	121.1 (5)
C6—C1—C2	117.76 (16)	C14A—C13A—H13A	119.4
C6—C1—C7	120.72 (15)	C12A—C13A—H13A	119.4
C2—C1—C7	121.51 (15)	C13A—C14A—C15A	119.1 (5)
C3—C2—C1	120.50 (16)	C13A—C14A—H14A	120.4
C3—C2—Cl1	119.98 (14)	C15A—C14A—H14A	120.4
C1—C2—Cl1	119.51 (13)	C10A—C15A—C14A	121.3 (3)
C4—C3—C2	120.50 (18)	C10A—C15A—H15A	119.3
C4—C3—Cl2	119.01 (15)	C14A—C15A—H15A	119.3
C2—C3—Cl2	120.48 (15)	N6A—C16A—C10A	178.7 (3)
C3—C4—C5	119.90 (18)	C11B—C10B—C15B	120.5 (2)
C3—C4—H4	120.1	C11B—C10B—C16B	119.6 (2)
C5—C4—H4	120.1	C15B—C10B—C16B	120.0 (2)
C4—C5—C6	120.19 (18)	C12B—C11B—C10B	120.0 (2)
C4—C5—H5	119.9	C12B—C11B—H11B	120.0
C6—C5—H5	119.9	C10B—C11B—H11B	120.0
C5—C6—C1	121.15 (18)	C13B—C12B—C11B	120.1 (3)
C5—C6—H6	119.4	C13B—C12B—H12B	120.0
C1—C6—H6	119.4	C11B—C12B—H12B	120.0
N1—C7—C9	120.29 (15)	C12B—C13B—C14B	120.9 (3)
N1—C7—C1	118.55 (14)	C12B—C13B—H13B	119.5
C9—C7—C1	121.09 (14)	C14B—C13B—H13B	119.5
N4—C9—N5	118.86 (14)	C13B—C14B—C15B	120.4 (2)
N4—C9—C7	119.61 (14)	C13B—C14B—H14B	119.8
N5—C9—C7	121.53 (15)	C15B—C14B—H14B	119.8
N2—C8—N3	117.26 (15)	C10B—C15B—C14B	118.2 (3)
N2—C8—N4	125.76 (16)	C10B—C15B—H15B	120.9
N3—C8—N4	116.95 (15)	C14B—C15B—H15B	120.9
C11A—C10A—C15A	119.6 (3)	N6B—C16B—C10B	179.4 (3)

C7—N1—N2—C8	−1.0 (2)	C1—C7—C9—N4	−177.45 (15)
C6—C1—C2—C3	−0.4 (2)	N1—C7—C9—N5	−174.57 (17)
C7—C1—C2—C3	−179.06 (14)	C1—C7—C9—N5	2.4 (3)
C6—C1—C2—Cl1	−179.63 (12)	N1—N2—C8—N3	−177.65 (17)
C7—C1—C2—Cl1	1.7 (2)	N1—N2—C8—N4	4.4 (3)
C1—C2—C3—C4	0.6 (3)	C9—N4—C8—N2	−2.6 (3)
Cl1—C2—C3—C4	179.85 (14)	C9—N4—C8—N3	179.49 (17)
C1—C2—C3—Cl2	−178.49 (12)	C15A—C10A—C11A—C12A	0.1 (5)
Cl1—C2—C3—Cl2	0.8 (2)	C16A—C10A—C11A—C12A	178.9 (3)
C2—C3—C4—C5	−0.1 (3)	C10A—C11A—C12A—C13A	−0.6 (6)
Cl2—C3—C4—C5	179.03 (15)	C11A—C12A—C13A—C14A	0.4 (7)
C3—C4—C5—C6	−0.7 (3)	C12A—C13A—C14A—C15A	0.2 (7)
C4—C5—C6—C1	0.9 (3)	C11A—C10A—C15A—C14A	0.5 (5)
C2—C1—C6—C5	−0.3 (3)	C16A—C10A—C15A—C14A	−178.3 (3)
C7—C1—C6—C5	178.34 (16)	C13A—C14A—C15A—C10A	−0.7 (6)
N2—N1—C7—C9	−3.7 (2)	C15B—C10B—C11B—C12B	−0.1 (4)
N2—N1—C7—C1	179.21 (15)	C16B—C10B—C11B—C12B	179.4 (2)
C6—C1—C7—N1	69.5 (2)	C10B—C11B—C12B—C13B	0.7 (4)
C2—C1—C7—N1	−111.89 (18)	C11B—C12B—C13B—C14B	−0.4 (5)
C6—C1—C7—C9	−107.59 (19)	C12B—C13B—C14B—C15B	−0.4 (5)
C2—C1—C7—C9	71.0 (2)	C11B—C10B—C15B—C14B	−0.6 (4)
C8—N4—C9—N5	177.72 (17)	C16B—C10B—C15B—C14B	179.8 (2)
C8—N4—C9—C7	−2.4 (2)	C13B—C14B—C15B—C10B	0.9 (4)
N1—C7—C9—N4	5.5 (3)

(LAM_acetonitrile_solvate) top

Crystal data top

C₉H₇Cl₂N₅·C₂H₃N	Z = 2
M_r = 297.15	F(000) = 304
Triclinic, P1	D_x = 1.425 Mg m⁻³
a = 7.9855 (4) Å	Cu Kα radiation, λ = 1.54184 Å
b = 8.6004 (5) Å	Cell parameters from 2878 reflections
c = 10.9109 (7) Å	θ = 4.3–72.2°
α = 69.598 (6)°	µ = 4.19 mm⁻¹
β = 82.227 (5)°	T = 296 K
γ = 82.015 (5)°	Block prism, colourless
V = 692.48 (7) Å³	0.40 × 0.40 × 0.40 mm

Data collection top

Xcalibur, Sapphire3, Gemini diffractometer	2430 reflections with I > 2σ(I)
Radiation source: Enhance (Cu) X-ray Source	R_int = 0.020
ω scans	θ_max = 70.0°, θ_min = 4.3°
Absorption correction: multi-scan CrysAlisPro, Agilent Technologies, Version 1.171.36.21. Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −6→9
T_min = 0.210, T_max = 1.000	k = −10→10
5383 measured reflections	l = −13→12
2633 independent reflections

Refinement top

Refinement on F²	4 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.056	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.176	w = 1/[σ²(F_o²) + (0.1224P)² + 0.2081P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
2633 reflections	Δρ_max = 0.73 e Å⁻³
185 parameters	Δρ_min = −0.31 e Å⁻³

