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The title compounds, C10H12N4, (I), and C9H10N4, (II), have been synthesized and characterized both spectroscopically and structurally. The dihedral angles between the triazole and benzene ring planes are 26.59 (9) and 42.34 (2)°, respectively. In (I), mol­ecules are linked principally by N—H...N hydrogen bonds involving the amino NH2 group and a triazole N atom, forming R44(20) and R24(10) rings which link to give a three-dimensional network of mol­ecules. The hydrogen bonding is supported by two different C—H...π inter­actions from the tolyl ring to either a triazole ring or a tolyl ring in neighboring mol­ecules. In (II), inter­molecular hydrogen bonds and C—H...π inter­actions produce R34(15) and R44(21) rings.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106037668/my3010sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270106037668/my3010Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270106037668/my3010IIsup3.hkl
Contains datablock II

CCDC references: 628524; 628525

Comment top

1,2,4-Triazole and its derivatives belong to a class of exceptionally active compounds possessing a wide spectrum of biological properties, including anti-inflammatory, antifungal, antiviral (Mahomed et al., 1993; Massa et al., 1992; Mullican et al., 1993), analgesic, anticonvulsant and antidepressant activities (Bradbury & Rivett, 1991; Sughen & Yoloye, 1978; Kane et al., 1988). Some of these compounds are also known to exhibit anticancer activity, e.g. anastrozole, 2,2'-[5-(1H-1,2,4-triazol-1-ylmethyl)-1,3-phenylene]bis(2- methylpropiononitrile), and letrozole, 1-[bis(4-cyanophenyl)methyl]-1,2,4-triazole (Bonte, 2000; Lønning, 1996, 2001). These are completely selective and well tolerated modern, orally active, non-steroidal aromatase inhibitors which are increasingly being used in the treatment of advanced breast cancer in postmenopausal women. Apart from their pharmacological significance, 1,2,4-triazole derivatives exhibit interesting chemical properties. The ability of triazoles to form a bridge between metal ions makes such ligands very important for magnetochemical applications. Some complexes containing substituted 1,2,4-triazole ligands have potential uses as optical sensors or molecular-based memory devices (Kahn & Martinez, 1998; Garcia et al., 1997). In spite of the chemical and medicinal importance of this class of compounds, relatively few crystal structure determinations of 1,2,4-triazole derivatives have been reported (Cambridge Structural Database, Version 5.27 of November 2005; Allen, 2002). In addition to the X-ray structure determination reported here, the title compound, (I), has also been characterized by IR, 1H NMR and 13C NMR spectroscopies and by elemental analysis.

Compound (I) consists of a 1,2,4-triazole ring with methyl, amino and p-tolyl substituents at the 3-, 4- and 5-positions, respectively (Fig. 1). Least-squares mean-plane calculations for the triazole (N1/N2/C3/N4/C5) and phenyl (C1P–C6P) ring planes show that these are approximately planar, with respective maximum deviations of 0.0027 (10) Å for C5 and 0.0066 (11) Å for C1P, the two atoms forming the external bond linking the two rings. The dihedral angle between the triazole and phenyl ring planes is 26.59 (9)°.

The N4—N4A bond length (Table 1) is similar to the corresponding distance in 4-amino-3,5-bis(4-pyridyl)-1,2,4-triazole [1.411 (4) Å; Guo & Du, 2002]. The C3N2 and C5N1 distances are in good agreement with those found for structures containing the 1,2,4-triazole ring (see, for example, Özbey et al., 2000; Zhu et al., 2000). The N1—N2 bond length is elongated to 1.3859 (19) Å. This value is comparable to those observed in 1-methyl-3,5-diphenyl-1H-1,2,4-triazole (Yazıcı et al., 2004).

Compound (II) consists of a 1,2,4-triazole ring with methyl, amino and phenyl ring substituents at the 3-, 4- and 5-positions, respectively (Fig. 2). The 1,2,4-triazole ring (A; N1/N2/C3/N4/C5) plane and the phenyl ring (Ph; C1P–C6P) plane are approximately planar, the maximum deviations from the least-squares planes being 0.0028 (10) Å for atom C5 and 0.0056 (15) Å for atom C3P. The dihedral angle between the planes of rings A and Ph is 137.66 (2)°. The N1—N2 bond length (Table 3) agrees with the corresponding distance in 3,6-bis(2-chlorophenyl)-1,4-dihydro-1,2,4,5-tetrazine [1.395 (3) Å; Zachara et al., 2004]. The benzene ring is twisted about the external bond to the 1,2,4-triazole ring a torsion angle of −136.80 (19)°.

