3-Methyl-4-[(E)-3-thien­ylmethyl­idene­amino]-1H-1,2,4-triazole-5(4H)-thione

Asad, M.; Oo, C.-W.; Osman, H.; Yeap, C.S.; Fun, H.-K.

doi:10.1107/S1600536810041152

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 11| November 2010| Pages o2861-o2862

https://doi.org/10.1107/S1600536810041152

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3-Methyl-4-[(E)-3-thienylmethylideneamino]-1H-1,2,4-triazole-5(4H)-thione

Mohammad Asad,^a Chuan-Wei Oo,^a ‡ Hasnah Osman,^a Chin Sing Yeap ^b § and Hoong-Kun Fun ^b ^*¶

^aSchool of Chemical Sciences, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, and ^bX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
^*Correspondence e-mail: hkfun@usm.my

(Received 5 October 2010; accepted 13 October 2010; online 20 October 2010)

The asymmetric unit of the title compound, C₈H₈N₄S₂, contains two crystallographically independent molecules. The thiophene ring of one molecule is disordered over two positions with refined site occupancies of 0.6375 (19) and 0.3625 (19). One molecule is almost planar and the other one is twisted, the dihedral angles between the thiophene and triazole rings being 7.28 (7) and 48.9 (2)° [48.5 (4)° for the minor component], respectively. An intramolecular C—H⋯S hydrogen bond stabilizes the molecular conformation of the planar molecule. In the crystal, the two molecules are interconnected by N—H⋯S hydrogen bonds into dimers, which are further consolidated into chains along the b axis by C—H⋯N hydrogen bonds. Weak C–H⋯π and π–π interactions [centroid–centroid distance = 3.5149 (7) Å] are also observed.

Related literature

For general background and the biological activity of Schiff bases of 1,2,4-triazole derivatives, see: Ghazzali et al. (2010 ); Xia et al. (2010 ); Aytac et al. (2009 ); Siddiqui et al. (2006 ); Kucukguzel et al. (2008 ). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ).

Experimental

Crystal data

C₈H₈N₄S₂
M_r = 224.30
Triclinic, $[P \overline 1]$
a = 9.3108 (7) Å
b = 10.2848 (8) Å
c = 12.7798 (10) Å
α = 66.632 (2)°
β = 83.409 (2)°
γ = 63.974 (2)°
V = 1006.88 (13) Å³
Z = 4
Mo Kα radiation
μ = 0.49 mm⁻¹
T = 100 K
0.36 × 0.25 × 0.23 mm

Data collection

Bruker APEXII DUO CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.845, T_max = 0.896
23519 measured reflections
8745 independent reflections
7500 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.114
S = 1.06
8745 reflections
288 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.06 e Å⁻³
Δρ_min = −0.50 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3A—H3NA⋯S2Bⁱ	0.894 (19)	2.46 (2)	3.3494 (11)	177.7 (18)
N3B—H3NB⋯S2Aⁱⁱ	0.84 (2)	2.45 (2)	3.2728 (12)	167.7 (19)
C5A—H5AA⋯S2A	0.93	2.50	3.2311 (12)	135
C8B—H8BA⋯N4Aⁱⁱⁱ	0.96	2.59	3.5503 (16)	175
C5B—H5BA⋯Cg1^iv	0.93	2.91	3.4955 (12)	122
Symmetry codes: (i) x-1, y, z-1; (ii) x+1, y, z+1; (iii) x+1, y-1, z+1; (iv) -x+1, -y, -z+1.

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810041152/rz2500sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810041152/rz2500Isup2.hkl

checkCIF report

Comment top

Schiff bases of 1,2,4-triazole and its derivatives have been the subject of current research in the field of pharmacology and coordination chemistry (Ghazzali et al., 2010). Due to the bioactivity associated with substituted 1,2,4-triazoles, researchers and chemists are very much interested to study the chemistry of these compounds, as they exhibit a broad spectrum of biological properties such as anticancer (Xia et al., 2010), anti-inflammatory/analgesic (Aytac et al., 2009), antibacterial/antifungal (Siddiqui et al., 2006), antiviral/anti-HIV and anti-tuberculosis (Kucukguzel et al., 2008) activities.