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	0.46106 (8)	0.33991 (8)	0.73313 (7)	0.0666 (3)
Cl2	0.24043 (8)	0.04639 (10)	0.77877 (7)	0.0711 (3)
N1	0.8385 (3)	0.2641 (3)	0.92386 (19)	0.0517 (5)
N2	0.9300 (3)	0.3850 (3)	0.92135 (19)	0.0530 (5)
N3	1.0867 (3)	0.6000 (3)	0.8051 (2)	0.0550 (5)
N4	0.9872 (2)	0.4587 (2)	0.68806 (17)	0.0439 (4)
N5	0.8811 (3)	0.3112 (3)	0.5812 (2)	0.0578 (6)
N6	0.3554 (6)	0.8047 (7)	0.5603 (5)	0.1205 (14)
C1	0.7137 (3)	0.1019 (3)	0.8297 (2)	0.0426 (5)
C2	0.5468 (3)	0.1355 (3)	0.7964 (2)	0.0454 (5)
C3	0.4480 (3)	0.0056 (3)	0.8184 (2)	0.0487 (5)
C4	0.5145 (3)	−0.1578 (3)	0.8738 (2)	0.0540 (6)
H4	0.4479	−0.2444	0.8891	0.065*
C5	0.6790 (3)	−0.1919 (3)	0.9062 (3)	0.0544 (6)
H5	0.7239	−0.3020	0.9427	0.065*
C6	0.7794 (3)	−0.0632 (3)	0.8849 (2)	0.0490 (5)
H6	0.8906	−0.0876	0.9075	0.059*
C7	0.8183 (3)	0.2396 (3)	0.8155 (2)	0.0426 (5)
C8	0.9993 (3)	0.4774 (3)	0.8040 (2)	0.0430 (5)
C9	0.8963 (3)	0.3381 (3)	0.6926 (2)	0.0423 (5)
C10	0.4992 (7)	0.7841 (5)	0.5660 (4)	0.0895 (11)
C11	0.6768 (6)	0.7575 (6)	0.5731 (4)	0.1052 (14)
H11A	0.7014	0.6782	0.6572	0.158*
H11B	0.7198	0.8610	0.5617	0.158*
H11C	0.7297	0.7153	0.5050	0.158*
H2N3	1.093 (7)	0.625 (7)	0.874 (3)	0.126*
H2N5	0.927 (7)	0.375 (5)	0.509 (3)	0.126*
H1N3	1.135 (6)	0.664 (5)	0.734 (3)	0.126*
H1N5	0.823 (6)	0.236 (5)	0.579 (6)	0.126*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0577 (4)	0.0486 (4)	0.0803 (5)	0.0018 (3)	−0.0101 (3)	−0.0066 (3)
Cl2	0.0470 (4)	0.0837 (5)	0.0713 (5)	−0.0171 (3)	−0.0085 (3)	−0.0069 (4)
N1	0.0617 (12)	0.0522 (11)	0.0400 (9)	−0.0180 (9)	0.0017 (8)	−0.0118 (8)
N2	0.0660 (13)	0.0568 (11)	0.0383 (9)	−0.0206 (10)	−0.0005 (8)	−0.0146 (8)
N3	0.0670 (13)	0.0535 (11)	0.0476 (11)	−0.0209 (10)	0.0014 (9)	−0.0175 (9)
N4	0.0481 (10)	0.0440 (9)	0.0371 (9)	−0.0100 (8)	−0.0002 (7)	−0.0097 (7)
N5	0.0734 (14)	0.0654 (13)	0.0386 (10)	−0.0305 (11)	0.0045 (9)	−0.0168 (9)
N6	0.100 (3)	0.145 (4)	0.142 (4)	−0.033 (3)	−0.009 (3)	−0.073 (3)
C1	0.0450 (11)	0.0432 (11)	0.0363 (10)	−0.0081 (8)	0.0037 (8)	−0.0103 (8)
C2	0.0467 (12)	0.0439 (11)	0.0391 (10)	−0.0042 (9)	0.0011 (8)	−0.0078 (8)
C3	0.0429 (11)	0.0565 (13)	0.0423 (11)	−0.0117 (9)	0.0028 (9)	−0.0110 (10)
C4	0.0568 (14)	0.0500 (13)	0.0523 (13)	−0.0184 (10)	0.0072 (10)	−0.0133 (10)
C5	0.0587 (14)	0.0398 (11)	0.0563 (13)	−0.0060 (10)	0.0028 (11)	−0.0081 (10)
C6	0.0465 (12)	0.0461 (12)	0.0481 (12)	−0.0053 (9)	0.0005 (9)	−0.0096 (9)
C7	0.0423 (11)	0.0420 (10)	0.0395 (10)	−0.0062 (8)	0.0014 (8)	−0.0097 (8)
C8	0.0444 (11)	0.0428 (11)	0.0397 (10)	−0.0050 (8)	−0.0023 (8)	−0.0117 (8)
C9	0.0439 (11)	0.0432 (10)	0.0372 (10)	−0.0061 (8)	−0.0017 (8)	−0.0105 (8)
C10	0.113 (3)	0.073 (2)	0.080 (2)	−0.011 (2)	−0.007 (2)	−0.0221 (17)
C11	0.093 (3)	0.114 (3)	0.085 (3)	0.027 (2)	−0.014 (2)	−0.015 (2)

Geometric parameters (Å, º) top

Cl1—C2	1.727 (2)	C1—C2	1.394 (3)
Cl2—C3	1.727 (3)	C1—C7	1.495 (3)
N1—C7	1.305 (3)	C2—C3	1.392 (3)
N1—N2	1.342 (3)	C3—C4	1.381 (4)
N2—C8	1.341 (3)	C4—C5	1.373 (4)
N3—C8	1.346 (3)	C4—H4	0.9300
N3—H2N3	0.863 (10)	C5—C6	1.392 (3)
N3—H1N3	0.858 (10)	C5—H5	0.9300
N4—C9	1.330 (3)	C6—H6	0.9300
N4—C8	1.347 (3)	C7—C9	1.426 (3)
N5—C9	1.338 (3)	C10—C11	1.412 (7)
N5—H2N5	0.857 (10)	C11—H11A	0.9600
N5—H1N5	0.858 (10)	C11—H11B	0.9600
N6—C10	1.145 (6)	C11—H11C	0.9600
C1—C6	1.392 (3)

C7—N1—N2	120.63 (19)	C4—C5—H5	119.7
C8—N2—N1	117.33 (19)	C6—C5—H5	119.7
C8—N3—H2N3	124 (4)	C1—C6—C5	120.1 (2)
C8—N3—H1N3	121 (4)	C1—C6—H6	119.9
H2N3—N3—H1N3	115 (5)	C5—C6—H6	119.9
C9—N4—C8	115.90 (18)	N1—C7—C9	120.6 (2)
C9—N5—H2N5	118 (3)	N1—C7—C1	116.15 (19)
C9—N5—H1N5	123 (4)	C9—C7—C1	123.20 (19)
H2N5—N5—H1N5	119 (5)	N2—C8—N3	115.6 (2)
C6—C1—C2	118.9 (2)	N2—C8—N4	125.9 (2)
C6—C1—C7	119.8 (2)	N3—C8—N4	118.6 (2)
C2—C1—C7	121.2 (2)	N4—C9—N5	119.00 (19)
C3—C2—C1	120.3 (2)	N4—C9—C7	119.61 (19)
C3—C2—Cl1	120.20 (18)	N5—C9—C7	121.4 (2)
C1—C2—Cl1	119.48 (17)	N6—C10—C11	179.6 (5)
C4—C3—C2	120.2 (2)	C10—C11—H11A	109.5
C4—C3—Cl2	119.26 (19)	C10—C11—H11B	109.5
C2—C3—Cl2	120.53 (19)	H11A—C11—H11B	109.5
C5—C4—C3	119.9 (2)	C10—C11—H11C	109.5
C5—C4—H4	120.1	H11A—C11—H11C	109.5
C3—C4—H4	120.1	H11B—C11—H11C	109.5
C4—C5—C6	120.6 (2)

C7—N1—N2—C8	−0.3 (4)	N2—N1—C7—C1	−179.9 (2)
C6—C1—C2—C3	0.1 (3)	C6—C1—C7—N1	−72.2 (3)
C7—C1—C2—C3	−175.77 (19)	C2—C1—C7—N1	103.7 (3)
C6—C1—C2—Cl1	177.79 (16)	C6—C1—C7—C9	106.4 (3)
C7—C1—C2—Cl1	1.9 (3)	C2—C1—C7—C9	−77.8 (3)
C1—C2—C3—C4	0.2 (3)	N1—N2—C8—N3	178.4 (2)
Cl1—C2—C3—C4	−177.46 (18)	N1—N2—C8—N4	−0.9 (4)
C1—C2—C3—Cl2	179.41 (16)	C9—N4—C8—N2	0.7 (4)
Cl1—C2—C3—Cl2	1.7 (3)	C9—N4—C8—N3	−178.6 (2)
C2—C3—C4—C5	−0.6 (4)	C8—N4—C9—N5	−179.1 (2)
Cl2—C3—C4—C5	−179.77 (19)	C8—N4—C9—C7	0.5 (3)
C3—C4—C5—C6	0.6 (4)	N1—C7—C9—N4	−1.7 (3)
C2—C1—C6—C5	−0.1 (3)	C1—C7—C9—N4	179.8 (2)
C7—C1—C6—C5	175.9 (2)	N1—C7—C9—N5	178.0 (2)
C4—C5—C6—C1	−0.3 (4)	C1—C7—C9—N5	−0.5 (4)
N2—N1—C7—C9	1.5 (4)