Molecules are linked by intermolecular hydrogen bonding, and we employ graph-set notation (Bernstein et al., 1995) to describe the patterns of hydrogen bonding. In (I), the arrangement of the interactions (Fig. 3 and Table 2) can be described by the graph-set notation R44(20). The interlinking interactions are described by the notation R44(10). The combined effect of the linked R44(20) and R44(10) motifs is to generate a three dimensional network of molecules.

In (II), the one-dimensional assemblies formed by hydrogen bonding are enforced by weaker intermolecular interactions. N—H···N contacts are observed along the main chains, between the 4-amino-1,2,4-triazole rings of adjacent molecules. Amino atom N4A in the molecule at (x, y, z) acts as a hydrogen-bond donor, via H4AB, to N1 in the molecule at (x − 1, y, z), while N4A at (x − 1, y, z), in turn, acts as a donor to N1 at (x − 2, y, z). In this manner, a C(5) (motif g) chain is formed, running along the a axis. The arrangement of N4A—H4AB···N1i, N4Aii—H4AAii···N2i, N4Aii—H4ABii···N1iii and N4Aiii—H4AAiii···N2 interactions [symmetry codes: (i) x − 1, y, z; (ii) −x, 1/2 + y, 3/2 − z; (iii) 1 − x, 1/2 + y, 3/2 − z] can be described by the graph-set notation R44(15). Amino atom N4A in the molecule at (1 − x, 1/2 + y, 3/2 − z) acts as a hydrogen-bond donor, via H4AA, to N2 in the molecule at (x, y, z), while N4A at (x, y, z), in turn, acts as a donor to N2 at (1 − x, y − 1/2, 3/2 − z). In this manner, a C(5) (motif f) chain is formed, running along the b axis (Fig. 4). The geometry of the hydrogen bonding is given in Table 4.

Compound (I) also contains two intermolecular C—H···π contacts from the 1,2,4-triazole ring to two different symmetry-related molecules (Fig. 5)·The first is from atom C2P in the tolyl ring of the reference molecule to the centroid (d) of the triazole ring related by the symmetry operation (1/4 − y, −1/4 + x, −1/4 + z) [C2P···d = 3.8088 (19) Å, H2P···d = 2.9639 Å, C2P—H2P···d = 152°]. The second C—H···π contact is between C5P in the tolyl ring to the centroid (e) of the symmetry-related tolyl ring at (−1/4 + y, 1/4 − x, 1/4 − z) [C5P···e = 3.7366 (19) Å, H5P···e = 2.8850 Å, C5P—H5P···e = 153°].

In compound (II), the interlinked C3Pi—H3Pi···Ph [C3Pi···Ph = 3.659 (2) Å, H3Pi···Ph = 2.9668 Å and C3Pi—H3Pi···Ph = 132.34°; symmetry code: (i) −1/2 + x, 3/2 − y, −z], C6P—H6P···Phii [C6P···Phii = 3.574 (2) Å, H6P···Phii = 2.8771 Å and C6P—H6P···Phii = 132.74°; symmetry code: (ii) 1/2 + x, 1/2 − y, −z], N4Aiii—H4AAiii···N2ii [symmetry code: (iii) 1/2 − x, 1 − y, z − 1/2] and N4Ai—H4AAi···N2iii interactions, which define an R44(21) ring pattern (Fig. 6).