The asymmetric unit of the title compound consists of two crystallographically independent molecules (Fig. 1). The thiophene ring of molecule B is disordered over two positions with refined site occupancies of 0.6375 (19) and 0.3625 (19). Both molecules exist in an E configuration with respect to the central C=N double bond. Molecule A is almost planar and molecule B is twisted, the dihedral angles between the thiophene ring and the triazole ring being 7.28 (7)° and 48.9 (2)° [48.5 (4)° for the minor component] respectively. Intramolecular C—H···S hydrogen bonds stabilize the molecular structures. In the crystal structure, the two molecules are interconnected by N3A—H3NA···S2B and N3B—H3NB···S2A hydrogen bonds (Table 1) into dimers and these dimers are further consolidated into chains along the b axis (Fig. 2) by C8B—H8BA···N4A hydrogen bonds (Table 1). Weak C–H···π and π···π interactions are also observed [Cg1···Cg2^v = 3.5149 (7) Å; (v) 1 - x, -y, -z. Cg1 and Cg2 are centroids of S1A–C1A–C4A–C3A–C2A and N2A–C6A–N3A–N4A–C7A ring, respectively].

Related literature top

For general background and the biological activity of Schiff bases of 1,2,4-triazole derivatives, see: Ghazzali et al. (2010); Xia et al. (2010); Aytac et al. (2009); Siddiqui et al. (2006); Kucukguzel et al. (2008). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986).

Experimental top

A mixture of 3-methyl-4-amino-5-mercapto-1,2,4-triazole (4.46 mmol, 0.58 g) and thiophene-3-carboxaldehyde (4.46 mmol, 0.5 g) containing pyridine (0.1 ml) in ethanol was refluxed for about 13 to 14 h. The reaction mixture was cooled to room temperature and the light yellow solid was filtered off, washed with water, dried and recrystallized from chloroform-methanol (1:1 v/v) to get the title compound in 65% yield.

Structure description top

For general background and the biological activity of Schiff bases of 1,2,4-triazole derivatives, see: Ghazzali et al. (2010); Xia et al. (2010); Aytac et al. (2009); Siddiqui et al. (2006); Kucukguzel et al. (2008). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound with atom labels and 50% probability ellipsoids for non-H atoms.
	Fig. 2. The crystal packing of the title compound viewed down the c axis showing chains along the b axis. Only the major component of disorder is shown. Intermolecular hydrogen bonds are shown as dashed lines.

3-Methyl-4-[(E)-3-thienylmethylideneamino]-1H-1,2,4-triazole- 5(4H)-thione top

Crystal data top

C₈H₈N₄S₂	Z = 4
M_r = 224.30	F(000) = 464
Triclinic, P1	D_x = 1.480 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.3108 (7) Å	Cell parameters from 9994 reflections
b = 10.2848 (8) Å	θ = 2.4–35.0°
c = 12.7798 (10) Å	µ = 0.49 mm⁻¹
α = 66.632 (2)°	T = 100 K
β = 83.409 (2)°	Block, colourless
γ = 63.974 (2)°	0.36 × 0.25 × 0.23 mm
V = 1006.88 (13) Å³

Data collection top

Bruker APEXII DUO CCD area-detector diffractometer	8745 independent reflections
Radiation source: fine-focus sealed tube	7500 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
φ and ω scans	θ_max = 35.1°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −15→13
T_min = 0.845, T_max = 0.896	k = −16→16
23519 measured reflections	l = −17→20

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.114	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0606P)² + 0.2963P] where P = (F_o² + 2F_c²)/3
8745 reflections	(Δ/σ)_max = 0.001
288 parameters	Δρ_max = 1.06 e Å⁻³
1 restraint	Δρ_min = −0.50 e Å⁻³

