(E)-N-Benzyl­idene-4H-1,2,4-triazol-4-amine

Thenmozhi, M.; Kavitha, T.; Reddy, B.P.; Vijayakumar, V.; Ponnuswamy, M.N.

doi:10.1107/S1600536810003946

organic compounds

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ISSN: 2056-9890

Volume 66| Part 3| March 2010| Page o558

doi:10.1107/S1600536810003946

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(E)-N-Benzylidene-4H-1,2,4-triazol-4-amine

M. Thenmozhi,^a T. Kavitha,^a B. Palakshi Reddy,^b V. Vijayakumar ^b and M. N. Ponnuswamy ^a ^*

^aCentre of Advanced Study in Crystallography and Biophysics, University of Madras, Guindy Campus, Chennai 600 025, India, and ^bOrganic Chemistry Division, School of Advanced Sciences, VIT University, Vellore 632 014, India
^*Correspondence e-mail: mnpsy2004@yahoo.com

(Received 29 December 2009; accepted 1 February 2010; online 6 February 2010)

The title compound, C₉H₈N₄, crystallizes with three independent molecules (A, B and C) per asymmetric unit. The independent molecules differ slightly in their conformations, the dihedral angles between the triazole and phenyl rings in molecules A, B and C being 4.8 (2), 9.7 (2) and 7.2 (2)°, respectively. In the crystal, the independent molecules are linked into a trimer by C—H⋯N hydrogen bonds.

Related literature

For the biological activity of triazole derivatives, see: Demirbas et al. (2002 ); Foroumadi et al. (2003 ); He et al. (2006 ); Kritsanida et al. (2002 ); Manfredini et al. (2000 ). For C—N and C=N bond-length data, see: Jin et al. (2004 ); Xiang et al. (2004 ). For graph-set analysis, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₉H₈N₄
M_r = 172.19
Monoclinic, C 2
a = 33.0059 (11) Å
b = 4.0639 (1) Å
c = 20.6535 (7) Å
β = 111.067 (2)°
V = 2585.14 (14) Å³
Z = 12
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.20 × 0.15 × 0.12 mm

Data collection

Bruker Kappa APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2001 ) T_min = 0.983, T_max = 0.990
14802 measured reflections
3418 independent reflections
2582 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.133
S = 0.99
3418 reflections
352 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.13 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3C—H3C⋯N1B	0.93	2.54	3.414 (4)	157
C7C—H7C⋯N1B	0.93	2.49	3.405 (3)	167
C3A—H3A⋯N2Cⁱ	0.93	2.47	3.387 (4)	169
C7A—H7A⋯N2Cⁱ	0.93	2.58	3.503 (3)	174
C5B—H5B⋯N2Aⁱⁱ	0.93	2.47	3.371 (4)	162
Symmetry codes: (i) $[x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (ii) $[x-{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ .

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ) and ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810003946/ci5006sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810003946/ci5006Isup2.hkl

checkCIF report

Comment top

1,2,4-Triazole is a basic aromatic ring and possesses good coordination ability due to the presence of nitrogen atoms. The 1,2,4-triazole derivatives are used to build polymetallic complexes (He et al., 2006). Compounds derived from triazole possess antimicrobial, analgesic, anti-inflammatory, local anesthetic, antineoplastic and antimalarial properties (Foroumadi et al., 2003). Some triazole Schiff bases also exhibit antiproliferative and anticancer activities (Manfredini et al., 2000). Due to their significant biological applications, triazoles have gained much attention in bioinorganic and metal-based drug discovery (Demirbas et al., 2002; Kritsanida et al., 2002).