Experimental top

For the preparation of (I), acyl hydrazone (0.005 mol) was added to a solution of hydrazine hydrate (0.01 mol) in 1-propanol (50 ml) and the mixture was refluxed for 24 h. On cooling, a precipitate was formed, and this product was filtered off and dried. The dry product was washed with benzene (20 ml). The insoluble part in benzene was recrystallized from 1-propanol to afford the pure compound. Recrystallization from ethyl acetate gave a white product (yield 87%). Single crystals of (I) were obtained from ethyl acetate at room temperature by slow evaporation (m.p. 488–489 K). IR (KBr, cm−1): 3245–3142 (vNH2), 1652 (VC=N); 1H NMR (DMSO-d6, p.p.m.): δ 2.38 (6H, CH3), 6.05 (s, 2H, NH2), [ar-H: 7.30 (d, 2H, J = 7.80 Hz), 7.92 (d, 2H, J = 7.80 Hz)]; 13C NMR (DMSO-d6, p.p.m.): δ 153.06 (triazole C3), 152.10 (triazole C5), [ar-C: 138.67, 128.81 (2 C), 127.57 (2 C), 124.71], 20.83 (ar-CH3), 9.80 (CH3). Elemental analysis, calculated for C10H12N4: C 63.81, H 6.43, N 29.76%; found: C 63.80, H 6.41, N 29.73%. For the preparation of compound (II), acyl hydrazone (0.005 mol) was added to a solution of hydrazine hydrate (0.01 mol) in 1- propanol (50 ml) and the mixture was refluxed for 24 h. On cooling, a precipitate was formed, and this product was filtered off and dried. The dry product was washed with benzene (20 ml). The insoluble part in benzene was recrystallized from 1-propanol to afford the pure compound. Recrystallization from ethyl acetate gave a white product (yield 75%). Single crystals of (II) were obtained from ethyl acetate at room temperature by slow evaporation (m.p. 467–468 K). IR (KBr, cm−1): 3255–3150 (vNH2), 1645 (vC=N); 1H NMR (DMSO-d6, p.p.m.): δ 2.40 (s, 3H, CH3), 6.06 (s, 2H, NH2), [ar-H: 7.40–7.70 (m, 3H), 8.00–8.20 (m, 2H)]; 13C NMR (DMSO-d6, p.p.m.): δ 53.86 (triazole C3), 152.33 (triazole C5), [ar-C: 129.00, 128.22 (2 C), 127.65 (2 C), 127.38], 9.73 (CH3). Elemental analysis, calculated for C9H10N4: C 62.05, H 5.79, N 32.16%; found: C 62.04, H 5.77, N 32.76%.

Refinement top

For both compounds, methyl H atoms were located in a difference Fourier synthesis and then refined as rigid rotating groups [C—H = 0.96 Å and Uiso(H) = 1.5Ueq(C)]. Aromatic H atoms were placed geometrically and refined using a riding model [C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C)]. Atoms H4AA and H4AB bound to N4A were refined freely.

Computing details top

For both compounds, data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2006); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. A view of (I), showing the atom numbering scheme and with displacement ellipsoids drawn at the 40% probability level.
[Figure 2] Fig. 2. A view of (II), with the atom-numbering scheme and 40% probability displacement ellipsoids.
[Figure 3] Fig. 3. A view, parallel to (101), of the three-dimensional hydrogen-bonding network in (I). Dashed lines indicate N—H···N hydrogen bonds. [Symmetry codes: (i) x, y − 1, z; (ii) y − 3/4, −x + 3/4, −z + 7/4; (iii) −x + 1, −y + 3/2, z; (iv) −y + 7/4, x − 1/4, −z + 7/4; (v) x + 1/2, y − 1, −z + 3/2; (vi) y − 1/4, −x + 3/4, z − 1/4.]
[Figure 4] Fig. 4. The packing of (II), showing the R44(15) ring pattern. Dashed lines indicate hydrogen bonds. Other H atoms and phenyl rings have been omitted for clarity. Symmetry codes: (i) x − 1, y, z; (ii) −x, y + 1/2, −z + 3/2; (iii) −x + 1, y + 1/2, −z + 3/2.
[Figure 5] Fig. 5. A view of (I), showing the C—H···π interactions, parallel to (110), between (d) triazole and tolyl groups and (e) tolyl and tolyl groups as dashed lines.
[Figure 6] Fig. 6. The packing of (II), showing the R44(21) ring pattern. Dashed lines indicate hydrogen bonds and C—H···π interactions. Other H atoms have been omitted for clarity. [Symmetry codes: (i) x − 1/2, −y + 3/2, −z + 1; (ii) x − 1/2, −y + 1/2, −z + 1; (iii) −x + 1/2, −y + 1, z − 1/2.]
(I) 4-amino-3-methyl-5-(p-tolyl)-4H-1,2,4-triazole top
Crystal data top
C10H12N4Dx = 1.182 Mg m3
Mr = 188.24Melting point = 488–489 K
Tetragonal, I41/aMo Kα radiation, λ = 0.71073 Å
Hall symbol: -I4adCell parameters from 7427 reflections
a = 16.4033 (11) Åθ = 1.8–27.9°
c = 15.7192 (12) ŵ = 0.08 mm1
V = 4229.5 (5) Å3T = 296 K
Z = 16Square prism, colorless
F(000) = 16000.66 × 0.57 × 0.51 mm
Data collection top
STOE IPDS-II
diffractometer
1511 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.061
Graphite monochromatorθmax = 26.0°, θmin = 1.8°
Detector resolution: 6.67 pixels mm-1h = 199
ω scank = 2019
7427 measured reflectionsl = 1819
2082 independent reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.041H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.115 w = 1/[σ2(Fo2) + (0.0594P)2 + 0.2861P]
where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max = 0.001
2082 reflectionsΔρmax = 0.11 e Å3
138 parametersΔρmin = 0.11 e Å3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0019 (6)
Crystal data top
C10H12N4Z = 16
Mr = 188.24Mo Kα radiation
Tetragonal, I41/aµ = 0.08 mm1
a = 16.4033 (11) ÅT = 296 K
c = 15.7192 (12) Å0.66 × 0.57 × 0.51 mm
V = 4229.5 (5) Å3
Data collection top
STOE IPDS-II
diffractometer
1511 reflections with I > 2σ(I)
7427 measured reflectionsRint = 0.061
2082 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0410 restraints
wR(F2) = 0.115H atoms treated by a mixture of independent and constrained refinement
S = 1.01Δρmax = 0.11 e Å3
2082 reflectionsΔρmin = 0.11 e Å3
138 parameters
Special details top