Crystal data top

C₈H₈N₄S₂	γ = 63.974 (2)°
M_r = 224.30	V = 1006.88 (13) Å³
Triclinic, P1	Z = 4
a = 9.3108 (7) Å	Mo Kα radiation
b = 10.2848 (8) Å	µ = 0.49 mm⁻¹
c = 12.7798 (10) Å	T = 100 K
α = 66.632 (2)°	0.36 × 0.25 × 0.23 mm
β = 83.409 (2)°

Data collection top

Bruker APEXII DUO CCD area-detector diffractometer	8745 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	7500 reflections with I > 2σ(I)
T_min = 0.845, T_max = 0.896	R_int = 0.025
23519 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	1 restraint
wR(F²) = 0.114	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 1.06 e Å⁻³
8745 reflections	Δρ_min = −0.50 e Å⁻³
288 parameters

Special details top

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
S1A	0.76095 (4)	−0.34744 (4)	0.39899 (2)	0.02948 (7)
S2A	0.22259 (3)	−0.11508 (3)	−0.03400 (2)	0.02363 (6)
N1A	0.35008 (11)	0.05807 (10)	0.09471 (7)	0.02091 (15)
N2A	0.24129 (11)	0.12778 (10)	0.00194 (7)	0.01941 (14)
N3A	0.07864 (12)	0.20250 (10)	−0.13672 (8)	0.02245 (16)
N4A	0.06835 (12)	0.33875 (11)	−0.13366 (8)	0.02392 (17)
C1A	0.63594 (14)	−0.31400 (13)	0.29387 (9)	0.02447 (19)
H1AA	0.6348	−0.3924	0.2755	0.029*
C2A	0.68112 (15)	−0.15163 (15)	0.37468 (10)	0.0279 (2)
H2AA	0.7137	−0.1108	0.4157	0.033*
C3A	0.56310 (14)	−0.06294 (13)	0.28710 (9)	0.02428 (19)
H3AA	0.5065	0.0456	0.2614	0.029*
C4A	0.53698 (12)	−0.15641 (12)	0.23970 (8)	0.02067 (16)
C5A	0.42312 (13)	−0.09238 (12)	0.14318 (8)	0.02136 (17)
H5AA	0.4042	−0.1571	0.1179	0.026*
C6A	0.18194 (12)	0.07072 (11)	−0.05621 (8)	0.01945 (16)
C7A	0.16892 (13)	0.29067 (12)	−0.04888 (8)	0.02199 (17)
C8A	0.20936 (16)	0.39193 (13)	−0.01317 (10)	0.0285 (2)
H8AA	0.1551	0.4992	−0.0654	0.043*
H8AB	0.3230	0.3597	−0.0134	0.043*
H8AC	0.1762	0.3825	0.0624	0.043*
S2B	0.88542 (4)	0.23323 (3)	0.64301 (2)	0.02461 (7)
N1B	0.78425 (11)	0.05827 (10)	0.51301 (7)	0.02158 (16)
N2B	0.85328 (11)	−0.01306 (10)	0.62466 (7)	0.01962 (15)
N3B	0.97744 (12)	−0.07490 (11)	0.77934 (8)	0.02242 (16)
N4B	0.98117 (13)	−0.21239 (11)	0.78403 (8)	0.02472 (17)
C4B	0.58641 (12)	0.28766 (11)	0.37606 (8)	0.01978 (16)
S1B	0.38121 (11)	0.51444 (11)	0.21591 (7)	0.02699 (15)	0.6375 (19)
C1B	0.4516 (4)	0.4333 (3)	0.3522 (3)	0.0172 (6)	0.6375 (19)
H1BA	0.4077	0.4784	0.4054	0.021*	0.6375 (19)
C2B	0.5300 (10)	0.3569 (8)	0.1808 (6)	0.0429 (15)	0.6375 (19)
H2BA	0.5390	0.3496	0.1099	0.051*	0.6375 (19)
C3B	0.6279 (10)	0.2492 (8)	0.2775 (7)	0.0299 (7)	0.6375 (19)
H3BA	0.7151	0.1577	0.2789	0.036*	0.6375 (19)
S1X	0.5125 (4)	0.3829 (3)	0.1634 (2)	0.0288 (4)	0.3625 (19)
C1X	0.6323 (13)	0.2441 (10)	0.2839 (10)	0.0172 (6)	0.3625 (19)
H1XA	0.7179	0.1506	0.2871	0.021*	0.3625 (19)
C2X	0.3997 (10)	0.5014 (10)	0.2362 (7)	0.0429 (15)	0.3625 (19)
H2XA	0.3132	0.5990	0.2040	0.051*	0.3625 (19)
C3X	0.4540 (11)	0.4332 (11)	0.3424 (8)	0.048 (2)	0.3625 (19)
H3XA	0.4062	0.4799	0.3943	0.057*	0.3625 (19)