There are three crystallographically independent molecules (A, B and C) in the asymmetric unit (Fig. 1). The 1,2,4-triazole ring (N1/N2/C3/N4/C5) is planar and attached to the phenyl ring (C8-C13) through the C═N bond. The dihedral angles between triazole and phenyl rings are 4.8 (2)°, 9.7 (2)° and 7.2 (2)° for molecules A, B and C, respectively. The C—N bond lengths in the triazole ring of all molecules lie in the range of 1.260 (3)–1.349 (4) Å. These are longer than a typical double C═N bond [1.269 (2) Å] (Xiang et al., 2004), but shorter than a C—N single bond [1.443 (4) Å] (Jin et al., 2004), indicating the possibility of electron delocalization.

The crystal packing (Fig 2) shows that the indepentent molecules exist as C—H···N hydrogen-bonded trimers.

Related literature top

For the biological activity of triazole derivatives, see: Demirbas et al. (2002); Foroumadi et al. (2003); He et al. (2006); Kritsanida et al. (2002); Manfredini et al. (2000). For C—N and C═N bond-length data, see: Jin et al. (2004); Xiang et al. (2004). For graph-set analysis, see: Bernstein et al. (1995).

Experimental top

A mixture of benzaldehyde (10 mmol) and 4-amino-4H-1,2,4-triazole (10 mmol) in ethanol was refluxed on a steam-bath for 30 min. The colour of the solution changed to reddish-orange and was kept under ice-cold conditions to obtain a white solid product. Single crystals were formed in the mother liquor after five days.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009) and ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. The crystal packing of the title compound, showing the formation of hydrogen-bonded (dashed lines) trimers.

(E)-N-Benzylidene-4H-1,2,4-triazol-4-amine top

Crystal data top

C₉H₈N₄	F(000) = 1080
M_r = 172.19	D_x = 1.327 Mg m⁻³
Monoclinic, C2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2y	Cell parameters from 14802 reflections
a = 33.0059 (11) Å	θ = 2.1–27.6°
b = 4.0639 (1) Å	µ = 0.09 mm⁻¹
c = 20.6535 (7) Å	T = 293 K
β = 111.067 (2)°	Block, colourless
V = 2585.14 (14) Å³	0.20 × 0.15 × 0.12 mm
Z = 12

Data collection top

Bruker Kappa APEXII area-detector diffractometer	3418 independent reflections
Radiation source: fine-focus sealed tube	2582 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
ω and ϕ scans	θ_max = 27.6°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −42→42
T_min = 0.983, T_max = 0.990	k = −4→5
14802 measured reflections	l = −26→26

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.133	H-atom parameters constrained
S = 0.99	w = 1/[σ²(F_o²) + (0.0936P)²] where P = (F_o² + 2F_c²)/3
3418 reflections	(Δ/σ)_max = 0.005
352 parameters	Δρ_max = 0.13 e Å⁻³
1 restraint	Δρ_min = −0.16 e Å⁻³

Crystal data top

C₉H₈N₄	V = 2585.14 (14) Å³
M_r = 172.19	Z = 12
Monoclinic, C2	Mo Kα radiation
a = 33.0059 (11) Å	µ = 0.09 mm⁻¹
b = 4.0639 (1) Å	T = 293 K
c = 20.6535 (7) Å	0.20 × 0.15 × 0.12 mm
β = 111.067 (2)°

Data collection top

Bruker Kappa APEXII area-detector diffractometer	3418 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	2582 reflections with I > 2σ(I)
T_min = 0.983, T_max = 0.990	R_int = 0.032
14802 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	1 restraint
wR(F²) = 0.133	H-atom parameters constrained
S = 0.99	Δρ_max = 0.13 e Å⁻³
3418 reflections	Δρ_min = −0.16 e Å⁻³
352 parameters

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.