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 of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) 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
xyzUiso*/Ueq
N10.33618 (10)1.10610 (9)0.74921 (8)0.0808 (5)
N20.33372 (10)1.14100 (9)0.82946 (9)0.0837 (5)
C30.38287 (10)1.09962 (9)0.87798 (9)0.0627 (4)
C3M0.39951 (12)1.11687 (11)0.96885 (10)0.0795 (5)
H3MA0.37331.16690.98480.119*
H3MB0.45721.12180.97740.119*
H3MC0.37871.07311.00310.119*
N40.41736 (7)1.03854 (7)0.83185 (6)0.0503 (3)
N4A0.46926 (8)0.97643 (8)0.86186 (7)0.0571 (3)
H4AB0.4381 (11)0.9481 (11)0.9056 (11)0.077 (5)*
H4AA0.5115 (12)1.0046 (11)0.8885 (11)0.080 (5)*
C50.38650 (9)1.04420 (8)0.75176 (8)0.0552 (4)
C1P0.40449 (9)0.99300 (8)0.67790 (8)0.0551 (4)
C2P0.34685 (11)0.98820 (10)0.61326 (9)0.0681 (4)
H2P0.29661.01380.61990.082*
C3P0.36338 (12)0.94590 (11)0.53944 (10)0.0745 (5)
H3P0.32410.94380.49680.089*
C4P0.43693 (12)0.90659 (10)0.52731 (10)0.0693 (5)
C5P0.49363 (11)0.91111 (10)0.59214 (10)0.0712 (5)
H5P0.54370.88530.58550.085*
C6P0.47794 (9)0.95301 (10)0.66656 (9)0.0640 (4)
H6P0.51700.95430.70940.077*
C4M0.45477 (15)0.86136 (13)0.44633 (11)0.0972 (7)
H4MA0.51240.85190.44190.146*
H4MB0.43680.89320.39860.146*
H4MC0.42660.81010.44670.146*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.1050 (11)0.0752 (9)0.0623 (8)0.0333 (8)0.0179 (7)0.0036 (7)
N20.1115 (12)0.0745 (9)0.0649 (8)0.0339 (8)0.0160 (8)0.0096 (7)
C30.0725 (10)0.0586 (9)0.0570 (8)0.0062 (8)0.0034 (7)0.0017 (7)
C3M0.0995 (13)0.0794 (12)0.0598 (9)0.0104 (10)0.0058 (9)0.0101 (8)
N40.0522 (6)0.0504 (6)0.0484 (6)0.0004 (5)0.0040 (5)0.0047 (5)
N4A0.0558 (7)0.0609 (7)0.0546 (7)0.0057 (6)0.0065 (6)0.0103 (6)
C50.0605 (8)0.0540 (8)0.0512 (8)0.0049 (7)0.0065 (6)0.0049 (6)
C1P0.0627 (9)0.0538 (8)0.0487 (7)0.0003 (7)0.0051 (6)0.0073 (6)
C2P0.0757 (10)0.0665 (9)0.0620 (9)0.0094 (8)0.0152 (8)0.0014 (7)
C3P0.0935 (13)0.0721 (11)0.0580 (9)0.0021 (9)0.0206 (8)0.0006 (7)
C4P0.0949 (13)0.0576 (9)0.0555 (8)0.0059 (9)0.0048 (8)0.0013 (7)
C5P0.0750 (11)0.0721 (10)0.0664 (9)0.0078 (8)0.0074 (8)0.0013 (8)
C6P0.0630 (9)0.0695 (9)0.0595 (8)0.0038 (7)0.0053 (7)0.0005 (7)
C4M0.1394 (19)0.0825 (13)0.0697 (11)0.0080 (12)0.0113 (11)0.0126 (9)
Geometric parameters (Å, º) top
N1—N21.3859 (19)C1P—C51.4629 (19)
N1—C51.3091 (19)C2P—C3P1.379 (2)
N2—C31.301 (2)C2P—H2P0.9300
C3—N41.3600 (18)C3P—C4P1.381 (3)
C3—C3M1.481 (2)C3P—H3P0.9300
C3M—H3MA0.9600C4P—C5P1.382 (2)
C3M—H3MB0.9600C4P—C4M1.502 (2)
C3M—H3MC0.9600C5P—C6P1.381 (2)
N4—N4A1.4090 (16)C5P—H5P0.9300
N4A—H4AB0.975 (19)C6P—H6P0.9300
N4A—H4AA0.932 (19)C4M—H4MA0.9600
N4—C51.3602 (16)C4M—H4MB0.9600
C1P—C6P1.383 (2)C4M—H4MC0.9600
C1P—C2P1.390 (2)
C3—N4—C5106.76 (11)C4P—C5P—H5P119.1
C3—N4—N4A127.27 (11)C5P—C6P—C1P120.50 (14)
C5—N4—N4A125.74 (11)C5P—C6P—H6P119.8
C3—N2—N1107.45 (13)C1P—C6P—H6P119.8
C5—N1—N2108.12 (12)C4P—C4M—H4MA109.5
N4—N4A—H4AB105.3 (10)C4P—C4M—H4MB109.5
N4—N4A—H4AA104.0 (11)H4MA—C4M—H4MB109.5
H4AB—N4A—H4AA108.1 (14)C4P—C4M—H4MC109.5
C6P—C1P—C2P118.11 (14)H4MA—C4M—H4MC109.5
C6P—C1P—C5123.38 (13)H4MB—C4M—H4MC109.5
C2P—C1P—C5118.39 (14)N1—C5—N4108.42 (12)