(LAM_DMSO_solvate) top

Crystal data top

C₉H₇Cl₂N₅·C₂H₆OS	F(000) = 688
M_r = 334.22	D_x = 1.440 Mg m⁻³
Monoclinic, P2₁/n	Cu Kα radiation, λ = 1.54184 Å
a = 10.6626 (3) Å	Cell parameters from 3373 reflections
b = 7.3529 (2) Å	θ = 4.1–67.2°
c = 19.6714 (5) Å	µ = 5.09 mm⁻¹
β = 92.096 (2)°	T = 296 K
V = 1541.23 (7) Å³	Prism, colourless
Z = 4	0.30 × 0.25 × 0.25 mm

Data collection top

Goniometer Xcalibur, detector: Sapphire3 (Gemini Cu) diffractometer	2135 reflections with I > 2σ(I)
Radiation source: Enhance (Cu) X-ray Source	R_int = 0.026
ω scans	θ_max = 67.4°, θ_min = 4.5°
Absorption correction: multi-scan CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.33.34d. Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −12→9
T_min = 0.585, T_max = 1.000	k = −8→8
7391 measured reflections	l = −21→23
2747 independent reflections

Refinement top

Refinement on F²	7 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.042	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.118	w = 1/[σ²(F_o²) + (0.0845P)²] where P = (F_o² + 2F_c²)/3
S = 0.95	(Δ/σ)_max = 0.001
2747 reflections	Δρ_max = 0.28 e Å⁻³
211 parameters	Δρ_min = −0.27 e Å⁻³

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cl1	0.95196 (7)	0.71206 (8)	0.21238 (3)	0.0723 (2)
Cl2	1.01288 (7)	1.04096 (9)	0.30952 (3)	0.0769 (2)
N1	0.66814 (15)	0.7751 (2)	0.07757 (9)	0.0526 (4)
N2	0.62188 (15)	0.6423 (3)	0.03726 (9)	0.0547 (5)
N3	0.65635 (17)	0.3996 (3)	−0.03171 (10)	0.0616 (5)
H3NA	0.5764 (10)	0.382 (4)	−0.0325 (14)	0.074*
H3NB	0.707 (2)	0.325 (3)	−0.0507 (13)	0.074*
N4	0.82971 (15)	0.5544 (2)	0.01022 (9)	0.0521 (4)
N5	0.99699 (18)	0.7244 (3)	0.04827 (13)	0.0738 (7)
H5NA	1.031 (3)	0.810 (3)	0.0719 (13)	0.089*
H5NB	1.045 (2)	0.636 (3)	0.0353 (15)	0.089*
C10	0.5781 (3)	−0.0654 (5)	−0.11071 (19)	0.0934 (10)
H10A	0.5208	−0.1326	−0.1399	0.140*	0.69
H10B	0.6038	−0.1396	−0.0726	0.140*	0.69
H10C	0.5374	0.0421	−0.0948	0.140*	0.69
H10D	0.5395	−0.1740	−0.0942	0.140*	0.31
H10E	0.5449	0.0384	−0.0878	0.140*	0.31
H10F	0.5607	−0.0543	−0.1588	0.140*	0.31
S1A	0.70995 (10)	−0.00363 (13)	−0.15605 (5)	0.0733 (3)	0.69
O1A	0.7922 (10)	0.1041 (11)	−0.1004 (4)	0.140 (3)	0.69
S1B	0.7388 (2)	−0.0767 (3)	−0.09500 (12)	0.0769 (6)	0.31
O1B	0.7842 (19)	0.1104 (18)	−0.1252 (6)	0.079 (3)	0.31
C11	0.7870 (3)	−0.2207 (5)	−0.1574 (2)	0.1148 (14)
H11A	0.7444	−0.2984	−0.1899	0.172*	0.69
H11B	0.8725	−0.2046	−0.1699	0.172*	0.69
H11C	0.7853	−0.2751	−0.1131	0.172*	0.69
H11D	0.7654	−0.3434	−0.1460	0.172*	0.31
H11E	0.7463	−0.1881	−0.2000	0.172*	0.31
H11F	0.8763	−0.2111	−0.1611	0.172*	0.31
C1	0.82694 (18)	0.9540 (3)	0.13121 (10)	0.0472 (5)
C2	0.89866 (18)	0.9275 (3)	0.19127 (10)	0.0478 (5)
C3	0.92277 (19)	1.0719 (3)	0.23544 (11)	0.0509 (5)
C4	0.8755 (2)	1.2420 (3)	0.22109 (13)	0.0598 (6)
H4	0.8912	1.3378	0.2511	0.072*
C5	0.8049 (3)	1.2696 (3)	0.16214 (14)	0.0681 (6)
H5	0.7727	1.3845	0.1523	0.082*
C6	0.7815 (2)	1.1278 (3)	0.11748 (12)	0.0594 (5)
H6	0.7345	1.1489	0.0775	0.071*
C7	0.78953 (17)	0.8012 (3)	0.08515 (10)	0.0472 (5)
C8	0.70424 (18)	0.5354 (3)	0.00655 (10)	0.0474 (5)
C9	0.87470 (18)	0.6919 (3)	0.04823 (11)	0.0516 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0956 (5)	0.0482 (3)	0.0714 (4)	0.0105 (3)	−0.0221 (3)	−0.0054 (3)
Cl2	0.1000 (5)	0.0720 (4)	0.0567 (3)	0.0047 (3)	−0.0250 (3)	−0.0133 (3)
N1	0.0418 (9)	0.0611 (11)	0.0549 (10)	−0.0042 (7)	−0.0002 (7)	−0.0130 (8)
N2	0.0394 (8)	0.0669 (11)	0.0572 (10)	−0.0069 (8)	−0.0036 (7)	−0.0157 (9)
N3	0.0425 (9)	0.0737 (13)	0.0680 (12)	−0.0073 (9)	−0.0068 (8)	−0.0270 (10)
N4	0.0393 (8)	0.0627 (11)	0.0541 (10)	−0.0054 (7)	−0.0025 (7)	−0.0172 (8)
N5	0.0404 (9)	0.0874 (15)	0.0938 (16)	−0.0113 (9)	0.0048 (9)	−0.0484 (13)
C10	0.0674 (16)	0.090 (2)	0.123 (3)	−0.0078 (15)	0.0034 (17)	−0.0176 (19)
S1A	0.0770 (6)	0.0683 (6)	0.0747 (6)	−0.0200 (4)	0.0050 (5)	−0.0100 (5)
O1A	0.068 (3)	0.149 (5)	0.203 (8)	−0.025 (3)	−0.010 (5)	−0.125 (5)
S1B	0.0691 (12)	0.0813 (14)	0.0801 (14)	0.0066 (10)	−0.0001 (10)	−0.0020 (12)
O1B	0.067 (5)	0.091 (6)	0.079 (5)	−0.035 (4)	−0.006 (4)	−0.038 (5)
C11	0.097 (2)	0.100 (3)	0.151 (4)	−0.0109 (19)	0.046 (2)	−0.025 (2)
C1	0.0413 (9)	0.0493 (11)	0.0511 (11)	−0.0040 (8)	0.0015 (8)	−0.0061 (9)
C2	0.0494 (10)	0.0441 (10)	0.0498 (11)	−0.0003 (8)	−0.0004 (8)	−0.0043 (9)
C3	0.0553 (11)	0.0516 (12)	0.0454 (10)	−0.0049 (9)	−0.0026 (9)	−0.0058 (9)
C4	0.0693 (14)	0.0475 (11)	0.0624 (13)	−0.0024 (10)	0.0003 (11)	−0.0114 (10)
C5	0.0806 (16)	0.0464 (12)	0.0766 (16)	0.0062 (11)	−0.0058 (13)	−0.0015 (11)
C6	0.0609 (13)	0.0554 (13)	0.0612 (13)	0.0016 (10)	−0.0084 (10)	−0.0014 (11)
C7	0.0417 (10)	0.0527 (11)	0.0468 (10)	−0.0049 (8)	−0.0024 (8)	−0.0068 (9)
C8	0.0421 (10)	0.0577 (12)	0.0421 (10)	−0.0051 (9)	−0.0043 (8)	−0.0049 (9)
C9	0.0409 (10)	0.0605 (12)	0.0533 (11)	−0.0063 (9)	−0.0014 (8)	−0.0138 (10)