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 > 2sigma(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

	x	y	z	U_iso*/U_eq
N1A	1.09649 (8)	0.8835 (8)	0.61511 (13)	0.0763 (7)
N2A	1.10029 (7)	0.8972 (8)	0.68405 (12)	0.0759 (7)
C3A	1.06740 (8)	0.7385 (9)	0.68915 (13)	0.0669 (8)
H3A	1.0622	0.7106	0.7302	0.080*
N4A	1.04188 (6)	0.6199 (6)	0.62682 (10)	0.0531 (5)
C5A	1.06160 (9)	0.7183 (9)	0.58349 (14)	0.0683 (8)
H5A	1.0513	0.6726	0.5362	0.082*
N6A	1.00305 (6)	0.4455 (6)	0.60450 (10)	0.0534 (5)
C7A	0.98725 (7)	0.3748 (7)	0.64995 (11)	0.0499 (5)
H7A	1.0022	0.4344	0.6959	0.060*
C8A	0.94615 (7)	0.2018 (6)	0.63197 (11)	0.0480 (5)
C9A	0.92932 (8)	0.1395 (8)	0.68311 (12)	0.0566 (6)
H9A	0.9448	0.2018	0.7287	0.068*
C10A	0.88964 (9)	−0.0149 (8)	0.66666 (14)	0.0678 (8)
H10A	0.8782	−0.0523	0.7011	0.081*
C11A	0.86711 (8)	−0.1130 (8)	0.60023 (14)	0.0643 (7)
H11A	0.8404	−0.2169	0.5895	0.077*
C12A	0.88395 (8)	−0.0582 (8)	0.54891 (13)	0.0601 (6)
H12A	0.8689	−0.1293	0.5038	0.072*
C13A	0.92287 (8)	0.1007 (7)	0.56441 (12)	0.0533 (6)
H13A	0.9338	0.1415	0.5295	0.064*
N1B	0.65846 (7)	0.6473 (9)	0.90074 (12)	0.0818 (9)
N2B	0.69659 (7)	0.7618 (10)	0.94996 (11)	0.0836 (9)
C3B	0.71899 (8)	0.8843 (11)	0.91654 (12)	0.0724 (9)
H3B	0.7461	0.9809	0.9374	0.087*
N4B	0.69836 (6)	0.8560 (7)	0.84744 (9)	0.0559 (6)
C5B	0.66061 (8)	0.7056 (10)	0.84063 (13)	0.0710 (9)
H5B	0.6391	0.6515	0.7985	0.085*
N6B	0.71639 (6)	0.9630 (7)	0.79949 (9)	0.0548 (5)
C7B	0.69559 (7)	0.8917 (7)	0.73663 (11)	0.0500 (6)
H7B	0.6691	0.7835	0.7244	0.060*
C8B	0.71297 (7)	0.9785 (7)	0.68307 (11)	0.0474 (5)
C9B	0.75212 (8)	1.1431 (8)	0.69885 (13)	0.0561 (6)
H9B	0.7673	1.2118	0.7441	0.067*
C10B	0.76865 (8)	1.2052 (8)	0.64756 (14)	0.0630 (7)
H10B	0.7951	1.3128	0.6583	0.076*
C11B	0.74595 (9)	1.1078 (8)	0.58065 (13)	0.0636 (7)
H11B	0.7570	1.1516	0.5460	0.076*
C12B	0.70704 (8)	0.9466 (8)	0.56432 (12)	0.0601 (7)
H12B	0.6919	0.8808	0.5189	0.072*
C13B	0.69040 (7)	0.8821 (7)	0.61552 (11)	0.0535 (6)
H13B	0.6640	0.7737	0.6045	0.064*
