5-(3-Nitro-benz-yl)-1,3,4-thia-diazol-2-amine.

In the title mol-ecule, C(9)H(8)N(4)O(2)S, the dihedral angle between the thia-diazole and benzene rings is 73.92 (8)° and the thia-diazole group S atom is orientated towards the benzene ring, the central S-C-C-C torsion angle being 45.44 (18)°. In the crystal, supra-molecular tapes mediated by N-H⋯N hydrogen bonds and comprising alternating eight-membered {⋯HNCN}(2) and 10-membered {⋯HNH⋯NN}(2) synthons are formed along [010]. The tapes are consolidated into a three-dimensional network by a combination of C-H⋯O, C-H⋯S and C-H⋯π inter-actions.

Related literature

For background to the biological inter­est of 1,3,4-thia­diazo­les, see: Thomasco et al. (2003 ▶); Oruç et al. (2004 ▶); Moise et al. (2009 ▶); Amir et al. (2009 ▶). For the development of anti-trypanosomal compounds, see: Carvalho et al. (2004 ▶); Boechat et al. (2006 ▶); Boechat et al. (2008 ▶); Carvalho et al. (2008 ▶); Poorrajab et al. (2009 ▶) Riente et al. (2009 ▶). For the synthesis, see: Turner et al. (1988 ▶).

Experimental

Crystal data

C9H8N4O2S

M = 236.26

Triclinic,

a = 5.0878 (2) Å

b = 5.6213 (3) Å

c = 17.8035 (9) Å

α = 80.980 (3)°

β = 85.677 (3)°

γ = 79.855 (3)°

V = 494.42 (4) Å3

Z = 2

Mo Kα radiation

μ = 0.32 mm−1

T = 120 K

0.38 × 0.20 × 0.09 mm

Data collection

Nonius KappaCCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ▶) T min = 0.639, T max = 0.746

9074 measured reflections

2256 independent reflections

1973 reflections with I > 2σ(I)

R int = 0.040

Refinement

R[F 2 > 2σ(F 2)] = 0.035

wR(F 2) = 0.086

S = 1.05

2256 reflections

151 parameters

2 restraints

H-atom parameters constrained

Δρmax = 0.29 e Å−3

Δρmin = −0.33 e Å−3

Data collection: COLLECT (Hooft, 1998 ▶); cell refinement: DENZO (Otwinowski & Minor, 1997 ▶) and COLLECT; data reduction: DEn class="Chemical">NZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809049654/lh2958sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809049654/lh2958Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C9H8N4O2S	Z = 2
Mr = 236.26	F(000) = 244
Triclinic, P1	Dx = 1.587 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.0878 (2) Å	Cell parameters from 11753 reflections
b = 5.6213 (3) Å	θ = 2.9–27.5°
c = 17.8035 (9) Å	µ = 0.32 mm−1
α = 80.980 (3)°	T = 120 K
β = 85.677 (3)°	Block, colourless
γ = 79.855 (3)°	0.38 × 0.20 × 0.09 mm
V = 494.42 (4) Å3

Nonius KappaCCD area-detector diffractometer	2256 independent reflections
Radiation source: Enraf Nonius FR591 rotating anode	1973 reflections with I > 2σ(I)
10 cm confocal mirrors	Rint = 0.040
Detector resolution: 9.091 pixels mm-1	θmax = 27.5°, θmin = 3.5°
φ and ω scans	h = −6→5
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −7→7
Tmin = 0.639, Tmax = 0.746	l = −23→23
9074 measured reflections

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.086	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.0347P)2 + 0.3167P] where P = (Fo2 + 2Fc2)/3
2256 reflections	(Δ/σ)max = 0.001
151 parameters	Δρmax = 0.29 e Å−3
2 restraints	Δρmin = −0.33 e Å−3

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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.