Geometric parameters (Å, º) top

Cl1—C2	1.728 (2)	S1A—O1A	1.589 (7)
Cl2—C3	1.731 (2)	S1A—C11	1.795 (4)
N1—C7	1.312 (3)	S1B—O1B	1.581 (9)
N1—N2	1.341 (2)	S1B—C11	1.714 (4)
N2—C8	1.339 (3)	C11—H11A	0.9600
N3—C8	1.340 (3)	C11—H11B	0.9600
N3—H3NA	0.861 (10)	C11—H11C	0.9600
N3—H3NB	0.865 (10)	C11—H11D	0.9600
N4—C9	1.336 (3)	C11—H11E	0.9600
N4—C8	1.345 (3)	C11—H11F	0.9600
N5—C9	1.326 (3)	C1—C6	1.390 (3)
N5—H5NA	0.858 (10)	C1—C2	1.397 (3)
N5—H5NB	0.867 (10)	C1—C7	1.489 (3)
C10—S1B	1.732 (3)	C2—C3	1.390 (3)
C10—S1A	1.752 (3)	C3—C4	1.374 (3)
C10—H10A	0.9600	C4—C5	1.374 (4)
C10—H10B	0.9600	C4—H4	0.9300
C10—H10C	0.9600	C5—C6	1.380 (3)
C10—H10D	0.9600	C5—H5	0.9300
C10—H10E	0.9600	C6—H6	0.9300
C10—H10F	0.9600	C7—C9	1.430 (3)

C7—N1—N2	120.92 (17)	S1B—C11—H11D	109.5
N1—N2—C8	117.48 (16)	S1B—C11—H11E	109.5
C8—N3—H3NA	118.5 (18)	H11D—C11—H11E	109.5
C8—N3—H3NB	118.6 (19)	S1B—C11—H11F	109.5
H3NA—N3—H3NB	123 (3)	H11D—C11—H11F	109.5
C9—N4—C8	116.44 (17)	H11E—C11—H11F	109.5
C9—N5—H5NA	122 (2)	C6—C1—C2	117.97 (19)
C9—N5—H5NB	117 (2)	C6—C1—C7	119.47 (19)
H5NA—N5—H5NB	118 (3)	C2—C1—C7	122.37 (19)
S1A—C10—H10A	109.5	C3—C2—C1	120.3 (2)
S1A—C10—H10B	109.5	C3—C2—Cl1	119.89 (16)
H10A—C10—H10B	109.5	C1—C2—Cl1	119.74 (16)
S1A—C10—H10C	109.5	C4—C3—C2	120.6 (2)
H10A—C10—H10C	109.5	C4—C3—Cl2	118.74 (17)
H10B—C10—H10C	109.5	C2—C3—Cl2	120.66 (17)
S1B—C10—H10D	109.5	C3—C4—C5	119.5 (2)
S1B—C10—H10E	109.5	C3—C4—H4	120.2
H10D—C10—H10E	109.5	C5—C4—H4	120.2
S1B—C10—H10F	109.5	C4—C5—C6	120.4 (2)
H10D—C10—H10F	109.5	C4—C5—H5	119.8
H10E—C10—H10F	109.5	C6—C5—H5	119.8
O1A—S1A—C10	102.2 (4)	C5—C6—C1	121.1 (2)
O1A—S1A—C11	102.2 (4)	C5—C6—H6	119.4
C10—S1A—C11	98.80 (17)	C1—C6—H6	119.4
O1B—S1B—C11	99.5 (7)	N1—C7—C9	120.17 (18)
O1B—S1B—C10	101.9 (8)	N1—C7—C1	114.89 (17)
C11—S1B—C10	102.9 (2)	C9—C7—C1	124.88 (17)
S1A—C11—H11A	109.5	N3—C8—N2	116.62 (18)
S1A—C11—H11B	109.5	N3—C8—N4	117.77 (18)
H11A—C11—H11B	109.5	N2—C8—N4	125.61 (18)
S1A—C11—H11C	109.5	N5—C9—N4	118.00 (19)
H11A—C11—H11C	109.5	N5—C9—C7	122.79 (19)
H11B—C11—H11C	109.5	N4—C9—C7	119.17 (17)

C7—N1—N2—C8	1.5 (3)	N2—N1—C7—C1	179.77 (18)
C6—C1—C2—C3	0.1 (3)	C6—C1—C7—N1	−57.0 (3)
C7—C1—C2—C3	−174.77 (18)	C2—C1—C7—N1	117.8 (2)
C6—C1—C2—Cl1	177.36 (16)	C6—C1—C7—C9	120.2 (2)
C7—C1—C2—Cl1	2.5 (3)	C2—C1—C7—C9	−65.0 (3)
C1—C2—C3—C4	0.7 (3)	N1—N2—C8—N3	177.8 (2)
Cl1—C2—C3—C4	−176.59 (17)	N1—N2—C8—N4	−3.1 (3)
C1—C2—C3—Cl2	−179.32 (15)	C9—N4—C8—N3	179.4 (2)
Cl1—C2—C3—Cl2	3.4 (3)	C9—N4—C8—N2	0.3 (3)
C2—C3—C4—C5	−0.7 (3)	C8—N4—C9—N5	−174.3 (2)
Cl2—C3—C4—C5	179.30 (19)	C8—N4—C9—C7	3.7 (3)
C3—C4—C5—C6	−0.1 (4)	N1—C7—C9—N5	172.7 (2)
C4—C5—C6—C1	0.8 (4)	C1—C7—C9—N5	−4.4 (4)
C2—C1—C6—C5	−0.9 (3)	N1—C7—C9—N4	−5.2 (3)
C7—C1—C6—C5	174.2 (2)	C1—C7—C9—N4	177.8 (2)
N2—N1—C7—C9	2.4 (3)

(LAM_dioxane_solvate) top

Crystal data top

2(C₉H₇Cl₂N₅)·1.5(C₄H₈O₂)	Z = 2
M_r = 644.35	F(000) = 664
Triclinic, P1	D_x = 1.432 Mg m⁻³
a = 10.2684 (12) Å	Cu Kα radiation, λ = 1.54184 Å
b = 10.7665 (6) Å	Cell parameters from 2601 reflections
c = 14.9036 (12) Å	θ = 4.4–72.8°
α = 71.197 (6)°	µ = 3.99 mm⁻¹
β = 78.435 (8)°	T = 296 K
γ = 74.957 (7)°	Prism, colourless
V = 1493.9 (2) Å³	0.50 × 0.30 × 0.30 mm