N1C	0.49788 (8)	0.0614 (8)	0.83722 (13)	0.0784 (7)
N2C	0.53653 (9)	0.0797 (9)	0.82568 (12)	0.0807 (8)
C3C	0.56350 (9)	0.2426 (10)	0.87673 (13)	0.0710 (8)
H3C	0.5920	0.2902	0.8817	0.085*
N4C	0.54458 (6)	0.3340 (6)	0.92178 (10)	0.0537 (5)
C5C	0.50405 (9)	0.2134 (9)	0.89449 (15)	0.0684 (8)
H5C	0.4831	0.2370	0.9145	0.082*
N6C	0.55923 (6)	0.5052 (6)	0.98418 (10)	0.0539 (5)
C7C	0.59724 (7)	0.6207 (7)	1.00274 (11)	0.0515 (6)
H7C	0.6134	0.5897	0.9745	0.062*
C8C	0.61623 (7)	0.8013 (6)	1.06753 (11)	0.0470 (5)
C9C	0.65723 (7)	0.9332 (8)	1.08465 (12)	0.0563 (6)
H9C	0.6722	0.9077	1.0545	0.068*
C10C	0.67619 (8)	1.1023 (8)	1.14589 (13)	0.0597 (6)
H10C	0.7038	1.1912	1.1570	0.072*
C11C	0.65420 (8)	1.1391 (8)	1.19040 (13)	0.0610 (7)
H11C	0.6671	1.2517	1.2320	0.073*
C12C	0.61298 (8)	1.0098 (8)	1.17387 (13)	0.0600 (7)
H12C	0.5981	1.0367	1.2041	0.072*
C13C	0.59415 (7)	0.8429 (7)	1.11312 (12)	0.0539 (6)
H13C	0.5664	0.7563	1.1021	0.065*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1A	0.0707 (14)	0.0899 (19)	0.0753 (15)	−0.0164 (15)	0.0347 (12)	−0.0053 (15)
N2A	0.0619 (13)	0.095 (2)	0.0652 (13)	−0.0217 (15)	0.0155 (11)	−0.0066 (14)
C3A	0.0572 (14)	0.087 (2)	0.0529 (13)	−0.0134 (16)	0.0155 (11)	−0.0027 (15)
N4A	0.0480 (10)	0.0627 (13)	0.0492 (10)	−0.0038 (10)	0.0182 (8)	−0.0027 (10)
C5A	0.0688 (16)	0.082 (2)	0.0625 (14)	−0.0130 (17)	0.0333 (13)	−0.0075 (15)
N6A	0.0476 (10)	0.0621 (13)	0.0494 (10)	−0.0056 (10)	0.0161 (8)	−0.0055 (10)
C7A	0.0499 (12)	0.0533 (14)	0.0449 (11)	0.0011 (11)	0.0152 (9)	−0.0030 (11)
C8A	0.0477 (12)	0.0482 (13)	0.0464 (11)	0.0034 (11)	0.0150 (9)	0.0016 (10)
C9A	0.0611 (14)	0.0658 (17)	0.0431 (11)	−0.0012 (13)	0.0191 (11)	0.0038 (12)
C10A	0.0656 (15)	0.078 (2)	0.0652 (15)	−0.0065 (16)	0.0305 (13)	0.0109 (16)
C11A	0.0503 (13)	0.0653 (17)	0.0736 (16)	−0.0079 (14)	0.0177 (12)	0.0058 (15)
C12A	0.0560 (14)	0.0621 (16)	0.0549 (13)	−0.0034 (13)	0.0109 (11)	−0.0022 (13)
C13A	0.0560 (13)	0.0593 (15)	0.0451 (11)	−0.0007 (12)	0.0190 (10)	−0.0021 (11)
