2-[6-(1H-Benzimidazol-2-yl)-2-pyridyl]-1H-benzimidazol-3-ium perchlorate monohydrate

Boča, M.; Valigura, D.; Svoboda, I.; Fuess, H.; Linert, W.

doi:10.1107/S0108270100004376

2-[6-(1H-Benzimidazol-2-yl)-2-pyridyl]-1H-benzimidazol-3-ium perchlorate monohydrate

M. Boca, D. Valigura, I. Svoboda, H. Fuess and W. Linert

The title compound, C₁₉H₁₄N₅⁺·ClO₄^-·H₂O, contains planar C₁₉H₁₄N₅⁺ cations, perchlorate anions and water molecules. The two closest parallel cations (plane-to-plane distance of 3.41 Å), together with two neighbouring perchlorate anions and two water molecules, form an electrically neutral quasi-dimeric unit. Two acidic H atoms of the cation, both H atoms of the water molecule, the N atoms of the imidazole rings and three of the four O atoms of the perchlorate anion are involved in the hydrogen-bonding network within the dimeric unit. The remaining third acidic H atom of the imidazole rings and the water molecules complete a two-dimensional network of hydrogen bonds, thus forming puckered layers of dimers. The angle between the planes of two neighbouring dimeric units in the same layer is 33.25 (3)°.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100004376/ln1095sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S0108270100004376/ln1095Isup2.hkl Contains datablock I

CCDC reference: 147649

Comment top

Complexes of 2,6-bis(benzimidazol-2-yl)pyridine and its derivatives have been studied for more than 30 years because of their unusual coordination properties (Rüttimanm et al., 1992) and unusual magnetic properties (Gütlich, 1981; Boča et al., 1998). However, the structures of the free ligands are reported only occasionally. We are aware of only one such example, the structure of 2-(1-methyl-3-benzimidazolinium-2-yl)-6-(1-methylbenzimidazol- 2-yl)pyridine perchlorate, (II) (Petoud et al., 1997). Here, we present the structure of the title compound, a similar free ligand as its perchlorate monohydrate, (I). \sch

A view of (I) is shown in Fig. 1 and selected bond lengths and angles are given in Table 1. A l l C and N atoms of the cation lie on one almost perfect plane. The mean deviation from this plane is 0.052 Å and the greatest deviation is 0.108 (2) Å for C4. In contrast, the corresponding cation in compound (II) is quite bent, with the planes of the benzimidazole units forming angles of about 30.5 and 45.3° with that of the central pyridine ring because of steric interactions between the opposing methyl groups that are in a cis-cis position with respect to the pyridine N atom. The positions of N3 and N5 are trans-trans with respect to N1. A similar conformation was observed in (II). In all metal complexes this position changes to cis-cis.

The aromatic C—C and C—N distances from both the benzimidazole and pyridine rings are within the usual range and this confirms the aromatic character of the pyridine and benzimidazole moieties. The protonation of the atom N5 has no influence on the aromatic character of the benzimidazole moiety.

The structure of (I) contains cations stacked along the a axis. The neighbouring cations from adjacent stacks form a puckered layer in which the angle between the planes of adjacent cations is 33.25 (3)°. Pairs of puckered layers are held together by a system of hydrogen bonds involving the H atoms of the water molecules, the N atoms of the benzimidazole moieties and the O atoms of the perchlorate anions, and by van der Waals interactions. The hydrogen-bonding system (Table 2) thus connects together two stacked cations to form a quasi-dimeric unit with a plane-to-plane distance of 3.41 Å. Additional hydrogen bonds involving the water molecules and H14 of the benzimidazole moieties connect the quasi-dimers end on, to form the extended stacked puckered layers. Adjacent bilayers of dimers are held together by van der Waals interactions. It is very interesting that the interplanar distance between neighbouring cations that do not interconnect via hydrogen bonds is very similar (3.4 Å) to that for the cations that are linked by the hydrogen-bonding system.

The π-stacking found in (II) was not observed for (I); thus, an interaction of the π orbitals of two cations is not facilitated. The proton originating from the perchloric acid is localized on the N5 atom and interacts with the O atom from the water molecule, thus forming interdimer hydrogen bonds. In compound (II), the acid H atoms are involved in hydrogen bonds between the unprotonated benzimidazole unit of one cation and the protonated unit of an adjacent cation, and vice versa, thus forming a quasi-dimeric unit (Petoud et al., 1997). The hydrogen-bonding network in (I) is shown in Fig. 2.

