5-(2-Methyl­phen­yl)-1,3,4-thia­diazol-2-amine

Wang, Y.; Kong, X.-J.; Wan, R.; Han, F.; Wang, P.

doi:10.1107/S1600536809011234

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 5| May 2009| Page o961

doi:10.1107/S1600536809011234

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5-(2-Methylphenyl)-1,3,4-thiadiazol-2-amine

Yao Wang,^a Xiang-Jun Kong,^a Rong Wan,^a ^* Feng Han ^a and Peng Wang ^a

^aDepartment of Applied Chemistry, College of Science, Nanjing University of Technology, No. 5 Xinmofan Road, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: rwan@njut.edu.cn

(Received 26 February 2009; accepted 26 March 2009; online 2 April 2009)

The asymmetric unit of the title compound, C₉H₉N₃S, contains two crystallographically independent molecules, in which the thiadiazole and tolyl rings are oriented at dihedral angles of 32.25 (3) and 74.50 (3)°. An intramolecular C—H⋯S interaction results in the formation of a five-membered ring. In the crystal structure, intermolecular N—H⋯N hydrogen bonds link the molecules into chains along the a axis. A π–π contact between the thiadiazole rings [centroid–centroid distance = 3.910 (3) Å] may further stabilize the structure. There is also a weak C—H⋯π interaction.

Related literature

For the biological activity of 1,3,4-thiadiazole derivatives, see: Nakagawa et al. (1996 ); Wang et al. (1999 ). For a related structure, see: Han et al. (2007 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₉H₉N₃S
M_r = 191.26
Monoclinic, P 2₁
a = 10.792 (2) Å
b = 7.3400 (15) Å
c = 11.831 (2) Å
β = 96.15 (3)°
V = 931.8 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.30 mm⁻¹
T = 294 K
0.20 × 0.10 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.942, T_max = 0.971
2190 measured reflections
2190 independent reflections
1620 reflections with I > 2σ(I)
R_int = 0.0000
3 standard reflections frequency: 120 min intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.053
wR(F²) = 0.162
S = 1.00
2190 reflections
237 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.27 e Å⁻³
Absolute structure: Flack (1983 ), 113 Friedel pairs
Flack parameter: 0.04 (18)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3A—H3A⋯N2Bⁱ	0.86	2.23	3.079 (8)	167
N3A—H3B⋯N1Bⁱⁱ	0.86	2.16	2.990 (6)	162
N3B—H6B⋯N2Aⁱⁱⁱ	0.86	2.22	3.006 (8)	153
N3B—H6C⋯N1A	0.86	2.23	3.035 (6)	156
C6A—H6A⋯S1A	0.93	2.71	3.090 (8)	105
C1B—H10A⋯Cg3^iv	0.96	2.89	3.623 (3)	134
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+2]$ ; (ii) x+1, y, z; (iii) $[-x+1, y-{\script{1\over 2}}, -z+2]$ ; (iv) x, y-1, z.

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: CAD-4 Software ; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809011234/hk2633sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809011234/hk2633Isup2.hkl

checkCIF report

Comment top

1,3,4-Thiadiazole derivatives represent an interesting class of compounds possessing broad spectrum biological activities (Nakagawa et al., 1996; Wang et al., 1999). These compounds are known to exhibit diverse biological effects, such as insecticidal and fungicidal activities (Wang et al., 1999). We are focused our synthetic and structural studies on 1,3,4 -thiadiazole derivatives and we have published the structure of 5-m -tolyl-1,3,4-thiadiazol-2-ylamine (Han et al., 2007). We report herein the crystal structure of the title compound.

The asymmetric unit of the title compound contains two crystallographically independent molecules (Fig. 1), in which the bond lengths (Allen et al., 1987) and angles are generally within normal ranges. Rings A (C2A-C7A), B (S1A/N1A/N2A/C8A/C9A) and C (C2B-C7B), D (S1B/N1B/N2B/C8B/C9B) are, of course, planar, and they are oriented at dihedral angles of A/B = 32.25 (3) and C/D = 74.50 (3) °. The intramolecular C-H···S interaction (Table 1) results in the formation of a five-membered ring E (S1A/C6A-C8A/H6A) adopting envelope conformation with S1A atom displaced by 0.813 (3) Å from the plane of the other ring atoms.