Data collection top

Xcalibur, Sapphire3, Gemini diffractometer	4048 reflections with I > 2σ(I)
Radiation source: Enhance (Cu) X-ray Source	R_int = 0.048
ω scans	θ_max = 70.0°, θ_min = 4.4°
Absorption correction: multi-scan CrysAlisPro, Agilent Technologies, Version 1.171.36.21. Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −12→12
T_min = 0.356, T_max = 1.000	k = −13→9
14176 measured reflections	l = −17→18
5657 independent reflections

Refinement top

Refinement on F²	8 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.075	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.236	w = 1/[σ²(F_o²) + (0.1342P)² + 0.1319P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max < 0.001
5657 reflections	Δρ_max = 0.53 e Å⁻³
394 parameters	Δρ_min = −0.58 e Å⁻³

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl1A	0.04256 (12)	0.86674 (17)	0.88105 (9)	0.1077 (5)
Cl2A	0.10999 (17)	1.05056 (11)	0.67562 (8)	0.1011 (5)
Cl1B	0.49067 (10)	0.23919 (11)	0.58107 (7)	0.0798 (3)
Cl2B	0.47911 (12)	0.44319 (11)	0.37583 (8)	0.0877 (4)
O1A	0.7258 (3)	0.8913 (2)	0.08189 (18)	0.0753 (8)
O1B	0.8971 (3)	0.4806 (3)	0.57812 (19)	0.0781 (8)
O2A	0.7170 (5)	0.6364 (3)	0.2062 (3)	0.1139 (13)
N1A	0.2783 (4)	0.5402 (3)	0.9862 (2)	0.0651 (8)
N2A	0.2516 (4)	0.4590 (3)	1.0763 (2)	0.0671 (8)
N3A	0.1966 (4)	0.4327 (3)	1.2365 (2)	0.0708 (9)
H13A	0.182 (5)	0.461 (4)	1.287 (2)	0.085*
H23A	0.203 (5)	0.3518 (18)	1.236 (3)	0.085*
N4A	0.2278 (3)	0.6403 (2)	1.1413 (2)	0.0610 (7)
N5A	0.2593 (5)	0.8450 (3)	1.0423 (2)	0.0769 (10)
H15A	0.272 (5)	0.898 (4)	0.9856 (15)	0.092*
H25A	0.254 (5)	0.878 (5)	1.089 (2)	0.092*
N1B	0.7809 (3)	−0.0519 (2)	0.64053 (19)	0.0570 (7)
N2B	0.7774 (3)	−0.1362 (2)	0.73029 (19)	0.0583 (7)
N3B	0.7306 (4)	−0.1635 (3)	0.8912 (2)	0.0633 (8)
H13B	0.740 (4)	−0.135 (4)	0.937 (2)	0.076*
H23B	0.736 (4)	−0.2480 (14)	0.902 (3)	0.076*
N4B	0.7453 (3)	0.0481 (2)	0.79442 (18)	0.0529 (6)
N5B	0.7608 (3)	0.2564 (3)	0.6932 (2)	0.0603 (7)
H15B	0.764 (5)	0.278 (4)	0.7432 (18)	0.072*
H25B	0.770 (4)	0.306 (4)	0.6349 (12)	0.072*
C1A	0.3089 (3)	0.7506 (3)	0.8732 (2)	0.0549 (7)
C2A	0.2065 (4)	0.8489 (3)	0.8264 (3)	0.0610 (8)
C3A	0.2378 (5)	0.9289 (4)	0.7344 (3)	0.0674 (9)
C4A	0.3673 (5)	0.9126 (4)	0.6888 (3)	0.0793 (12)
H4A	0.3874	0.9669	0.6273	0.095*
C5A	0.4676 (5)	0.8159 (5)	0.7341 (3)	0.0872 (13)
H5A	0.5559	0.8040	0.7028	0.105*
C6A	0.4392 (4)	0.7345 (4)	0.8269 (3)	0.0756 (10)
H6A	0.5084	0.6697	0.8572	0.091*
C7A	0.2776 (4)	0.6652 (3)	0.9731 (2)	0.0566 (7)
C8A	0.2259 (4)	0.5128 (3)	1.1486 (2)	0.0577 (8)
C9A	0.2539 (4)	0.7182 (3)	1.0534 (2)	0.0590 (8)
C1B	0.7615 (3)	0.1683 (3)	0.5283 (2)	0.0523 (7)
C2B	0.6373 (4)	0.2506 (3)	0.5012 (2)	0.0569 (8)
C3B	0.6309 (4)	0.3406 (3)	0.4095 (2)	0.0617 (8)
C4B	0.7484 (4)	0.3455 (3)	0.3447 (3)	0.0653 (9)
H4B	0.7445	0.4043	0.2834	0.078*
C5B	0.8700 (4)	0.2646 (3)	0.3702 (2)	0.0648 (9)
H5B	0.9480	0.2683	0.3260	0.078*
C6B	0.8778 (4)	0.1768 (3)	0.4619 (2)	0.0595 (8)
H6B	0.9612	0.1235	0.4788	0.071*
C7B	0.7661 (3)	0.0778 (3)	0.6269 (2)	0.0513 (7)
C8B	0.7523 (3)	−0.0819 (3)	0.8028 (2)	0.0514 (7)
C9B	0.7573 (3)	0.1283 (3)	0.7064 (2)	0.0511 (7)
C10B	1.0356 (5)	0.4299 (4)	0.5889 (3)	0.0820 (12)
H10A	1.0451	0.3485	0.6418	0.098*
H10B	1.0709	0.4950	0.6041	0.098*
C11B	0.8833 (5)	0.5998 (4)	0.4994 (3)	0.0843 (12)
H11A	0.9149	0.6684	0.5130	0.101*
H11B	0.7884	0.6333	0.4899	0.101*
C10A	0.6043 (5)	0.8612 (4)	0.1410 (3)	0.0903 (14)
H10C	0.5263	0.9163	0.1093	0.108*
H10D	0.5979	0.8819	0.2006	0.108*
C11A	0.6028 (6)	0.7183 (5)	0.1609 (4)	0.1021 (16)
H11C	0.5200	0.6990	0.2019	0.123*
H11D	0.6042	0.6987	0.1016	0.123*
C12A	0.8358 (6)	0.6631 (5)	0.1453 (4)	0.0981 (15)
H12A	0.8372	0.6439	0.0858	0.118*
H12B	0.9147	0.6058	0.1749	0.118*
C13A	0.8413 (5)	0.8063 (5)	0.1254 (3)	0.0891 (13)
H13C	0.8432	0.8247	0.1847	0.107*
H13D	0.9237	0.8242	0.0833	0.107*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1A	0.0642 (7)	0.1434 (12)	0.0830 (7)	0.0025 (6)	−0.0101 (5)	−0.0074 (7)
Cl2A	0.1463 (12)	0.0677 (6)	0.0801 (7)	−0.0009 (6)	−0.0480 (7)	−0.0055 (5)
Cl1B	0.0659 (6)	0.0812 (6)	0.0733 (6)	−0.0144 (4)	−0.0052 (4)	0.0004 (5)
Cl2B	0.0894 (7)	0.0689 (6)	0.0860 (7)	−0.0029 (5)	−0.0303 (6)	0.0038 (5)
O1A	0.103 (2)	0.0487 (13)	0.0634 (14)	−0.0233 (13)	−0.0033 (14)	0.0005 (10)
O1B	0.0822 (19)	0.0580 (14)	0.0736 (16)	−0.0170 (13)	0.0054 (14)	0.0013 (12)
O2A	0.140 (3)	0.0615 (18)	0.107 (2)	−0.0310 (19)	−0.007 (2)	0.0229 (17)
N1A	0.093 (2)	0.0423 (14)	0.0599 (16)	−0.0141 (13)	−0.0143 (15)	−0.0117 (11)
N2A	0.104 (2)	0.0353 (12)	0.0615 (16)	−0.0199 (14)	−0.0129 (16)	−0.0079 (11)
N3A	0.111 (3)	0.0380 (13)	0.0604 (17)	−0.0233 (15)	−0.0049 (17)	−0.0071 (12)
N4A	0.091 (2)	0.0345 (12)	0.0567 (15)	−0.0159 (12)	−0.0103 (14)	−0.0086 (10)
N5A	0.141 (3)	0.0398 (14)	0.0524 (16)	−0.0328 (17)	−0.0137 (18)	−0.0049 (11)
N1B	0.0775 (18)	0.0387 (12)	0.0530 (14)	−0.0143 (12)	−0.0109 (13)	−0.0074 (10)
N2B	0.0853 (19)	0.0319 (11)	0.0553 (14)	−0.0165 (11)	−0.0105 (13)	−0.0050 (10)
N3B	0.098 (2)	0.0383 (13)	0.0529 (14)	−0.0250 (14)	−0.0087 (14)	−0.0044 (11)
N4B	0.0663 (16)	0.0358 (12)	0.0547 (14)	−0.0158 (11)	−0.0050 (12)	−0.0083 (10)
N5B	0.092 (2)	0.0351 (12)	0.0519 (14)	−0.0197 (13)	−0.0083 (14)	−0.0050 (10)
C1A	0.0616 (18)	0.0427 (15)	0.0614 (18)	−0.0119 (13)	−0.0142 (15)	−0.0117 (13)
C2A	0.064 (2)	0.0551 (18)	0.0611 (19)	−0.0105 (15)	−0.0132 (16)	−0.0118 (14)
C3A	0.093 (3)	0.0525 (18)	0.0606 (19)	−0.0208 (18)	−0.0157 (19)	−0.0136 (15)
C4A	0.112 (4)	0.064 (2)	0.067 (2)	−0.040 (2)	−0.010 (2)	−0.0103 (17)
C5A	0.080 (3)	0.100 (3)	0.084 (3)	−0.040 (3)	0.014 (2)	−0.027 (2)
C6A	0.068 (2)	0.075 (2)	0.084 (3)	−0.0182 (19)	−0.006 (2)	−0.022 (2)
C7A	0.068 (2)	0.0409 (15)	0.0594 (18)	−0.0109 (13)	−0.0137 (15)	−0.0093 (13)
C8A	0.074 (2)	0.0379 (14)	0.0575 (17)	−0.0147 (13)	−0.0092 (15)	−0.0053 (12)
C9A	0.080 (2)	0.0371 (14)	0.0596 (18)	−0.0176 (14)	−0.0128 (16)	−0.0068 (12)
C1B	0.0676 (19)	0.0340 (13)	0.0544 (16)	−0.0135 (12)	−0.0105 (14)	−0.0077 (11)
C2B	0.070 (2)	0.0460 (16)	0.0545 (17)	−0.0195 (14)	−0.0086 (15)	−0.0074 (13)
C3B	0.078 (2)	0.0427 (15)	0.0609 (19)	−0.0148 (15)	−0.0172 (17)	−0.0031 (13)
C4B	0.092 (3)	0.0424 (16)	0.0562 (18)	−0.0207 (16)	−0.0127 (18)	−0.0001 (13)
C5B	0.081 (2)	0.0505 (17)	0.0582 (19)	−0.0240 (16)	0.0027 (17)	−0.0076 (14)
C6B	0.070 (2)	0.0440 (15)	0.0599 (18)	−0.0138 (14)	−0.0043 (16)	−0.0106 (13)
C7B	0.0573 (17)	0.0374 (14)	0.0559 (17)	−0.0124 (12)	−0.0080 (14)	−0.0064 (12)
C8B	0.0611 (18)	0.0389 (14)	0.0522 (16)	−0.0171 (12)	−0.0083 (13)	−0.0046 (12)
C9B	0.0600 (18)	0.0331 (13)	0.0553 (16)	−0.0125 (12)	−0.0077 (14)	−0.0036 (11)
C10B	0.115 (4)	0.057 (2)	0.068 (2)	−0.024 (2)	−0.019 (2)	0.0011 (17)
C11B	0.088 (3)	0.065 (2)	0.083 (3)	−0.014 (2)	−0.006 (2)	−0.0026 (19)
C10A	0.095 (3)	0.068 (2)	0.079 (3)	−0.009 (2)	0.009 (2)	0.000 (2)
C11A	0.096 (3)	0.075 (3)	0.112 (4)	−0.034 (3)	0.003 (3)	0.007 (3)
C12A	0.101 (4)	0.071 (3)	0.101 (3)	−0.002 (2)	−0.019 (3)	−0.004 (2)
C13A	0.102 (3)	0.086 (3)	0.078 (3)	−0.034 (3)	−0.013 (2)	−0.011 (2)