C3P—C2P—C1P120.66 (16)N1—C5—C1P123.24 (12)
C3P—C2P—H2P119.7N4—C5—C1P128.34 (12)
C1P—C2P—H2P119.7N2—C3—N4109.25 (12)
C2P—C3P—C4P121.52 (15)N2—C3—C3M125.43 (14)
C2P—C3P—H3P119.2N4—C3—C3M125.32 (14)
C4P—C3P—H3P119.2C3—C3M—H3MA109.5
C3P—C4P—C5P117.46 (14)C3—C3M—H3MB109.5
C3P—C4P—C4M121.18 (17)H3MA—C3M—H3MB109.5
C5P—C4P—C4M121.36 (18)C3—C3M—H3MC109.5
C6P—C5P—C4P121.74 (16)H3MA—C3M—H3MC109.5
C6P—C5P—H5P119.1H3MB—C3M—H3MC109.5
C3—N2—N1—C50.4 (2)N4A—N4—C5—N1175.27 (14)
C6P—C1P—C2P—C3P1.2 (2)C3—N4—C5—C1P179.62 (15)
C5—C1P—C2P—C3P174.99 (14)N4A—N4—C5—C1P5.6 (2)
C1P—C2P—C3P—C4P0.5 (3)C6P—C1P—C5—N1151.09 (17)
C2P—C3P—C4P—C5P0.1 (2)C2P—C1P—C5—N124.8 (2)
C2P—C3P—C4P—C4M179.38 (17)C6P—C1P—C5—N428.0 (2)
C3P—C4P—C5P—C6P0.1 (2)C2P—C1P—C5—N4156.11 (15)
C4M—C4P—C5P—C6P179.57 (16)N1—N2—C3—N40.1 (2)
C4P—C5P—C6P—C1P0.9 (3)N1—N2—C3—C3M179.20 (17)
C2P—C1P—C6P—C5P1.3 (2)C5—N4—C3—N20.21 (18)
C5—C1P—C6P—C5P174.59 (14)N4A—N4—C3—N2174.93 (14)
N2—N1—C5—N40.5 (2)C5—N4—C3—C3M179.50 (16)
N2—N1—C5—C1P179.73 (14)N4A—N4—C3—C3M5.8 (3)
C3—N4—C5—N10.45 (18)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N4A—H4AB···N1i0.975 (19)2.072 (19)3.0269 (19)166.2 (14)
N4A—H4AA···N2ii0.932 (19)2.12 (2)3.033 (2)166.2 (15)
Symmetry codes: (i) y3/4, x+5/4, z+1/4; (ii) y+7/4, x+3/4, z+7/4.
(II) 4-amino-3-methyl-5-phenyl-4H-1,2,4-triazole top
Crystal data top
C9H10N4Dx = 1.303 Mg m3
Mr = 174.21Melting point = 467–468 K
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P2ac2abCell parameters from 4368 reflections
a = 6.1062 (8) Åθ = 2.8–27.9°
b = 7.3981 (11) ŵ = 0.09 mm1
c = 19.653 (4) ÅT = 296 K
V = 887.8 (3) Å3Prism, colorless
Z = 40.62 × 0.52 × 0.40 mm
F(000) = 368
Data collection top
STOE IPDS-II
diffractometer
1556 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.080
Graphite monochromatorθmax = 26.0°, θmin = 2.9°
Detector resolution: 6.67 pixels mm-1h = 77
w scank = 98
4368 measured reflectionsl = 1724
1692 independent reflections
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.040 w = 1/[σ2(Fo2) + (0.0683P)2]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.107(Δ/σ)max < 0.001
S = 1.04Δρmax = 0.19 e Å3
1692 reflectionsΔρmin = 0.22 e Å3
128 parametersExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraintsExtinction coefficient: 0.056 (11)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983), 660 Friedel pairs
Secondary atom site location: difference Fourier mapAbsolute structure parameter: 0 (2)
Crystal data top
C9H10N4V = 887.8 (3) Å3
Mr = 174.21Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 6.1062 (8) ŵ = 0.09 mm1
b = 7.3981 (11) ÅT = 296 K
c = 19.653 (4) Å0.62 × 0.52 × 0.40 mm
Data collection top
STOE IPDS-II
diffractometer
1556 reflections with I > 2σ(I)
4368 measured reflectionsRint = 0.080
1692 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.040H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.107Δρmax = 0.19 e Å3
S = 1.04Δρmin = 0.22 e Å3
1692 reflectionsAbsolute structure: Flack (1983), 660 Friedel pairs
128 parametersAbsolute structure parameter: 0 (2)
0 restraints
Special details top