C5B	0.66610 (12)	0.19528 (11)	0.49031 (8)	0.01976 (16)
H5BA	0.6319	0.2350	0.5472	0.024*
C6B	0.90351 (12)	0.04953 (11)	0.68276 (8)	0.01932 (16)
C7B	0.90578 (13)	−0.17204 (11)	0.68809 (8)	0.02196 (17)
C8B	0.87796 (17)	−0.27885 (13)	0.65086 (10)	0.0302 (2)
H8BA	0.9231	−0.3832	0.7087	0.045*
H8BB	0.9279	−0.2790	0.5809	0.045*
H8BC	0.7649	−0.2436	0.6389	0.045*
H3NA	0.025 (2)	0.210 (2)	−0.1941 (16)	0.035 (5)*
H3NB	1.027 (2)	−0.077 (2)	0.8312 (17)	0.037 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1A	0.02947 (14)	0.02718 (13)	0.02285 (12)	−0.01128 (11)	−0.00947 (10)	0.00081 (10)
S2A	0.02878 (13)	0.01789 (11)	0.02143 (11)	−0.00851 (9)	−0.00820 (9)	−0.00404 (8)
N1A	0.0232 (4)	0.0199 (3)	0.0164 (3)	−0.0082 (3)	−0.0052 (3)	−0.0033 (3)
N2A	0.0224 (4)	0.0171 (3)	0.0158 (3)	−0.0077 (3)	−0.0046 (3)	−0.0028 (3)
N3A	0.0257 (4)	0.0188 (3)	0.0196 (3)	−0.0092 (3)	−0.0074 (3)	−0.0025 (3)
N4A	0.0279 (4)	0.0187 (4)	0.0213 (4)	−0.0091 (3)	−0.0065 (3)	−0.0029 (3)
C1A	0.0253 (5)	0.0209 (4)	0.0227 (4)	−0.0103 (4)	−0.0057 (3)	−0.0018 (3)
C2A	0.0320 (5)	0.0301 (5)	0.0219 (4)	−0.0149 (4)	−0.0066 (4)	−0.0064 (4)
C3A	0.0295 (5)	0.0233 (4)	0.0187 (4)	−0.0119 (4)	−0.0053 (3)	−0.0044 (3)
C4A	0.0223 (4)	0.0200 (4)	0.0166 (3)	−0.0098 (3)	−0.0041 (3)	−0.0019 (3)
C5A	0.0230 (4)	0.0197 (4)	0.0187 (4)	−0.0088 (3)	−0.0051 (3)	−0.0035 (3)
C6A	0.0209 (4)	0.0187 (4)	0.0160 (3)	−0.0081 (3)	−0.0034 (3)	−0.0034 (3)
C7A	0.0260 (4)	0.0172 (4)	0.0190 (4)	−0.0084 (3)	−0.0043 (3)	−0.0028 (3)
C8A	0.0369 (6)	0.0209 (4)	0.0266 (5)	−0.0126 (4)	−0.0080 (4)	−0.0052 (4)
S2B	0.03028 (13)	0.01731 (11)	0.02452 (12)	−0.00988 (9)	−0.00816 (9)	−0.00420 (9)
N1B	0.0251 (4)	0.0173 (3)	0.0176 (3)	−0.0066 (3)	−0.0066 (3)	−0.0029 (3)
N2B	0.0229 (4)	0.0144 (3)	0.0173 (3)	−0.0064 (3)	−0.0061 (3)	−0.0019 (3)
N3B	0.0275 (4)	0.0197 (4)	0.0183 (3)	−0.0108 (3)	−0.0063 (3)	−0.0028 (3)
N4B	0.0316 (5)	0.0182 (3)	0.0205 (4)	−0.0107 (3)	−0.0081 (3)	−0.0011 (3)
C4B	0.0219 (4)	0.0163 (4)	0.0181 (4)	−0.0083 (3)	−0.0035 (3)	−0.0024 (3)
S1B	0.0283 (3)	0.0208 (2)	0.0227 (2)	−0.00926 (19)	−0.00948 (18)	0.00179 (17)
C1B	0.0168 (9)	0.0083 (7)	0.0140 (7)	0.0010 (6)	−0.0091 (7)	0.0030 (6)
C2B	0.0343 (17)	0.0261 (19)	0.063 (4)	−0.0096 (14)	−0.002 (2)	−0.014 (2)
C3B	0.0346 (15)	0.0358 (15)	0.0226 (16)	−0.0165 (12)	0.0019 (11)	−0.0131 (12)
S1X	0.0313 (8)	0.0265 (9)	0.0240 (5)	−0.0102 (7)	−0.0031 (5)	−0.0066 (5)
C1X	0.0168 (9)	0.0083 (7)	0.0140 (7)	0.0010 (6)	−0.0091 (7)	0.0030 (6)
C2X	0.0343 (17)	0.0261 (19)	0.063 (4)	−0.0096 (14)	−0.002 (2)	−0.014 (2)
C3X	0.053 (4)	0.056 (4)	0.069 (5)	−0.041 (3)	0.029 (3)	−0.044 (4)
C5B	0.0215 (4)	0.0172 (4)	0.0180 (4)	−0.0080 (3)	−0.0034 (3)	−0.0034 (3)
C6B	0.0202 (4)	0.0172 (4)	0.0184 (4)	−0.0075 (3)	−0.0034 (3)	−0.0041 (3)
C7B	0.0268 (4)	0.0152 (4)	0.0190 (4)	−0.0080 (3)	−0.0067 (3)	−0.0010 (3)
C8B	0.0433 (6)	0.0178 (4)	0.0266 (5)	−0.0125 (4)	−0.0124 (4)	−0.0027 (4)