Geometric parameters (Å, º) top

Cl1A—C2A	1.708 (4)	C2A—C3A	1.389 (5)
Cl2A—C3A	1.742 (4)	C3A—C4A	1.362 (6)
Cl1B—C2B	1.726 (4)	C4A—C5A	1.367 (7)
Cl2B—C3B	1.721 (4)	C4A—H4A	0.9300
O1A—C10A	1.422 (5)	C5A—C6A	1.398 (6)
O1A—C13A	1.424 (6)	C5A—H5A	0.9300
O1B—C10B	1.406 (6)	C6A—H6A	0.9300
O1B—C11B	1.430 (5)	C7A—C9A	1.438 (5)
O2A—C12A	1.401 (7)	C1B—C6B	1.393 (5)
O2A—C11A	1.416 (7)	C1B—C2B	1.401 (5)
N1A—C7A	1.294 (4)	C1B—C7B	1.481 (4)
N1A—N2A	1.365 (4)	C2B—C3B	1.400 (4)
N2A—C8A	1.331 (5)	C3B—C4B	1.387 (6)
N3A—C8A	1.342 (4)	C4B—C5B	1.370 (6)
N3A—H13A	0.863 (10)	C4B—H4B	0.9300
N3A—H23A	0.858 (10)	C5B—C6B	1.392 (5)
N4A—C9A	1.326 (4)	C5B—H5B	0.9300
N4A—C8A	1.347 (4)	C6B—H6B	0.9300
N5A—C9A	1.336 (4)	C7B—C9B	1.433 (5)
N5A—H15A	0.858 (10)	C10B—C11Bⁱ	1.490 (7)
N5A—H25A	0.862 (10)	C10B—H10A	0.9700
N1B—C7B	1.317 (4)	C10B—H10B	0.9700
N1B—N2B	1.353 (4)	C11B—C10Bⁱ	1.490 (7)
N2B—C8B	1.339 (4)	C11B—H11A	0.9700
N3B—C8B	1.340 (4)	C11B—H11B	0.9700
N3B—H13B	0.861 (10)	C10A—C11A	1.473 (7)
N3B—H23B	0.861 (10)	C10A—H10C	0.9700
N4B—C9B	1.320 (4)	C10A—H10D	0.9700
N4B—C8B	1.349 (4)	C11A—H11C	0.9700
N5B—C9B	1.338 (4)	C11A—H11D	0.9700
N5B—H15B	0.859 (10)	C12A—C13A	1.487 (7)
N5B—H25B	0.861 (10)	C12A—H12A	0.9700
C1A—C6A	1.372 (5)	C12A—H12B	0.9700
C1A—C2A	1.398 (5)	C13A—H13C	0.9700
C1A—C7A	1.498 (4)	C13A—H13D	0.9700