N1B	0.0627 (13)	0.129 (3)	0.0611 (13)	−0.0159 (17)	0.0309 (11)	0.0037 (16)
N2B	0.0653 (14)	0.138 (3)	0.0515 (11)	−0.0044 (17)	0.0259 (11)	−0.0004 (16)
C3B	0.0552 (14)	0.117 (3)	0.0464 (12)	−0.0110 (18)	0.0202 (11)	−0.0078 (16)
N4B	0.0439 (10)	0.0822 (16)	0.0428 (9)	−0.0034 (11)	0.0171 (8)	−0.0026 (11)
C5B	0.0501 (13)	0.112 (3)	0.0515 (13)	−0.0165 (17)	0.0192 (11)	−0.0008 (16)
N6B	0.0440 (10)	0.0778 (16)	0.0455 (10)	−0.0073 (11)	0.0195 (8)	−0.0016 (10)
C7B	0.0395 (10)	0.0629 (15)	0.0464 (11)	−0.0009 (11)	0.0141 (9)	−0.0009 (11)
C8B	0.0421 (11)	0.0538 (14)	0.0459 (11)	0.0053 (10)	0.0153 (9)	0.0042 (11)
C9B	0.0500 (12)	0.0650 (17)	0.0522 (12)	−0.0025 (12)	0.0171 (10)	0.0005 (12)
C10B	0.0571 (14)	0.0670 (17)	0.0684 (15)	−0.0072 (14)	0.0267 (12)	0.0075 (14)
C11B	0.0725 (16)	0.0701 (18)	0.0584 (14)	0.0083 (15)	0.0359 (13)	0.0132 (14)
C12B	0.0618 (14)	0.0728 (18)	0.0436 (11)	0.0079 (15)	0.0163 (10)	0.0030 (13)
C13B	0.0472 (12)	0.0651 (16)	0.0459 (11)	0.0025 (12)	0.0138 (9)	−0.0010 (12)
N1C	0.0705 (15)	0.0883 (19)	0.0681 (14)	−0.0135 (14)	0.0149 (12)	−0.0114 (15)
N2C	0.0887 (17)	0.096 (2)	0.0575 (12)	−0.0238 (17)	0.0267 (12)	−0.0143 (15)
C3C	0.0706 (16)	0.093 (2)	0.0567 (14)	−0.0223 (17)	0.0310 (13)	−0.0140 (16)
N4C	0.0526 (11)	0.0584 (13)	0.0481 (10)	−0.0033 (10)	0.0159 (8)	0.0010 (10)
C5C	0.0530 (14)	0.077 (2)	0.0696 (16)	−0.0061 (15)	0.0148 (13)	−0.0102 (16)
N6C	0.0498 (10)	0.0622 (14)	0.0493 (10)	0.0010 (10)	0.0173 (8)	−0.0001 (10)
C7C	0.0500 (12)	0.0584 (15)	0.0483 (11)	0.0014 (12)	0.0203 (10)	0.0027 (12)
C8C	0.0430 (11)	0.0496 (13)	0.0475 (11)	0.0048 (10)	0.0152 (9)	0.0060 (10)
C9C	0.0470 (12)	0.0671 (16)	0.0562 (12)	−0.0006 (13)	0.0201 (10)	0.0000 (13)
C10C	0.0447 (12)	0.0682 (17)	0.0610 (14)	−0.0027 (13)	0.0128 (11)	−0.0013 (14)
C11C	0.0598 (14)	0.0662 (18)	0.0509 (12)	0.0048 (14)	0.0123 (11)	−0.0057 (13)
C12C	0.0619 (14)	0.0639 (17)	0.0604 (14)	0.0010 (13)	0.0296 (12)	−0.0061 (13)
C13C	0.0467 (12)	0.0607 (16)	0.0565 (13)	0.0009 (12)	0.0213 (10)	0.0012 (12)