Geometric parameters (Å, º) top

S1A—C1A	1.7085 (11)	N2B—C7B	1.3812 (12)
S1A—C2A	1.7170 (13)	N3B—C6B	1.3430 (12)
S2A—C6A	1.6838 (10)	N3B—N4B	1.3765 (13)
N1A—C5A	1.2859 (13)	N3B—H3NB	0.84 (2)
N1A—N2A	1.3820 (11)	N4B—C7B	1.3063 (13)
N2A—C6A	1.3881 (12)	C4B—C1X	1.381 (13)
N2A—C7A	1.3889 (13)	C4B—C3X	1.392 (10)
N3A—C6A	1.3408 (13)	C4B—C1B	1.410 (3)
N3A—N4A	1.3781 (13)	C4B—C3B	1.429 (8)
N3A—H3NA	0.896 (19)	C4B—C5B	1.4542 (13)
N4A—C7A	1.3026 (13)	S1B—C1B	1.670 (3)
C1A—C4A	1.3787 (15)	S1B—C2B	1.791 (9)
C1A—H1AA	0.9300	C1B—H1BA	0.9300
C2A—C3A	1.3730 (15)	C2B—C3B	1.367 (9)
C2A—H2AA	0.9300	C2B—H2BA	0.9300
C3A—C4A	1.4322 (15)	C3B—H3BA	0.9300
C3A—H3AA	0.9300	S1X—C1X	1.705 (9)
C4A—C5A	1.4568 (13)	S1X—C2X	1.734 (8)
C5A—H5AA	0.9300	C1X—H1XA	0.9300
C7A—C8A	1.4816 (15)	C2X—C3X	1.297 (13)
C8A—H8AA	0.9600	C2X—H2XA	0.9300
C8A—H8AB	0.9600	C3X—H3XA	0.9300
C8A—H8AC	0.9600	C5B—H5BA	0.9300
S2B—C6B	1.6837 (10)	C7B—C8B	1.4809 (15)
N1B—C5B	1.2917 (13)	C8B—H8BA	0.9600
N1B—N2B	1.3977 (11)	C8B—H8BB	0.9600
N2B—C6B	1.3811 (12)	C8B—H8BC	0.9600