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 of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) 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
xyzUiso*/Ueq
N40.41918 (18)0.58192 (19)0.67928 (7)0.0341 (3)
N20.6840 (2)0.6841 (2)0.74308 (8)0.0444 (4)
N10.7641 (2)0.6558 (2)0.67741 (8)0.0402 (4)
N4A0.2212 (2)0.4999 (2)0.65931 (8)0.0432 (4)
H4AA0.205 (4)0.397 (4)0.6874 (15)0.068 (7)*
H4AB0.111 (3)0.584 (3)0.6635 (13)0.052 (6)*
C1P0.6165 (2)0.5460 (2)0.56770 (8)0.0338 (4)
C2P0.8001 (2)0.4531 (3)0.54390 (9)0.0425 (4)
H2P0.91070.42010.57400.051*
C3P0.8177 (3)0.4102 (3)0.47548 (10)0.0513 (5)
H3P0.93930.34680.45990.062*
C4P0.6560 (3)0.4609 (3)0.43047 (10)0.0532 (5)
H4P0.66890.43330.38450.064*
C5P0.4755 (3)0.5526 (3)0.45396 (10)0.0519 (5)
H5P0.36650.58670.42350.062*
C6P0.4534 (3)0.5947 (3)0.52204 (9)0.0429 (4)
H6P0.32950.65560.53730.052*
C50.6030 (2)0.5941 (2)0.64035 (8)0.0325 (4)
C30.4768 (3)0.6382 (2)0.74262 (10)0.0394 (4)
C3M0.3229 (4)0.6466 (3)0.80075 (11)0.0567 (5)
H3MA0.39680.69550.83970.085*
H3MB0.27100.52720.81110.085*
H3MC0.20110.72260.78910.085*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N40.0264 (5)0.0426 (7)0.0333 (7)0.0003 (5)0.0002 (5)0.0022 (6)
N20.0403 (7)0.0538 (8)0.0391 (8)0.0053 (6)0.0025 (6)0.0064 (7)
N10.0322 (6)0.0512 (8)0.0371 (7)0.0021 (5)0.0017 (5)0.0033 (6)
N4A0.0248 (6)0.0588 (10)0.0460 (8)0.0038 (6)0.0037 (5)0.0027 (7)
C1P0.0327 (7)0.0363 (8)0.0325 (8)0.0015 (6)0.0003 (6)0.0000 (6)
C2P0.0370 (8)0.0506 (9)0.0399 (9)0.0060 (7)0.0025 (7)0.0030 (8)
C3P0.0508 (9)0.0569 (11)0.0461 (10)0.0082 (8)0.0078 (8)0.0096 (9)
C4P0.0695 (11)0.0561 (11)0.0338 (9)0.0006 (9)0.0019 (8)0.0070 (8)
C5P0.0581 (10)0.0575 (11)0.0401 (9)0.0065 (9)0.0138 (8)0.0001 (9)
C6P0.0415 (8)0.0470 (9)0.0403 (9)0.0094 (7)0.0048 (6)0.0003 (8)
C50.0276 (6)0.0365 (8)0.0335 (8)0.0024 (6)0.0002 (6)0.0014 (6)
C30.0371 (7)0.0416 (8)0.0395 (9)0.0000 (6)0.0012 (6)0.0043 (7)