C10A—O1A—C13A	110.1 (3)	C2B—C3B—Cl2B	120.9 (3)
C10B—O1B—C11B	109.2 (3)	C5B—C4B—C3B	120.5 (3)
C12A—O2A—C11A	109.0 (3)	C5B—C4B—H4B	119.7
C7A—N1A—N2A	120.1 (3)	C3B—C4B—H4B	119.7
C8A—N2A—N1A	117.8 (3)	C4B—C5B—C6B	120.5 (3)
C8A—N3A—H13A	122 (3)	C4B—C5B—H5B	119.7
C8A—N3A—H23A	112 (3)	C6B—C5B—H5B	119.7
H13A—N3A—H23A	126 (4)	C5B—C6B—C1B	120.4 (3)
C9A—N4A—C8A	115.8 (3)	C5B—C6B—H6B	119.8
C9A—N5A—H15A	119 (3)	C1B—C6B—H6B	119.8
C9A—N5A—H25A	124 (3)	N1B—C7B—C9B	120.0 (3)
H15A—N5A—H25A	117 (5)	N1B—C7B—C1B	118.5 (3)
C7B—N1B—N2B	119.9 (3)	C9B—C7B—C1B	121.5 (2)
C8B—N2B—N1B	117.6 (2)	N2B—C8B—N3B	117.1 (3)
C8B—N3B—H13B	116 (3)	N2B—C8B—N4B	125.6 (3)
C8B—N3B—H23B	122 (3)	N3B—C8B—N4B	117.2 (3)
H13B—N3B—H23B	119 (4)	N4B—C9B—N5B	118.8 (3)
C9B—N4B—C8B	116.0 (3)	N4B—C9B—C7B	120.0 (2)
C9B—N5B—H15B	117 (3)	N5B—C9B—C7B	121.1 (3)
C9B—N5B—H25B	116 (3)	O1B—C10B—C11Bⁱ	111.8 (4)
H15B—N5B—H25B	127 (4)	O1B—C10B—H10A	109.3
C6A—C1A—C2A	119.1 (3)	C11Bⁱ—C10B—H10A	109.3
C6A—C1A—C7A	120.4 (3)	O1B—C10B—H10B	109.3
C2A—C1A—C7A	120.6 (3)	C11Bⁱ—C10B—H10B	109.3
C3A—C2A—C1A	119.8 (4)	H10A—C10B—H10B	107.9
C3A—C2A—Cl1A	120.3 (3)	O1B—C11B—C10Bⁱ	109.8 (4)
C1A—C2A—Cl1A	119.9 (3)	O1B—C11B—H11A	109.7
C4A—C3A—C2A	120.8 (4)	C10Bⁱ—C11B—H11A	109.7
C4A—C3A—Cl2A	119.3 (3)	O1B—C11B—H11B	109.7
C2A—C3A—Cl2A	119.9 (3)	C10Bⁱ—C11B—H11B	109.7
C3A—C4A—C5A	119.5 (4)	H11A—C11B—H11B	108.2
C3A—C4A—H4A	120.3	O1A—C10A—C11A	110.5 (4)
C5A—C4A—H4A	120.3	O1A—C10A—H10C	109.5
C4A—C5A—C6A	120.9 (4)	C11A—C10A—H10C	109.5
C4A—C5A—H5A	119.6	O1A—C10A—H10D	109.5
C6A—C5A—H5A	119.6	C11A—C10A—H10D	109.5
C1A—C6A—C5A	119.9 (4)	H10C—C10A—H10D	108.1
C1A—C6A—H6A	120.1	O2A—C11A—C10A	110.3 (5)
C5A—C6A—H6A	120.1	O2A—C11A—H11C	109.6
N1A—C7A—C9A	120.4 (3)	C10A—C11A—H11C	109.6
N1A—C7A—C1A	118.4 (3)	O2A—C11A—H11D	109.6
C9A—C7A—C1A	121.2 (3)	C10A—C11A—H11D	109.6
N2A—C8A—N3A	117.2 (3)	H11C—C11A—H11D	108.1
N2A—C8A—N4A	125.8 (3)	O2A—C12A—C13A	110.0 (4)
N3A—C8A—N4A	117.0 (3)	O2A—C12A—H12A	109.7
N4A—C9A—N5A	118.3 (3)	C13A—C12A—H12A	109.7
N4A—C9A—C7A	120.1 (3)	O2A—C12A—H12B	109.7
N5A—C9A—C7A	121.6 (3)	C13A—C12A—H12B	109.7
C6B—C1B—C2B	118.7 (3)	H12A—C12A—H12B	108.2
C6B—C1B—C7B	122.0 (3)	O1A—C13A—C12A	110.1 (4)
C2B—C1B—C7B	119.3 (3)	O1A—C13A—H13C	109.6
C3B—C2B—C1B	120.5 (3)	C12A—C13A—H13C	109.6
C3B—C2B—Cl1B	119.8 (3)	O1A—C13A—H13D	109.6
C1B—C2B—Cl1B	119.7 (2)	C12A—C13A—H13D	109.6
C4B—C3B—C2B	119.4 (3)	H13C—C13A—H13D	108.2
C4B—C3B—Cl2B	119.7 (3)

C7A—N1A—N2A—C8A	−0.2 (6)	C7B—C1B—C2B—Cl1B	−3.3 (4)
C7B—N1B—N2B—C8B	3.0 (5)	C1B—C2B—C3B—C4B	1.4 (5)
C6A—C1A—C2A—C3A	−0.3 (5)	Cl1B—C2B—C3B—C4B	−177.6 (3)
C7A—C1A—C2A—C3A	178.8 (3)	C1B—C2B—C3B—Cl2B	−179.5 (2)
C6A—C1A—C2A—Cl1A	177.7 (3)	Cl1B—C2B—C3B—Cl2B	1.5 (4)
C7A—C1A—C2A—Cl1A	−3.2 (4)	C2B—C3B—C4B—C5B	−0.8 (5)
C1A—C2A—C3A—C4A	0.3 (5)	Cl2B—C3B—C4B—C5B	−180.0 (3)
Cl1A—C2A—C3A—C4A	−177.8 (3)	C3B—C4B—C5B—C6B	−0.5 (5)
C1A—C2A—C3A—Cl2A	179.5 (3)	C4B—C5B—C6B—C1B	1.2 (5)
Cl1A—C2A—C3A—Cl2A	1.4 (4)	C2B—C1B—C6B—C5B	−0.7 (5)
C2A—C3A—C4A—C5A	0.2 (6)	C7B—C1B—C6B—C5B	−178.9 (3)
Cl2A—C3A—C4A—C5A	−179.0 (3)	N2B—N1B—C7B—C9B	5.1 (5)
C3A—C4A—C5A—C6A	−0.7 (7)	N2B—N1B—C7B—C1B	−176.1 (3)
C2A—C1A—C6A—C5A	−0.1 (6)	C6B—C1B—C7B—N1B	−74.9 (4)
C7A—C1A—C6A—C5A	−179.2 (3)	C2B—C1B—C7B—N1B	106.9 (4)
C4A—C5A—C6A—C1A	0.6 (7)	C6B—C1B—C7B—C9B	104.0 (4)
N2A—N1A—C7A—C9A	2.4 (6)	C2B—C1B—C7B—C9B	−74.3 (4)
N2A—N1A—C7A—C1A	179.3 (3)	N1B—N2B—C8B—N3B	171.1 (3)
C6A—C1A—C7A—N1A	−72.4 (5)	N1B—N2B—C8B—N4B	−8.0 (5)
C2A—C1A—C7A—N1A	108.4 (4)	C9B—N4B—C8B—N2B	3.8 (5)
C6A—C1A—C7A—C9A	104.5 (4)	C9B—N4B—C8B—N3B	−175.3 (3)
C2A—C1A—C7A—C9A	−74.6 (4)	C8B—N4B—C9B—N5B	−175.4 (3)
N1A—N2A—C8A—N3A	178.4 (3)	C8B—N4B—C9B—C7B	4.8 (4)
N1A—N2A—C8A—N4A	−2.2 (6)	N1B—C7B—C9B—N4B	−9.3 (5)
C9A—N4A—C8A—N2A	2.1 (6)	C1B—C7B—C9B—N4B	171.9 (3)
C9A—N4A—C8A—N3A	−178.5 (4)	N1B—C7B—C9B—N5B	170.8 (3)
C8A—N4A—C9A—N5A	−178.9 (4)	C1B—C7B—C9B—N5B	−8.0 (5)
C8A—N4A—C9A—C7A	0.2 (5)	C11B—O1B—C10B—C11Bⁱ	−58.2 (5)
N1A—C7A—C9A—N4A	−2.4 (6)	C10B—O1B—C11B—C10Bⁱ	57.1 (5)
C1A—C7A—C9A—N4A	−179.2 (3)	C13A—O1A—C10A—C11A	−56.2 (6)
N1A—C7A—C9A—N5A	176.6 (4)	C12A—O2A—C11A—C10A	−60.6 (6)
C1A—C7A—C9A—N5A	−0.2 (6)	O1A—C10A—C11A—O2A	58.5 (6)
C6B—C1B—C2B—C3B	−0.6 (5)	C11A—O2A—C12A—C13A	60.8 (6)
C7B—C1B—C2B—C3B	177.7 (3)	C10A—O1A—C13A—C12A	56.4 (5)
C6B—C1B—C2B—Cl1B	178.4 (2)	O2A—C12A—C13A—O1A	−59.3 (6)