Experimental top

Single crystals of (I) suitable for X-ray analysis were obtained from a mixture of Fe(ClO₄)₃.10H₂O (0.267 g, 0.5 mmol) in ethanol (10 ml) and 2,6-bis(benzimidazol-2-yl)pyridine (0.311 g, 1 mmol) in ethanol (20 ml) after two weeks at room temperature. This was actually an attempt to obtain an iron(III) perchlorate complex of the ligand. Single crystals denature above 353 K due to the loss of water, but they do not melt until 533 K.

Computing details top

Data collection: CAD-4 Diffractometer Control Software (Enraf-Nonius, 1993); cell refinement: CAD-4 Diffractometer Control Software; data reduction: REDU4 (Stoe & Cie, 1988); program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1998); software used to prepare material for publication: SHELXL97.

Figures top

	Fig. 1. The structure and atom-numbering scheme of (I), showing 50% probability displacement ellipsoids. H atoms are shown as circles of arbitrary radius.
	Fig. 2. A packing diagram illustrating the hydrogen-bonding network in (I) and the system of puckered layers.

2-(1,3-Benzimidazol-2-io)-6-(1,3-benzimidazol-2-yl)pyridine perchlorate monohydrate top

Crystal data top

C₁₉H₁₄N₅·ClO₄·H₂O	D_x = 1.509 Mg m⁻³
M_r = 429.82	Melting point: >533 K K
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71093 Å
a = 9.168 (2) Å	Cell parameters from 25 reflections
b = 15.111 (3) Å	θ = 3.0–11.6°
c = 13.962 (3) Å	µ = 0.25 mm⁻¹
β = 101.98 (2)°	T = 304 K
V = 1892.1 (7) Å³	Needle, colourless
Z = 4	0.75 × 0.20 × 0.20 mm
F(000) = 888

Data collection top

Enraf-Nonius CAD4 diffractometer	2847 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.046
Graphite monochromator	θ_max = 26.0°, θ_min = 2.0°
ω/2θ scans	h = −11→2
Absorption correction: ψ-scan (North et al., 1968)	k = −18→0
T_min = 0.837, T_max = 0.952	l = −17→17
4491 measured reflections	3 standard reflections every 120 min
3716 independent reflections	intensity decay: 9.8%

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.041	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.125	Calculated w = 1/[σ²(F_o²) + (0.0728P)² + 0.5099P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.001
3716 reflections	Δρ_max = 0.26 e Å⁻³
322 parameters	Δρ_min = −0.36 e Å⁻³
7 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0026 (11)

Crystal data top

C₁₉H₁₄N₅·ClO₄·H₂O	V = 1892.1 (7) Å³
M_r = 429.82	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.168 (2) Å	µ = 0.25 mm⁻¹
b = 15.111 (3) Å	T = 304 K
c = 13.962 (3) Å	0.75 × 0.20 × 0.20 mm
β = 101.98 (2)°

Data collection top

Enraf-Nonius CAD4 diffractometer	2847 reflections with I > 2σ(I)
Absorption correction: ψ-scan (North et al., 1968)	R_int = 0.046
T_min = 0.837, T_max = 0.952	3 standard reflections every 120 min
4491 measured reflections	intensity decay: 9.8%
3716 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	7 restraints
wR(F²) = 0.125	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.26 e Å⁻³
3716 reflections	Δρ_min = −0.36 e Å⁻³
322 parameters

Special details top

Experimental. The size of the collimator was 0.8 mm.