	x	y	z	Uiso*/Ueq
S1	0.39352 (8)	0.87897 (7)	0.63466 (2)	0.01803 (12)
O1	−0.3420 (3)	0.5966 (2)	0.79836 (7)	0.0282 (3)
O2	−0.2766 (3)	0.4981 (2)	0.91883 (7)	0.0326 (3)
N1	0.7365 (3)	1.1393 (2)	0.56903 (8)	0.0187 (3)
N2	0.5591 (3)	1.2890 (2)	0.61221 (8)	0.0185 (3)
N3	0.8153 (3)	0.7356 (2)	0.54139 (8)	0.0198 (3)
H1N	0.7552	0.5959	0.5485	0.030*
H2N	0.9445	0.7652	0.5073	0.030*
N4	−0.2396 (3)	0.6204 (2)	0.85639 (8)	0.0218 (3)
C1	0.6754 (3)	0.9177 (3)	0.57569 (9)	0.0160 (3)
C2	0.3731 (3)	1.1810 (3)	0.64921 (9)	0.0161 (3)
C3	0.1583 (3)	1.2978 (3)	0.70123 (9)	0.0189 (3)
H3A	−0.0131	1.3369	0.6754	0.023*
H3B	0.2049	1.4528	0.7116	0.023*
C4	0.1235 (3)	1.1329 (3)	0.77600 (9)	0.0167 (3)
C5	−0.0430 (3)	0.9582 (3)	0.78225 (9)	0.0164 (3)
H5	−0.1411	0.9442	0.7403	0.020*
C6	−0.0634 (3)	0.8046 (3)	0.85083 (9)	0.0180 (3)
C7	0.0726 (3)	0.8188 (3)	0.91408 (10)	0.0231 (4)
H7	0.0545	0.7117	0.9604	0.028*
C8	0.2360 (3)	0.9947 (3)	0.90746 (10)	0.0249 (4)
H8	0.3309	1.0096	0.9500	0.030*
C9	0.2626 (3)	1.1498 (3)	0.83935 (10)	0.0208 (3)
H9	0.3766	1.2684	0.8358	0.025*

	U11	U22	U33	U12	U13	U23
S1	0.0196 (2)	0.0135 (2)	0.0218 (2)	−0.00748 (15)	0.00547 (15)	−0.00271 (14)
O1	0.0321 (7)	0.0250 (6)	0.0306 (7)	−0.0141 (5)	−0.0028 (5)	−0.0022 (5)
O2	0.0328 (7)	0.0306 (7)	0.0307 (7)	−0.0112 (6)	0.0028 (6)	0.0113 (5)
N1	0.0184 (7)	0.0156 (6)	0.0228 (7)	−0.0061 (5)	0.0044 (5)	−0.0039 (5)
N2	0.0186 (7)	0.0152 (6)	0.0225 (7)	−0.0061 (5)	0.0034 (5)	−0.0036 (5)
N3	0.0206 (7)	0.0140 (6)	0.0252 (8)	−0.0067 (5)	0.0064 (5)	−0.0036 (5)
N4	0.0193 (7)	0.0170 (7)	0.0271 (8)	−0.0029 (5)	0.0029 (6)	0.0012 (6)
C1	0.0156 (7)	0.0165 (7)	0.0162 (8)	−0.0058 (6)	−0.0008 (6)	0.0001 (6)
C2	0.0188 (7)	0.0130 (7)	0.0174 (8)	−0.0060 (6)	−0.0006 (6)	−0.0014 (6)
C3	0.0214 (8)	0.0131 (7)	0.0225 (8)	−0.0052 (6)	0.0035 (6)	−0.0024 (6)
C4	0.0143 (7)	0.0145 (7)	0.0210 (8)	−0.0018 (6)	0.0046 (6)	−0.0049 (6)
C5	0.0156 (7)	0.0163 (7)	0.0170 (8)	−0.0020 (6)	0.0006 (6)	−0.0033 (6)
C6	0.0150 (7)	0.0156 (7)	0.0226 (8)	−0.0024 (6)	0.0025 (6)	−0.0020 (6)
C7	0.0226 (8)	0.0262 (9)	0.0174 (8)	0.0002 (7)	0.0019 (6)	−0.0001 (7)
C8	0.0228 (9)	0.0325 (9)	0.0209 (9)	−0.0032 (7)	−0.0041 (7)	−0.0085 (7)
C9	0.0173 (8)	0.0220 (8)	0.0254 (9)	−0.0052 (6)	0.0017 (6)	−0.0096 (7)