C1A—S1A—C2A	92.44 (5)	C1X—C4B—C3X	109.6 (5)
C5A—N1A—N2A	120.12 (9)	C1X—C4B—C1B	114.6 (3)
N1A—N2A—C6A	134.03 (8)	C3X—C4B—C3B	107.0 (5)
N1A—N2A—C7A	117.69 (8)	C1B—C4B—C3B	112.0 (3)
C6A—N2A—C7A	108.28 (8)	C1X—C4B—C5B	124.8 (3)
C6A—N3A—N4A	114.25 (8)	C3X—C4B—C5B	125.6 (4)
C6A—N3A—H3NA	127.0 (12)	C1B—C4B—C5B	120.56 (16)
N4A—N3A—H3NA	118.5 (12)	C3B—C4B—C5B	127.5 (3)
C7A—N4A—N3A	104.29 (8)	C1B—S1B—C2B	94.2 (3)
C4A—C1A—S1A	111.67 (8)	C4B—C1B—S1B	111.2 (2)
C4A—C1A—H1AA	124.2	C4B—C1B—H1BA	124.4
S1A—C1A—H1AA	124.2	S1B—C1B—H1BA	124.4
C3A—C2A—S1A	111.42 (8)	C3B—C2B—S1B	107.5 (6)
C3A—C2A—H2AA	124.3	C3B—C2B—H2BA	126.3
S1A—C2A—H2AA	124.3	S1B—C2B—H2BA	126.3
C2A—C3A—C4A	112.42 (10)	C2B—C3B—C4B	115.1 (6)
C2A—C3A—H3AA	123.8	C2B—C3B—H3BA	122.4
C4A—C3A—H3AA	123.8	C4B—C3B—H3BA	122.4
C1A—C4A—C3A	112.04 (9)	C1X—S1X—C2X	91.4 (5)
C1A—C4A—C5A	123.85 (10)	C4B—C1X—S1X	111.6 (5)
C3A—C4A—C5A	124.08 (9)	C4B—C1X—H1XA	124.2
N1A—C5A—C4A	116.66 (9)	S1X—C1X—H1XA	124.2
N1A—C5A—H5AA	121.7	C3X—C2X—S1X	109.7 (7)
C4A—C5A—H5AA	121.7	C3X—C2X—H2XA	125.1
N3A—C6A—N2A	102.63 (8)	S1X—C2X—H2XA	125.1
N3A—C6A—S2A	126.98 (8)	C2X—C3X—C4B	117.6 (8)
N2A—C6A—S2A	130.38 (7)	C2X—C3X—H3XA	121.2
N4A—C7A—N2A	110.54 (9)	C4B—C3X—H3XA	121.2
N4A—C7A—C8A	125.91 (9)	N1B—C5B—C4B	120.21 (9)
N2A—C7A—C8A	123.48 (9)	N1B—C5B—H5BA	119.9
C7A—C8A—H8AA	109.5	C4B—C5B—H5BA	119.9
C7A—C8A—H8AB	109.5	N3B—C6B—N2B	102.76 (8)
H8AA—C8A—H8AB	109.5	N3B—C6B—S2B	127.50 (8)
C7A—C8A—H8AC	109.5	N2B—C6B—S2B	129.69 (7)
H8AA—C8A—H8AC	109.5	N4B—C7B—N2B	110.39 (9)
H8AB—C8A—H8AC	109.5	N4B—C7B—C8B	125.79 (9)
C5B—N1B—N2B	113.61 (9)	N2B—C7B—C8B	123.82 (9)
C6B—N2B—C7B	108.61 (8)	C7B—C8B—H8BA	109.5
C6B—N2B—N1B	128.38 (8)	C7B—C8B—H8BB	109.5
C7B—N2B—N1B	122.26 (8)	H8BA—C8B—H8BB	109.5
C6B—N3B—N4B	113.86 (8)	C7B—C8B—H8BC	109.5
C6B—N3B—H3NB	126.2 (13)	H8BA—C8B—H8BC	109.5
N4B—N3B—H3NB	119.7 (13)	H8BB—C8B—H8BC	109.5
C7B—N4B—N3B	104.32 (8)