Geometric parameters (Å, º) top

N1A—C5A	1.290 (4)	C8B—C13B	1.381 (3)
N1A—N2A	1.385 (3)	C8B—C9B	1.386 (3)
N2A—C3A	1.299 (4)	C9B—C10B	1.378 (3)
C3A—N4A	1.349 (3)	C9B—H9B	0.93
C3A—H3A	0.93	C10B—C11B	1.372 (4)
N4A—C5A	1.343 (3)	C10B—H10B	0.93
N4A—N6A	1.390 (3)	C11B—C12B	1.371 (4)
C5A—H5A	0.93	C11B—H11B	0.93
N6A—C7A	1.260 (3)	C12B—C13B	1.380 (3)
C7A—C8A	1.452 (3)	C12B—H12B	0.93
C7A—H7A	0.93	C13B—H13B	0.93
C8A—C9A	1.382 (3)	N1C—C5C	1.284 (4)
C8A—C13A	1.391 (3)	N1C—N2C	1.381 (3)
C9A—C10A	1.380 (4)	N2C—C3C	1.292 (4)
C9A—H9A	0.93	C3C—N4C	1.346 (3)
C10A—C11A	1.364 (4)	C3C—H3C	0.93
C10A—H10A	0.93	N4C—C5C	1.344 (3)
C11A—C12A	1.380 (4)	N4C—N6C	1.389 (3)
C11A—H11A	0.93	C5C—H5C	0.93
C12A—C13A	1.369 (4)	N6C—C7C	1.263 (3)
C12A—H12A	0.93	C7C—C8C	1.456 (3)
C13A—H13A	0.93	C7C—H7C	0.93
N1B—C5B	1.291 (3)	C8C—C9C	1.379 (3)
N1B—N2B	1.384 (4)	C8C—C13C	1.393 (3)
N2B—C3B	1.280 (4)	C9C—C10C	1.376 (4)
C3B—N4B	1.347 (3)	C9C—H9C	0.93
C3B—H3B	0.93	C10C—C11C	1.369 (3)
N4B—C5B	1.349 (3)	C10C—H10C	0.93
N4B—N6B	1.396 (2)	C11C—C12C	1.382 (4)
C5B—H5B	0.93	C11C—H11C	0.93
N6B—C7B	1.265 (3)	C12C—C13C	1.364 (4)
C7B—C8B	1.461 (3)	C12C—H12C	0.93
C7B—H7B	0.93	C13C—H13C	0.93