Symmetry code: (i) −x+2, −y+1, −z+1.

Acknowledgements

GP acknowledges Assoc. Professor Boris-Marko Kukovec from University of Split, Faculty of Chemistry and Technology, for providing the overlay diagram. There are no conflicts to declare.

References

Aakeröy, C. B. & Salmon, D. J. (2005). CrystEngComm, 7, 439–448. Web of Science CrossRef Google Scholar
Agilent (2010). CrysAlisPro, CrysAlis CCD and CrysAlis RED. Agilent Technologies (now Rigaku Oxford Diffraction), Yarnton, England. Google Scholar
Almarsson, Ö., Peterson, M. L. & Zaworotko, M. J. (2012). Pharm. Patent Anal. 1, 313–327. Google Scholar
Bernstein, J. (2007). Polymorphism in Molecular Crystals, International Union of Crystallography Monographs on Crystallography 14. Oxford University Press. Google Scholar
Bolla, G., Sarma, B. & Nangia, A. K. (2022). Chem. Rev. 122, 11514–11603. Web of Science CrossRef CAS PubMed Google Scholar
Braga, D., Grepioni, F. & Maini, L. (2010). Chem. Commun. 46, 6232–6242. Web of Science CrossRef CAS Google Scholar
Chadha, R., Saini, A., Arora, P., Jain, D. S., Dasgupta, A. & Guru Row, T. N. (2011). CrystEngComm, 13, 6271–6284. Web of Science CSD CrossRef CAS Google Scholar
Cheney, M. L., Shan, N., Healey, E. R., Hanna, M., Wojtas, L., Zaworotko, M. J., Sava, V., Song, S. & Sanchez-Ramos, J. R. (2010). Cryst. Growth Des. 10, 394–405. Web of Science CSD CrossRef CAS Google Scholar
Desiraju, G. R. (1995). Angew. Chem. Int. Ed. Engl. 34, 2311–2327. CrossRef CAS Web of Science Google Scholar
Duggirala, N. K., Perry, M. L., Almarsson, O. & Zaworotko, M. J. (2016). Chem. Commun. 52, 640–655. Web of Science CrossRef CAS Google Scholar
Etter, M. C. (1990). Acc. Chem. Res. 23, 120–126. CrossRef CAS Web of Science Google Scholar
Etter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256–262. CrossRef ICSD CAS Web of Science IUCr Journals Google Scholar
Évora, A. O. L., Castro, R. A. E., Maria, T. M. R., Ramos Silva, M., Canotilho, J. & Eusébio, E. S. (2019). Eur. J. Pharm. Sci. 129, 148–162. Web of Science PubMed Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Griesser, U. J. (2006). In Polymorphism: in the Pharmaceutical Industry, edited by R. Hilfiker, pp. 211–230. Wiley-VCH. Google Scholar
Hall, C. L., Potticary, J., Sparkes, H. A., Pridmore, N. E. & Hall, S. R. (2018). Acta Cryst. E74, 678–681. CSD CrossRef IUCr Journals Google Scholar
Haskins, M. M., Lusi, M. & Zaworotko, M. J. (2022). Cryst. Growth Des. 22, 3333–3342. Web of Science CSD CrossRef CAS PubMed Google Scholar
Khankari, R. K. & Grant, D. J. W. (1995). Thermochim. Acta, 248, 61–79. CrossRef CAS Web of Science Google Scholar
Kubicki, M. & Codding, P. W. (2001). J. Mol. Struct. 570, 53–60. Web of Science CSD CrossRef CAS Google Scholar
Lekšić, E. (2013). PhD thesis. University of Zagreb, Croatia. Google Scholar
Lekšić, E., Pavlović, G. & Meštrović, E. (2010). Cryst. Growth Des. 12, 1847–1858. Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CrossRef CAS IUCr Journals Google Scholar
Morris, K. R. (1999). In Polymorphism in Pharmaceutical Solids, edited by H. G. Brittain, pp. 125–181. Marcel Dekker, Inc. Google Scholar
Nardelli, M. (1983). Comput. Chem. 7, 95–98. CrossRef CAS Web of Science Google Scholar
Nardelli, M. (1995). J. Appl. Cryst. 28, 659–659. CrossRef CAS IUCr Journals Google Scholar
Qian, Y., Lv, P.-C., Shi, L., Fang, R.-Q., Song, Z.-C. & Zhu, H.-L. (2009). J. Chem. Sci. 121, 463–470. Web of Science CSD CrossRef CAS Google Scholar
Rodriguez-Hornedo, N., Nehm, S. J. & Jayasankar, A. (2007). Cocrystals. In Design, Properties and Formation Mechanisms, Encyclopedia of Pharmaceutical Technology, edited by J. Swarbrick, 3rd ed., pp. 615–635. InformaHealth Care. Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sridhar, B. & Ravikumar, K. (2011). J. Chem. Crystallogr. 41, 1289–1300. Web of Science CSD CrossRef CAS Google Scholar
Trask, A. V. (2007). Mol. Pharm. 4, 301–309. Web of Science CrossRef PubMed CAS Google Scholar

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research papers\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Supramolecular synthons in hydrates and solvates of lamotrigine: a tool for cocrystal design

1. Introduction

2. Materials and methods

2.1. Materials

2.2. Synthesis of the LAM hydrates and solvates

2.3. Single-crystal X-ray diffraction

3. Results and discussion

3.1. Analysis of supramolecular synthons

3.1.1. Robustness of LAM amino­pyridine synthon 1 in LAM solvates: P-P versus O-O topology

3.1.2. Emulation of LAM synthon 2

3.1.3. Supramolecular relationship of amino­pyridine synthon 1 [R22(8)] and topologically identical synthon B

4. Conclusion

Supporting information

Acknowledgements

References

research papers

3.1.1. Robustness of LAM aminopyridine synthon 1 in LAM solvates: P-P versus O-O topology

3.1.3. Supramolecular relationship of aminopyridine synthon 1 [R²₂(8)] and topologically identical synthon B