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

Refinement. Refinement on F² for ALL reflections except for 0 with very negative F² or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating _R_factor_obs etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cl1	0.16383 (6)	0.77420 (4)	0.93722 (4)	0.04998 (18)
N1	0.20055 (17)	0.57133 (11)	0.50065 (11)	0.0387 (4)
N2	0.13392 (19)	0.47630 (11)	0.65879 (12)	0.0419 (4)
H4	0.185 (3)	0.4471 (18)	0.6280 (19)	0.066 (8)*
N5	0.36428 (18)	0.60336 (11)	0.28842 (12)	0.0416 (4)
H14	0.351 (3)	0.6618 (18)	0.2653 (17)	0.061 (7)*
N4	0.36143 (18)	0.48703 (11)	0.37923 (12)	0.0423 (4)
H9	0.335 (3)	0.4511 (17)	0.4261 (18)	0.061 (7)*
C13	0.3175 (2)	0.57084 (12)	0.36520 (13)	0.0384 (4)
C6	0.0892 (2)	0.56049 (13)	0.64022 (13)	0.0391 (4)
N3	0.00878 (18)	0.59072 (11)	0.70164 (12)	0.0426 (4)
C5	0.1293 (2)	0.61341 (13)	0.56145 (14)	0.0398 (4)
C1	0.2349 (2)	0.61944 (13)	0.42772 (13)	0.0383 (4)
C12	0.0021 (2)	0.52080 (13)	0.76458 (13)	0.0406 (4)
C19	0.4409 (2)	0.53770 (13)	0.25045 (14)	0.0423 (4)
C2	0.2000 (2)	0.70780 (14)	0.41210 (16)	0.0477 (5)
H1	0.2233	0.7380	0.3592	0.057*
C7	0.0806 (2)	0.44821 (13)	0.73895 (14)	0.0415 (4)
C14	0.4388 (2)	0.46332 (13)	0.30806 (14)	0.0424 (4)
C11	−0.0677 (2)	0.51506 (15)	0.84440 (15)	0.0492 (5)
H8	−0.1203	0.5627	0.8624	0.059*
C18	0.5098 (3)	0.53745 (16)	0.17092 (16)	0.0545 (5)
H13	0.5094	0.5872	0.1316	0.065*
C17	0.5782 (3)	0.46066 (17)	0.15312 (18)	0.0614 (6)
H12	0.6263	0.4582	0.1007	0.074*
C10	−0.0560 (3)	0.43728 (16)	0.89485 (15)	0.0557 (6)
H7	−0.1034	0.4316	0.9473	0.067*
C16	0.5777 (3)	0.38597 (16)	0.21158 (18)	0.0607 (6)
H11	0.6260	0.3351	0.1972	0.073*
C15	0.5083 (2)	0.38510 (15)	0.28975 (17)	0.0533 (5)
H10	0.5078	0.3350	0.3283	0.064*
C3	0.1295 (3)	0.74988 (15)	0.47726 (18)	0.0551 (6)
H2	0.1060	0.8097	0.4699	0.066*
C4	0.0943 (2)	0.70257 (14)	0.55304 (16)	0.0509 (5)
H3	0.0475	0.7300	0.5982	0.061*
C8	0.0950 (3)	0.36991 (14)	0.79155 (16)	0.0534 (5)
H5	0.1491	0.3223	0.7749	0.064*
C9	0.0251 (3)	0.36604 (15)	0.86967 (16)	0.0577 (6)
H6	0.0323	0.3145	0.9067	0.069*
O1	0.1782 (2)	0.26268 (12)	0.29595 (14)	0.0567 (4)
H15	0.216 (3)	0.2594 (19)	0.352 (2)	0.067 (9)*
H16	0.121 (4)	0.305 (2)	0.289 (2)	0.085 (10)*
O2	0.2635 (2)	0.71005 (14)	0.98700 (16)	0.0825 (6)
O3	0.1728 (8)	0.7800 (4)	0.8351 (4)	0.0757 (15)	0.553 (9)
O7	0.0188 (6)	0.7619 (6)	0.9455 (7)	0.120 (4)	0.553 (9)
O5	0.2153 (8)	0.8640 (3)	0.9740 (3)	0.109 (2)	0.553 (9)
O8	0.0288 (8)	0.7249 (4)	0.9028 (5)	0.0725 (18)	0.447 (9)