C5A—N1A—N2A	106.0 (2)	C9B—C8B—C7B	121.7 (2)
C3A—N2A—N1A	107.1 (2)	C10B—C9B—C8B	120.1 (2)
N2A—C3A—N4A	110.7 (2)	C10B—C9B—H9B	120.0
N2A—C3A—H3A	124.7	C8B—C9B—H9B	120.0
N4A—C3A—H3A	124.7	C11B—C10B—C9B	119.8 (2)
C5A—N4A—C3A	104.1 (2)	C11B—C10B—H10B	120.1
C5A—N4A—N6A	122.7 (2)	C9B—C10B—H10B	120.1
C3A—N4A—N6A	133.1 (2)	C12B—C11B—C10B	120.6 (2)
N1A—C5A—N4A	112.1 (2)	C12B—C11B—H11B	119.7
N1A—C5A—H5A	124.0	C10B—C11B—H11B	119.7
N4A—C5A—H5A	124.0	C11B—C12B—C13B	119.8 (2)
C7A—N6A—N4A	116.64 (18)	C11B—C12B—H12B	120.1
N6A—C7A—C8A	121.2 (2)	C13B—C12B—H12B	120.1
N6A—C7A—H7A	119.4	C8B—C13B—C12B	120.1 (2)
C8A—C7A—H7A	119.4	C8B—C13B—H13B	120.0
C9A—C8A—C13A	118.9 (2)	C12B—C13B—H13B	120.0
C9A—C8A—C7A	119.2 (2)	C5C—N1C—N2C	106.4 (2)
C13A—C8A—C7A	121.9 (2)	C3C—N2C—N1C	107.2 (2)
C10A—C9A—C8A	120.1 (2)	N2C—C3C—N4C	110.5 (2)
C10A—C9A—H9A	119.9	N2C—C3C—H3C	124.7
C8A—C9A—H9A	119.9	N4C—C3C—H3C	124.7
C11A—C10A—C9A	120.4 (2)	C5C—N4C—C3C	104.4 (2)
C11A—C10A—H10A	119.8	C5C—N4C—N6C	122.2 (2)
C9A—C10A—H10A	119.8	C3C—N4C—N6C	133.3 (2)
C10A—C11A—C12A	120.0 (2)	N1C—C5C—N4C	111.5 (2)
C10A—C11A—H11A	120.0	N1C—C5C—H5C	124.3
C12A—C11A—H11A	120.0	N4C—C5C—H5C	124.3
C13A—C12A—C11A	120.0 (2)	C7C—N6C—N4C	116.35 (18)
C13A—C12A—H12A	120.0	N6C—C7C—C8C	121.2 (2)
C11A—C12A—H12A	120.0	N6C—C7C—H7C	119.4
C12A—C13A—C8A	120.5 (2)	C8C—C7C—H7C	119.4
C12A—C13A—H13A	119.7	C9C—C8C—C13C	118.9 (2)
C8A—C13A—H13A	119.7	C9C—C8C—C7C	119.4 (2)
C5B—N1B—N2B	107.2 (2)	C13C—C8C—C7C	121.7 (2)
C3B—N2B—N1B	106.5 (2)	C10C—C9C—C8C	120.7 (2)
N2B—C3B—N4B	111.6 (3)	C10C—C9C—H9C	119.7
N2B—C3B—H3B	124.2	C8C—C9C—H9C	119.7
N4B—C3B—H3B	124.2	C11C—C10C—C9C	119.7 (2)
C3B—N4B—C5B	104.2 (2)	C11C—C10C—H10C	120.1
C3B—N4B—N6B	122.9 (2)	C9C—C10C—H10C	120.1
C5B—N4B—N6B	132.90 (19)	C10C—C11C—C12C	120.3 (2)
N1B—C5B—N4B	110.6 (2)	C10C—C11C—H11C	119.8
N1B—C5B—H5B	124.7	C12C—C11C—H11C	119.8
N4B—C5B—H5B	124.7	C13C—C12C—C11C	119.9 (2)
C7B—N6B—N4B	116.38 (19)	C13C—C12C—H12C	120.0
N6B—C7B—C8B	120.4 (2)	C11C—C12C—H12C	120.0
N6B—C7B—H7B	119.8	C12C—C13C—C8C	120.4 (2)
C8B—C7B—H7B	119.8	C12C—C13C—H13C	119.8
C13B—C8B—C9B	119.6 (2)	C8C—C13C—H13C	119.8
C13B—C8B—C7B	118.7 (2)