C5A—N1A—N2A—C6A	2.18 (18)	S1B—C2B—C3B—C4B	0.9 (10)
C5A—N1A—N2A—C7A	−178.40 (10)	C1X—C4B—C3B—C2B	178 (100)
C6A—N3A—N4A—C7A	0.28 (13)	C3X—C4B—C3B—C2B	−1.7 (9)
C2A—S1A—C1A—C4A	1.06 (10)	C1B—C4B—C3B—C2B	−1.1 (9)
C1A—S1A—C2A—C3A	−0.79 (10)	C5B—C4B—C3B—C2B	178.9 (5)
S1A—C2A—C3A—C4A	0.34 (14)	C3X—C4B—C1X—S1X	0.3 (10)
S1A—C1A—C4A—C3A	−1.04 (13)	C1B—C4B—C1X—S1X	1.0 (10)
S1A—C1A—C4A—C5A	177.06 (9)	C3B—C4B—C1X—S1X	0 (19)
C2A—C3A—C4A—C1A	0.45 (15)	C5B—C4B—C1X—S1X	−179.1 (3)
C2A—C3A—C4A—C5A	−177.65 (11)	C2X—S1X—C1X—C4B	0.1 (9)
N2A—N1A—C5A—C4A	179.43 (9)	C1X—S1X—C2X—C3X	−0.6 (9)
C1A—C4A—C5A—N1A	−173.55 (11)	S1X—C2X—C3X—C4B	1.0 (11)
C3A—C4A—C5A—N1A	4.33 (16)	C1X—C4B—C3X—C2X	−0.9 (11)
N4A—N3A—C6A—N2A	−0.02 (12)	C1B—C4B—C3X—C2X	−174 (6)
N4A—N3A—C6A—S2A	179.17 (8)	C3B—C4B—C3X—C2X	−0.9 (10)
N1A—N2A—C6A—N3A	179.21 (11)	C5B—C4B—C3X—C2X	178.6 (6)
C7A—N2A—C6A—N3A	−0.24 (11)	N2B—N1B—C5B—C4B	177.18 (9)
N1A—N2A—C6A—S2A	0.07 (18)	C1X—C4B—C5B—N1B	−3.5 (7)
C7A—N2A—C6A—S2A	−179.39 (9)	C3X—C4B—C5B—N1B	177.1 (5)
N3A—N4A—C7A—N2A	−0.43 (12)	C1B—C4B—C5B—N1B	176.36 (19)
N3A—N4A—C7A—C8A	176.66 (11)	C3B—C4B—C5B—N1B	−3.6 (5)
N1A—N2A—C7A—N4A	−179.11 (9)	N4B—N3B—C6B—N2B	1.89 (12)
C6A—N2A—C7A—N4A	0.44 (13)	N4B—N3B—C6B—S2B	−175.95 (9)
N1A—N2A—C7A—C8A	3.72 (16)	C7B—N2B—C6B—N3B	−2.32 (12)
C6A—N2A—C7A—C8A	−176.73 (11)	N1B—N2B—C6B—N3B	−172.46 (10)
C5B—N1B—N2B—C6B	−49.59 (15)	C7B—N2B—C6B—S2B	175.46 (9)
C5B—N1B—N2B—C7B	141.48 (10)	N1B—N2B—C6B—S2B	5.31 (17)
C6B—N3B—N4B—C7B	−0.69 (13)	N3B—N4B—C7B—N2B	−0.87 (13)
C1X—C4B—C1B—S1B	0.7 (6)	N3B—N4B—C7B—C8B	179.50 (12)
C3X—C4B—C1B—S1B	7 (5)	C6B—N2B—C7B—N4B	2.09 (13)
C3B—C4B—C1B—S1B	0.7 (5)	N1B—N2B—C7B—N4B	172.96 (10)
C5B—C4B—C1B—S1B	−179.23 (13)	C6B—N2B—C7B—C8B	−178.27 (11)
C2B—S1B—C1B—C4B	−0.2 (4)	N1B—N2B—C7B—C8B	−7.40 (17)
C1B—S1B—C2B—C3B	−0.4 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3A—H3NA···S2Bⁱ	0.894 (19)	2.46 (2)	3.3494 (11)	177.7 (18)
N3B—H3NB···S2Aⁱⁱ	0.84 (2)	2.45 (2)	3.2728 (12)	167.7 (19)
C5A—H5AA···S2A	0.93	2.50	3.2311 (12)	135
C8B—H8BA···N4Aⁱⁱⁱ	0.96	2.59	3.5503 (16)	175
C5B—H5BA···Cg1^iv	0.93	2.91	3.4955 (12)	122