O6	0.1348 (7)	0.8294 (4)	1.0109 (4)	0.096 (3)	0.447 (9)
O4	0.2131 (10)	0.8116 (6)	0.8650 (7)	0.092 (2)	0.447 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0475 (3)	0.0548 (3)	0.0512 (3)	0.0017 (2)	0.0183 (2)	−0.0021 (2)
N1	0.0373 (8)	0.0401 (8)	0.0416 (8)	−0.0012 (6)	0.0147 (7)	0.0024 (7)
N2	0.0471 (9)	0.0398 (9)	0.0447 (9)	0.0016 (7)	0.0232 (7)	0.0001 (7)
N5	0.0479 (9)	0.0372 (9)	0.0438 (9)	−0.0042 (7)	0.0193 (7)	0.0008 (7)
N4	0.0448 (9)	0.0391 (9)	0.0467 (9)	−0.0014 (7)	0.0179 (7)	0.0047 (7)
C13	0.0373 (10)	0.0389 (10)	0.0413 (9)	−0.0051 (8)	0.0132 (8)	0.0020 (8)
C6	0.0393 (10)	0.0395 (10)	0.0414 (10)	−0.0006 (7)	0.0151 (8)	0.0007 (8)
N3	0.0445 (9)	0.0414 (9)	0.0469 (9)	0.0010 (7)	0.0214 (7)	0.0010 (7)
C5	0.0347 (9)	0.0433 (10)	0.0439 (10)	−0.0001 (7)	0.0137 (8)	0.0030 (8)
C1	0.0341 (9)	0.0412 (10)	0.0416 (10)	−0.0017 (7)	0.0125 (8)	0.0025 (8)
C12	0.0416 (10)	0.0428 (10)	0.0396 (9)	−0.0055 (8)	0.0136 (8)	−0.0023 (8)
C19	0.0426 (10)	0.0414 (10)	0.0459 (10)	−0.0075 (8)	0.0160 (8)	−0.0046 (8)
C2	0.0473 (11)	0.0468 (11)	0.0541 (11)	0.0048 (9)	0.0226 (9)	0.0126 (9)
C7	0.0436 (10)	0.0430 (10)	0.0407 (10)	−0.0062 (8)	0.0155 (8)	−0.0011 (8)
C14	0.0389 (10)	0.0427 (10)	0.0477 (10)	−0.0059 (8)	0.0137 (8)	−0.0039 (8)
C11	0.0518 (12)	0.0545 (12)	0.0470 (11)	−0.0063 (9)	0.0237 (9)	−0.0079 (9)
C18	0.0619 (13)	0.0558 (13)	0.0533 (12)	−0.0101 (10)	0.0291 (10)	−0.0049 (10)
C17	0.0623 (14)	0.0688 (16)	0.0617 (14)	−0.0084 (11)	0.0325 (11)	−0.0189 (12)
C10	0.0667 (14)	0.0619 (14)	0.0449 (11)	−0.0192 (11)	0.0261 (10)	−0.0039 (10)
C16	0.0540 (13)	0.0569 (14)	0.0745 (15)	0.0021 (10)	0.0211 (11)	−0.0209 (12)
C15	0.0537 (13)	0.0437 (12)	0.0642 (13)	0.0007 (9)	0.0165 (11)	−0.0035 (10)
C3	0.0586 (13)	0.0423 (11)	0.0717 (14)	0.0130 (10)	0.0301 (11)	0.0131 (10)
C4	0.0510 (12)	0.0479 (11)	0.0615 (12)	0.0099 (9)	0.0297 (10)	0.0068 (10)
C8	0.0681 (14)	0.0414 (11)	0.0562 (12)	−0.0010 (10)	0.0252 (11)	0.0035 (9)
C9	0.0754 (16)	0.0480 (12)	0.0540 (12)	−0.0125 (11)	0.0237 (11)	0.0059 (10)
O1	0.0615 (10)	0.0526 (10)	0.0566 (11)	0.0142 (8)	0.0139 (8)	−0.0129 (8)
O2	0.0607 (11)	0.0836 (14)	0.0992 (14)	0.0086 (9)	0.0074 (10)	0.0200 (11)
O3	0.092 (4)	0.081 (4)	0.058 (2)	0.001 (3)	0.027 (2)	−0.001 (2)
O7	0.048 (2)	0.176 (8)	0.150 (7)	0.031 (4)	0.054 (4)	0.100 (6)
O5	0.186 (6)	0.064 (3)	0.093 (3)	−0.014 (3)	0.070 (3)	−0.025 (2)
O8	0.050 (3)	0.079 (3)	0.084 (4)	−0.021 (2)	0.003 (2)	−0.001 (3)
O6	0.136 (5)	0.072 (3)	0.092 (4)	−0.019 (3)	0.052 (3)	−0.039 (3)
O4	0.125 (6)	0.083 (5)	0.084 (5)	−0.033 (4)	0.057 (4)	0.018 (4)