C5A—N1A—N2A—C3A	0.1 (4)	N6B—C7B—C8B—C13B	176.8 (3)
N1A—N2A—C3A—N4A	0.0 (4)	N6B—C7B—C8B—C9B	−0.7 (4)
N2A—C3A—N4A—C5A	−0.1 (4)	C13B—C8B—C9B—C10B	−1.0 (4)
N2A—C3A—N4A—N6A	−177.9 (3)	C7B—C8B—C9B—C10B	176.5 (3)
N2A—N1A—C5A—N4A	−0.2 (4)	C8B—C9B—C10B—C11B	0.9 (4)
C3A—N4A—C5A—N1A	0.2 (4)	C9B—C10B—C11B—C12B	−0.5 (5)
N6A—N4A—C5A—N1A	178.2 (3)	C10B—C11B—C12B—C13B	0.2 (5)
C5A—N4A—N6A—C7A	−178.2 (3)	C9B—C8B—C13B—C12B	0.7 (4)
C3A—N4A—N6A—C7A	−0.8 (4)	C7B—C8B—C13B—C12B	−176.9 (3)
N4A—N6A—C7A—C8A	178.1 (2)	C11B—C12B—C13B—C8B	−0.3 (4)
N6A—C7A—C8A—C9A	−177.8 (3)	C5C—N1C—N2C—C3C	−0.2 (4)
N6A—C7A—C8A—C13A	1.3 (4)	N1C—N2C—C3C—N4C	0.0 (4)
C13A—C8A—C9A—C10A	−1.2 (4)	N2C—C3C—N4C—C5C	0.2 (4)
C7A—C8A—C9A—C10A	177.9 (3)	N2C—C3C—N4C—N6C	178.9 (3)
C8A—C9A—C10A—C11A	1.3 (5)	N2C—N1C—C5C—N4C	0.3 (4)
C9A—C10A—C11A—C12A	0.0 (5)	C3C—N4C—C5C—N1C	−0.3 (4)
C10A—C11A—C12A—C13A	−1.4 (5)	N6C—N4C—C5C—N1C	−179.2 (3)
C11A—C12A—C13A—C8A	1.4 (4)	C5C—N4C—N6C—C7C	−176.6 (3)
C9A—C8A—C13A—C12A	−0.1 (4)	C3C—N4C—N6C—C7C	4.9 (4)
C7A—C8A—C13A—C12A	−179.2 (3)	N4C—N6C—C7C—C8C	−179.3 (2)
C5B—N1B—N2B—C3B	0.6 (5)	N6C—C7C—C8C—C9C	−177.7 (3)
N1B—N2B—C3B—N4B	−0.7 (5)	N6C—C7C—C8C—C13C	2.7 (4)
N2B—C3B—N4B—C5B	0.4 (4)	C13C—C8C—C9C—C10C	0.3 (4)
N2B—C3B—N4B—N6B	−178.3 (3)	C7C—C8C—C9C—C10C	−179.3 (3)
N2B—N1B—C5B—N4B	−0.4 (4)	C8C—C9C—C10C—C11C	0.2 (4)
C3B—N4B—C5B—N1B	0.0 (4)	C9C—C10C—C11C—C12C	−0.5 (4)
N6B—N4B—C5B—N1B	178.6 (3)	C10C—C11C—C12C—C13C	0.4 (4)
C3B—N4B—N6B—C7B	173.0 (3)	C11C—C12C—C13C—C8C	0.1 (4)
C5B—N4B—N6B—C7B	−5.3 (5)	C9C—C8C—C13C—C12C	−0.4 (4)
N4B—N6B—C7B—C8B	−176.9 (2)	C7C—C8C—C13C—C12C	179.2 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3C—H3C···N1B	0.93	2.54	3.414 (4)	157
C7C—H7C···N1B	0.93	2.49	3.405 (3)	167
C3A—H3A···N2Cⁱ	0.93	2.47	3.387 (4)	169
C7A—H7A···N2Cⁱ	0.93	2.58	3.503 (3)	174
C5B—H5B···N2Aⁱⁱ	0.93	2.47	3.371 (4)	162

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

Experimental details

Crystal data
Chemical formula	C₉H₈N₄
M_r	172.19
Crystal system, space group	Monoclinic, C2
Temperature (K)	293
a, b, c (Å)	33.0059 (11), 4.0639 (1), 20.6535 (7)
β (°)	111.067 (2)
V (Å³)	2585.14 (14)
Z	12
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.20 × 0.15 × 0.12

Data collection
Diffractometer	Bruker Kappa APEXII area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2001)
T_min, T_max	0.983, 0.990
No. of measured, independent and observed [I > 2σ(I)] reflections	14802, 3418, 2582
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.652

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.133, 0.99
No. of reflections	3418
No. of parameters	352
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.13, −0.16

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), PLATON (Spek, 2009) and ORTEP-3 (Farrugia, 1997), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3C—H3C···N1B	0.93	2.54	3.414 (4)	157
C7C—H7C···N1B	0.93	2.49	3.405 (3)	167
C3A—H3A···N2Cⁱ	0.93	2.47	3.387 (4)	169
C7A—H7A···N2Cⁱ	0.93	2.58	3.503 (3)	174
C5B—H5B···N2Aⁱⁱ	0.93	2.47	3.371 (4)	162

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

Acknowledgements

MT thanks Dr Babu Varghese, SAIF, IIT-Madras, Chennai, India, for his help with the data collection.

References

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