C3M0.0603 (10)0.0666 (13)0.0433 (10)0.0056 (9)0.0145 (8)0.0086 (9)
Geometric parameters (Å, º) top
N4—C31.359 (2)C2P—H2P0.9300
N4—C51.3615 (19)C3P—C4P1.378 (3)
N4—N4A1.4081 (18)C3P—H3P0.9300
N2—C31.310 (2)C4P—C5P1.374 (3)
N2—N11.396 (2)C4P—H4P0.9300
N1—C51.306 (2)C5P—C6P1.380 (3)
N4A—H4AA0.95 (3)C5P—H5P0.9300
N4A—H4AB0.92 (2)C6P—H6P0.9300
C1P—C6P1.388 (2)C3—C3M1.480 (3)
C1P—C2P1.396 (2)C3M—H3MA0.9600
C1P—C51.474 (2)C3M—H3MB0.9600
C2P—C3P1.386 (3)C3M—H3MC0.9600
C3—N4—C5106.32 (13)C3P—C4P—H4P120.2
C3—N4—N4A127.54 (14)C4P—C5P—C6P121.02 (17)
C5—N4—N4A125.43 (13)C4P—C5P—H5P119.5
C3—N2—N1107.04 (14)C6P—C5P—H5P119.5
C5—N1—N2107.71 (12)C5P—C6P—C1P119.86 (16)
N4—N4A—H4AA105.8 (16)C5P—C6P—H6P120.1
N4—N4A—H4AB108.2 (14)C1P—C6P—H6P120.1
H4AA—N4A—H4AB115 (2)N1—C5—N4109.31 (14)
C6P—C1P—C2P119.17 (16)N1—C5—C1P125.63 (13)
C6P—C1P—C5121.57 (14)N4—C5—C1P125.06 (13)
C2P—C1P—C5119.24 (14)N2—C3—N4109.61 (16)
C3P—C2P—C1P120.03 (16)N2—C3—C3M126.64 (18)
C3P—C2P—H2P120.0N4—C3—C3M123.75 (16)
C1P—C2P—H2P120.0C3—C3M—H3MA109.5
C4P—C3P—C2P120.32 (17)C3—C3M—H3MB109.5
C4P—C3P—H3P119.8H3MA—C3M—H3MB109.5
C2P—C3P—H3P119.8C3—C3M—H3MC109.5
C5P—C4P—C3P119.59 (17)H3MA—C3M—H3MC109.5
C5P—C4P—H4P120.2H3MB—C3M—H3MC109.5
C3—N2—N1—C50.16 (19)C3—N4—C5—C1P179.83 (15)
C6P—C1P—C2P—C3P0.2 (3)N4A—N4—C5—C1P8.9 (3)
C5—C1P—C2P—C3P178.64 (17)C6P—C1P—C5—N1136.80 (19)
C1P—C2P—C3P—C4P0.9 (3)C2P—C1P—C5—N141.6 (2)
C2P—C3P—C4P—C5P0.8 (3)C6P—C1P—C5—N442.8 (2)
C3P—C4P—C5P—C6P0.0 (3)C2P—C1P—C5—N4138.84 (17)
C4P—C5P—C6P—C1P0.7 (3)N1—N2—C3—N40.2 (2)
C2P—C1P—C6P—C5P0.6 (3)N1—N2—C3—C3M179.43 (19)
C5—C1P—C6P—C5P177.79 (16)C5—N4—C3—N20.5 (2)
N2—N1—C5—N40.44 (19)N4A—N4—C3—N2171.16 (16)
N2—N1—C5—C1P179.95 (15)C5—N4—C3—C3M179.72 (18)
C3—N4—C5—N10.56 (19)N4A—N4—C3—C3M9.6 (3)
N4A—N4—C5—N1171.52 (15)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N4A—H4AA···N2i0.95 (3)2.19 (3)3.078 (2)156 (2)
N4A—H4AB···N1ii0.92 (2)2.20 (2)3.0411 (19)151.4 (18)
Symmetry codes: (i) x+1, y1/2, z+3/2; (ii) x1, y, z.