S1—C1	1.7373 (16)	C3—H3A	0.9900
S1—C2	1.7412 (15)	C3—H3B	0.9900
O1—N4	1.2271 (19)	C4—C5	1.393 (2)
O2—N4	1.2321 (18)	C4—C9	1.400 (2)
N1—C1	1.321 (2)	C5—C6	1.389 (2)
N1—N2	1.3949 (19)	C5—H5	0.9500
N2—C2	1.297 (2)	C6—C7	1.385 (2)
N3—C1	1.342 (2)	C7—C8	1.386 (2)
N3—H1N	0.8800	C7—H7	0.9500
N3—H2N	0.8799	C8—C9	1.391 (2)
N4—C6	1.472 (2)	C8—H8	0.9500
C2—C3	1.506 (2)	C9—H9	0.9500
C3—C4	1.516 (2)
C1—S1—C2	87.36 (7)	H3A—C3—H3B	107.9
C1—N1—N2	111.82 (13)	C5—C4—C9	118.89 (15)
C2—N2—N1	113.45 (12)	C5—C4—C3	120.45 (14)
C1—N3—H1N	117.3	C9—C4—C3	120.64 (14)
C1—N3—H2N	119.9	C6—C5—C4	118.95 (14)
H1N—N3—H2N	122.0	C6—C5—H5	120.5
O1—N4—O2	123.37 (14)	C4—C5—H5	120.5
O1—N4—C6	118.11 (13)	C7—C6—C5	122.94 (15)
O2—N4—C6	118.52 (14)	C7—C6—N4	118.81 (14)
N1—C1—N3	124.39 (14)	C5—C6—N4	118.25 (14)
N1—C1—S1	113.68 (12)	C6—C7—C8	117.65 (15)
N3—C1—S1	121.93 (11)	C6—C7—H7	121.2
N2—C2—C3	124.72 (13)	C8—C7—H7	121.2
N2—C2—S1	113.68 (12)	C9—C8—C7	120.82 (15)
C3—C2—S1	121.59 (11)	C9—C8—H8	119.6
C2—C3—C4	112.03 (13)	C7—C8—H8	119.6
C2—C3—H3A	109.2	C8—C9—C4	120.74 (15)
C4—C3—H3A	109.2	C8—C9—H9	119.6
C2—C3—H3B	109.2	C4—C9—H9	119.6
C4—C3—H3B	109.2
C1—N1—N2—C2	−0.19 (19)	C3—C4—C5—C6	177.85 (14)
N2—N1—C1—N3	−178.79 (14)	C4—C5—C6—C7	0.8 (2)
N2—N1—C1—S1	0.65 (17)	C4—C5—C6—N4	−179.81 (13)
C2—S1—C1—N1	−0.70 (12)	O1—N4—C6—C7	−174.26 (14)
C2—S1—C1—N3	178.76 (14)	O2—N4—C6—C7	5.7 (2)
N1—N2—C2—C3	178.85 (14)	O1—N4—C6—C5	6.3 (2)
N1—N2—C2—S1	−0.36 (17)	O2—N4—C6—C5	−173.78 (14)
C1—S1—C2—N2	0.59 (12)	C5—C6—C7—C8	−0.2 (2)
C1—S1—C2—C3	−178.64 (14)	N4—C6—C7—C8	−179.63 (15)
N2—C2—C3—C4	−133.70 (16)	C6—C7—C8—C9	−0.4 (3)
S1—C2—C3—C4	45.44 (18)	C7—C8—C9—C4	0.5 (3)
C2—C3—C4—C5	−85.79 (18)	C5—C4—C9—C8	0.1 (2)
C2—C3—C4—C9	92.73 (17)	C3—C4—C9—C8	−178.44 (15)
C9—C4—C5—C6	−0.7 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H1n···N2i	0.88	2.25	3.0828 (19)	157
N3—H2n···N1ii	0.88	2.12	3.003 (2)	175
C3—H3a···N2iii	0.99	2.60	3.552 (2)	162
C3—H3b···S1iv	0.99	2.85	3.6687 (17)	141
C7—H7···O2v	0.95	2.53	3.355 (2)	145
C9—H9···O1vi	0.95	2.51	3.446 (2)	168
C5—H5···Cgiii	0.95	2.86	3.7708 (17)	160

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H1n⋯N2i	0.88	2.25	3.0828 (19)	157
N3—H2n⋯N1ii	0.88	2.12	3.003 (2)	175
C3—H3a⋯N2iii	0.99	2.60	3.552 (2)	162
C3—H3b⋯S1iv	0.99	2.85	3.6687 (17)	141
C7—H7⋯O2v	0.95	2.53	3.355 (2)	145
C9—H9⋯O1vi	0.95	2.51	3.446 (2)	168
C5—H5⋯Cg iii	0.95	2.86	3.7708 (17)	160

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) . Cg is the centroid of the S1/N1/N2/C1/C2 ring.