Geometric parameters (Å, º) top

Cl1—O4	1.316 (6)	C19—C14	1.385 (3)
Cl1—O7	1.371 (5)	C19—C18	1.387 (3)
Cl1—O6	1.392 (4)	C2—C3	1.376 (3)
Cl1—O2	1.412 (2)	C2—H1	0.9300
Cl1—O8	1.439 (6)	C7—C8	1.384 (3)
Cl1—O3	1.448 (5)	C14—C15	1.392 (3)
Cl1—O5	1.492 (5)	C11—C10	1.363 (3)
N1—C5	1.335 (2)	C11—H8	0.9300
N1—C1	1.341 (2)	C18—C17	1.366 (3)
N2—C6	1.345 (3)	C18—H13	0.9300
N2—C7	1.378 (2)	C17—C16	1.393 (4)
N2—H4	0.83 (3)	C17—H12	0.9300
N5—C13	1.329 (2)	C10—C9	1.394 (3)
N5—C19	1.383 (3)	C10—H7	0.9300
N5—H14	0.94 (3)	C16—C15	1.373 (3)
N4—C13	1.331 (3)	C16—H11	0.9300
N4—C14	1.382 (2)	C15—H10	0.9300
N4—H9	0.92 (3)	C3—C4	1.370 (3)
C13—C1	1.466 (3)	C3—H2	0.9300
C6—N3	1.323 (2)	C4—H3	0.9300
C6—C5	1.467 (3)	C8—C9	1.376 (3)
N3—C12	1.384 (2)	C8—H5	0.9300
C5—C4	1.384 (3)	C9—H6	0.9300
C1—C2	1.380 (3)	O1—H15	0.79 (3)
C12—C11	1.398 (3)	O1—H16	0.82 (4)
C12—C7	1.399 (3)

O4—Cl1—O7	128.1 (5)	N3—C12—C7	110.10 (16)
O4—Cl1—O6	117.2 (4)	C11—C12—C7	120.01 (19)
O7—Cl1—O6	71.4 (5)	N5—C19—C14	106.85 (16)
O4—Cl1—O2	112.5 (4)	N5—C19—C18	131.4 (2)
O7—Cl1—O2	113.9 (3)	C14—C19—C18	121.78 (19)
O6—Cl1—O2	104.6 (3)	C3—C2—C1	117.91 (18)
O4—Cl1—O8	112.0 (5)	C3—C2—H1	121.0
O7—Cl1—O8	34.5 (3)	C1—C2—H1	121.0
O6—Cl1—O8	105.9 (3)	N2—C7—C8	133.11 (19)
O2—Cl1—O8	103.5 (3)	N2—C7—C12	104.73 (17)
O4—Cl1—O3	28.4 (3)	C8—C7—C12	122.14 (18)
O7—Cl1—O3	110.2 (4)	N4—C14—C19	106.17 (17)
O6—Cl1—O3	138.6 (4)	N4—C14—C15	132.46 (19)
O2—Cl1—O3	111.3 (3)	C19—C14—C15	121.36 (19)
O8—Cl1—O3	85.6 (3)	C10—C11—C12	117.7 (2)
O4—Cl1—O5	74.8 (4)	C10—C11—H8	121.1
O7—Cl1—O5	109.7 (4)	C12—C11—H8	121.1
O6—Cl1—O5	45.3 (2)	C17—C18—C19	116.8 (2)
O2—Cl1—O5	109.2 (2)	C17—C18—H13	121.6
O8—Cl1—O5	140.7 (3)	C19—C18—H13	121.6
O3—Cl1—O5	101.8 (3)	C18—C17—C16	121.6 (2)
C5—N1—C1	116.59 (16)	C18—C17—H12	119.2
C6—N2—C7	107.61 (16)	C16—C17—H12	119.2
C6—N2—H4	126.0 (19)	C11—C10—C9	121.61 (19)
C7—N2—H4	126.4 (19)	C11—C10—H7	119.2
C13—N5—C19	108.59 (17)	C9—C10—H7	119.2
C13—N5—H14	125.9 (14)	C15—C16—C17	122.1 (2)
C19—N5—H14	125.5 (15)	C15—C16—H11	118.9
C13—N4—C14	109.00 (16)	C17—C16—H11	118.9
C13—N4—H9	123.5 (16)	C16—C15—C14	116.3 (2)
C14—N4—H9	127.3 (16)	C16—C15—H10	121.8
N5—C13—N4	109.38 (16)	C14—C15—H10	121.8
N5—C13—C1	126.04 (17)	C4—C3—C2	119.2 (2)
N4—C13—C1	124.55 (16)	C4—C3—H2	120.4
N3—C6—N2	112.97 (16)	C2—C3—H2	120.4
N3—C6—C5	123.91 (18)	C3—C4—C5	119.07 (19)
N2—C6—C5	123.10 (16)	C3—C4—H3	120.5
C6—N3—C12	104.59 (16)	C5—C4—H3	120.5
N1—C5—C4	123.05 (17)	C9—C8—C7	116.6 (2)
N1—C5—C6	116.68 (17)	C9—C8—H5	121.7
C4—C5—C6	120.27 (17)	C7—C8—H5	121.7
N1—C1—C2	124.15 (17)	C8—C9—C10	121.8 (2)
N1—C1—C13	114.35 (16)	C8—C9—H6	119.1
C2—C1—C13	121.49 (17)	C10—C9—H6	119.1
N3—C12—C11	129.89 (19)	H15—O1—H16	108 (3)