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

Experimental details

Crystal data
Chemical formula	C₈H₈N₄S₂
M_r	224.30
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	9.3108 (7), 10.2848 (8), 12.7798 (10)
α, β, γ (°)	66.632 (2), 83.409 (2), 63.974 (2)
V (Å³)	1006.88 (13)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.49
Crystal size (mm)	0.36 × 0.25 × 0.23

Data collection
Diffractometer	Bruker APEXII DUO CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.845, 0.896
No. of measured, independent and observed [I > 2σ(I)] reflections	23519, 8745, 7500
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.809

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.114, 1.06
No. of reflections	8745
No. of parameters	288
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.06, −0.50

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3A—H3NA···S2Bⁱ	0.894 (19)	2.46 (2)	3.3494 (11)	177.7 (18)
N3B—H3NB···S2Aⁱⁱ	0.84 (2)	2.45 (2)	3.2728 (12)	167.7 (19)
C5A—H5AA···S2A	0.9300	2.5000	3.2311 (12)	135.00
C8B—H8BA···N4Aⁱⁱⁱ	0.9600	2.5900	3.5503 (16)	175.00
C5B—H5BA···Cg1^iv	0.93	2.91	3.4955 (12)	122

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

Footnotes

‡Additional correspondence author, e-mail: oocw@usm.my.

§Thomson Reuters ResearcherID: A-5523-2009.

¶Thomson Reuters ResearcherID: A-3561-2009.

Acknowledgements

The authors are thankful to Universiti Sains Malaysia (USM) for providing the necessary research facilities and RU research funding under grant No. 1001/PKIMIA/811134. MA also thanks Universiti Sains Malaysia for the award of a post doctoral fellowship and HKF and CSY thank USM for the Research University Grant No. 1001/PFIZIK/811160.

References

Aytac, S. P., Tozkoparan, B., Kaynak, F. B., Aktay, G., Goktas, O. & Unuvar, S. (2009). Eur. J. Med. Chem. 44, 4528–4538. Web of Science CSD CrossRef PubMed CAS Google Scholar
Bruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cosier, J. & Glazer, A. M. (1986). J. Appl. Cryst. 19, 105–107. CrossRef CAS Web of Science IUCr Journals Google Scholar
Ghazzali, M., Al-Farhan, K., El-Faham, A. & Reedijk, J. (2010). Polyhedron, 29, 2829–2832. Web of Science CSD CrossRef CAS Google Scholar
Kucukguzel, I., Tatar, E., Kucukguzel, S. G., Rolollas, S. & Clercq, E. D. (2008). Eur. J. Med. Chem. 43, 381–392. Web of Science CrossRef PubMed Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Siddiqui, Z. N., Khuwaja, G. & Asad, M. (2006). Heterocycl. Commun. 12, 443–448. CrossRef CAS Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Xia, Y., Qu, F. & Peng, L. (2010). Mini-Rev. Med. Chem. 10, 806–821. CrossRef CAS Google Scholar