Experimental details

(I)(II)
Crystal data
Chemical formulaC10H12N4C9H10N4
Mr188.24174.21
Crystal system, space groupTetragonal, I41/aOrthorhombic, P212121
Temperature (K)296296
a, b, c (Å)16.4033 (11), 16.4033 (11), 15.7192 (12)6.1062 (8), 7.3981 (11), 19.653 (4)
α, β, γ (°)90, 90, 9090, 90, 90
V3)4229.5 (5)887.8 (3)
Z164
Radiation typeMo KαMo Kα
µ (mm1)0.080.09
Crystal size (mm)0.66 × 0.57 × 0.510.62 × 0.52 × 0.40
Data collection
DiffractometerSTOE IPDS-II
diffractometer
STOE IPDS-II
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
7427, 2082, 1511 4368, 1692, 1556
Rint0.0610.080
(sin θ/λ)max1)0.6170.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.041, 0.115, 1.01 0.040, 0.107, 1.04
No. of reflections20821692
No. of parameters138128
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.11, 0.110.19, 0.22
Absolute structure?Flack (1983), 660 Friedel pairs
Absolute structure parameter?0 (2)

Computer programs: X-AREA (Stoe & Cie, 2002), X-AREA, X-RED (Stoe & Cie, 2002), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2006), WinGX (Farrugia, 1999).

Selected geometric parameters (Å, º) for (I) top
N1—N21.3859 (19)N4—N4A1.4090 (16)
N1—C51.3091 (19)C1P—C51.4629 (19)
N2—C31.301 (2)
C5—N4—N4A125.74 (11)C5—N1—N2108.12 (12)
N4A—N4—C5—C1P5.6 (2)C6P—C1P—C5—N428.0 (2)
C6P—C1P—C5—N1151.09 (17)
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N4A—H4AB···N1i0.975 (19)2.072 (19)3.0269 (19)166.2 (14)
N4A—H4AA···N2ii0.932 (19)2.12 (2)3.033 (2)166.2 (15)
Symmetry codes: (i) y3/4, x+5/4, z+1/4; (ii) y+7/4, x+3/4, z+7/4.
Selected geometric parameters (Å, º) for (II) top
N4—N4A1.4081 (18)N1—C51.306 (2)
N2—C31.310 (2)C1P—C51.474 (2)
N2—N11.396 (2)
C5—N4—N4A125.43 (13)C5—N1—N2107.71 (12)
C6P—C1P—C5—N1136.80 (19)
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N4A—H4AA···N2i0.95 (3)2.19 (3)3.078 (2)156 (2)
N4A—H4AB···N1ii0.92 (2)2.20 (2)3.0411 (19)151.4 (18)
Symmetry codes: (i) x+1, y1/2, z+3/2; (ii) x1, y, z.
 

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