C19—N5—C13—N4	0.5 (2)	N3—C12—C7—N2	−0.2 (2)
C19—N5—C13—C1	178.46 (17)	C11—C12—C7—N2	180.00 (18)
C14—N4—C13—N5	−0.7 (2)	N3—C12—C7—C8	178.38 (19)
C14—N4—C13—C1	−178.72 (17)	C11—C12—C7—C8	−1.4 (3)
C7—N2—C6—N3	−0.5 (2)	C13—N4—C14—C19	0.6 (2)
C7—N2—C6—C5	178.02 (17)	C13—N4—C14—C15	179.5 (2)
N2—C6—N3—C12	0.3 (2)	N5—C19—C14—N4	−0.3 (2)
C5—C6—N3—C12	−178.17 (18)	C18—C19—C14—N4	−179.81 (19)
C1—N1—C5—C4	−1.5 (3)	N5—C19—C14—C15	−179.32 (19)
C1—N1—C5—C6	178.90 (16)	C18—C19—C14—C15	1.2 (3)
N3—C6—C5—N1	−174.67 (18)	N3—C12—C11—C10	−179.7 (2)
N2—C6—C5—N1	7.0 (3)	C7—C12—C11—C10	0.0 (3)
N3—C6—C5—C4	5.7 (3)	N5—C19—C18—C17	179.4 (2)
N2—C6—C5—C4	−172.6 (2)	C14—C19—C18—C17	−1.3 (3)
C5—N1—C1—C2	−0.7 (3)	C19—C18—C17—C16	0.5 (4)
C5—N1—C1—C13	178.00 (16)	C12—C11—C10—C9	1.3 (3)
N5—C13—C1—N1	179.97 (17)	C18—C17—C16—C15	0.3 (4)
N4—C13—C1—N1	−2.4 (3)	C17—C16—C15—C14	−0.4 (3)
N5—C13—C1—C2	−1.3 (3)	N4—C14—C15—C16	−179.0 (2)
N4—C13—C1—C2	176.35 (19)	C19—C14—C15—C16	−0.4 (3)
C6—N3—C12—C11	179.7 (2)	C1—C2—C3—C4	−1.3 (3)
C6—N3—C12—C7	0.0 (2)	C2—C3—C4—C5	−0.6 (4)
C13—N5—C19—C14	−0.1 (2)	N1—C5—C4—C3	2.2 (3)
C13—N5—C19—C18	179.3 (2)	C6—C5—C4—C3	−178.2 (2)
N1—C1—C2—C3	2.1 (3)	N2—C7—C8—C9	179.5 (2)
C13—C1—C2—C3	−176.5 (2)	C12—C7—C8—C9	1.4 (3)
C6—N2—C7—C8	−178.0 (2)	C7—C8—C9—C10	0.0 (4)
C6—N2—C7—C12	0.4 (2)	C11—C10—C9—C8	−1.4 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H4···O5ⁱ	0.82 (3)	2.23 (3)	3.048 (6)	170 (2)
N2—H4···O4ⁱ	0.82 (3)	2.22 (3)	2.910 (7)	138 (2)
N2—H4···O3ⁱ	0.82 (3)	2.84 (3)	3.448 (7)	132 (2)
N4—H9···O6ⁱ	0.92 (3)	2.03 (3)	2.830 (2)	144 (2)
N4—H9···O5ⁱ	0.92 (3)	2.04 (3)	2.959 (5)	176 (2)
N5—H14···O1ⁱⁱ	0.94 (4)	1.74 (4)	2.672 (3)	171 (3)
O1—H15···O2ⁱ	0.76 (4)	2.37 (4)	3.071 (3)	154 (3)
O1—H15···O6ⁱ	0.76 (4)	2.38 (4)	3.052 (7)	148 (3)
O1—H15···O5ⁱ	0.76 (4)	2.88 (3)	3.510 (6)	142 (3)
O1—H16···N3ⁱⁱⁱ	0.80 (4)	2.02 (4)	2.806 (2)	169 (3)

Symmetry codes: (i) −x+1/2, y−1/2, −z+3/2; (ii) −x+1/2, y+1/2, −z+1/2; (iii) −x, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₉H₁₄N₅·ClO₄·H₂O
M_r	429.82
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	304
a, b, c (Å)	9.168 (2), 15.111 (3), 13.962 (3)
β (°)	101.98 (2)
V (Å³)	1892.1 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.25
Crystal size (mm)	0.75 × 0.20 × 0.20

Data collection
Diffractometer	Enraf-Nonius CAD4 diffractometer
Absorption correction	ψ-scan (North et al., 1968)
T_min, T_max	0.837, 0.952
No. of measured, independent and observed [I > 2σ(I)] reflections	4491, 3716, 2847
R_int	0.046
(sin θ/λ)_max (Å⁻¹)	0.616

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.125, 1.02
No. of reflections	3716
No. of parameters	322
No. of restraints	7
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.36

Computer programs: CAD-4 Diffractometer Control Software (Enraf-Nonius, 1993), CAD-4 Diffractometer Control Software, REDU4 (Stoe & Cie, 1988), SHELXS86 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1998), SHELXL97.

Selected geometric parameters (Å, º) top

N1—C5	1.335 (2)	N4—C13	1.331 (3)
N1—C1	1.341 (2)	N4—C14	1.382 (2)
N2—C6	1.345 (3)	C13—C1	1.466 (3)
N2—C7	1.378 (2)	C6—N3	1.323 (2)
N5—C13	1.329 (2)	C6—C5	1.467 (3)
N5—C19	1.383 (3)	N3—C12	1.384 (2)

C5—N1—C1	116.59 (16)	C13—N4—C14	109.00 (16)
C6—N2—C7	107.61 (16)	C6—N3—C12	104.59 (16)
C13—N5—C19	108.59 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H4···O5ⁱ	0.82 (3)	2.23 (3)	3.048 (6)	170 (2)
N2—H4···O4ⁱ	0.82 (3)	2.22 (3)	2.910 (7)	138 (2)
N4—H9···O6ⁱ	0.92 (3)	2.03 (3)	2.830 (2)	144 (2)
N4—H9···O5ⁱ	0.92 (3)	2.04 (3)	2.959 (5)	176 (2)
N5—H14···O1ⁱⁱ	0.94 (4)	1.74 (4)	2.672 (3)	171 (3)
O1—H15···O2ⁱ	0.76 (4)	2.37 (4)	3.071 (3)	154 (3)
O1—H15···O6ⁱ	0.76 (4)	2.38 (4)	3.052 (7)	148 (3)
O1—H16···N3ⁱⁱⁱ	0.80 (4)	2.02 (4)	2.806 (2)	169 (3)

Symmetry codes: (i) −x+1/2, y−1/2, −z+3/2; (ii) −x+1/2, y+1/2, −z+1/2; (iii) −x, −y+1, −z+1.

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