In the crystal structure, intra- and intermolecular N-H···N hydrogen bonds (Table 1) link the molecules into chains along the a axis (Fig. 2), in which they may be effective in the stabilization of the structure. The π-π contact between the thiadiazole rings, Cg1—Cg2ⁱ [symmetry code: (i) x, 1 + y, -1 + z, where Cg1 and Cg2 are centroids of the rings B (S1A/N1A/N2A/C8A/C9A) and D (S1B/N1B/N2B/C8B/C9B), respectively] may further stabilize the structure, with centroid-centroid distance of 3.910 (3) Å. There also exists a weak C—H···π interaction (Table 1).

Related literature top

For general background, see: Nakagawa et al. (1996); Wang et al. (1999). For a related structure, see: Han et al. (2007). For bond-length data, see: Allen et al. (1987).

Experimental top

For the preparation of the title compound, 3-methyl-benzoic acid (5 mmol) and thiosemicarbazide (5 mmol) were added in toluene (50 ml), and kept in the oil bath at 363 K for 6 h. After cooling, the crude product precipitated and was filted. Crystals suitable for X-ray analysis were obtained by slow evaporation of an acetone solution.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen bonds are shown as dashed lines.
	Fig. 2. A partial packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.

5-(2-Methylphenyl)-1,3,4-thiadiazol-2-amine top

Crystal data top

C₉H₉N₃S	F(000) = 400
M_r = 191.26	D_x = 1.363 Mg m⁻³
Monoclinic, P2₁	Melting point: 541 K
Hall symbol: P 2yb	Mo Kα radiation, λ = 0.71073 Å
a = 10.792 (2) Å	Cell parameters from 25 reflections
b = 7.3400 (15) Å	θ = 10–13°
c = 11.831 (2) Å	µ = 0.30 mm⁻¹
β = 96.15 (3)°	T = 294 K
V = 931.8 (3) Å³	Block, colorless
Z = 4	0.20 × 0.10 × 0.10 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	1620 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.000
Graphite monochromator	θ_max = 27.0°, θ_min = 1.7°
ω/2θ scans	h = −13→13
Absorption correction: ψ scan (North et al., 1968)	k = 0→9
T_min = 0.942, T_max = 0.971	l = 0→15
2190 measured reflections	3 standard reflections every 120 min
2190 independent reflections	intensity decay: 1%

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)] = 0.053	H-atom parameters constrained
wR(F²) = 0.162	w = 1/[σ²(F_o²) + (0.1P)² + 0.06P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
2190 reflections	Δρ_max = 0.29 e Å⁻³
237 parameters	Δρ_min = −0.27 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 113 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.04 (18)

Crystal data top

C₉H₉N₃S	V = 931.8 (3) Å³
M_r = 191.26	Z = 4
Monoclinic, P2₁	Mo Kα radiation
a = 10.792 (2) Å	µ = 0.30 mm⁻¹
b = 7.3400 (15) Å	T = 294 K
c = 11.831 (2) Å	0.20 × 0.10 × 0.10 mm
β = 96.15 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1620 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.000
T_min = 0.942, T_max = 0.971	3 standard reflections every 120 min
2190 measured reflections	intensity decay: 1%
2190 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	H-atom parameters constrained
wR(F²) = 0.162	Δρ_max = 0.29 e Å⁻³
S = 1.00	Δρ_min = −0.27 e Å⁻³
2190 reflections	Absolute structure: Flack (1983), 113 Friedel pairs
237 parameters	Absolute structure parameter: 0.04 (18)
1 restraint

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

	x	y	z	U_iso*/U_eq
S1A	0.87687 (12)	0.61482 (19)	0.83012 (11)	0.0525 (4)
N1A	0.6530 (4)	0.6359 (8)	0.8777 (4)	0.0504 (12)
N2A	0.7123 (4)	0.7860 (7)	0.9302 (4)	0.0506 (12)
N3A	0.9083 (4)	0.9167 (8)	0.9573 (4)	0.0572 (13)
H3A	0.8827	1.0019	0.9990	0.069*
H3B	0.9850	0.9135	0.9439	0.069*
C1A	0.4713 (6)	0.4830 (15)	0.6920 (7)	0.102 (3)
H1B	0.4032	0.4467	0.6378	0.153*
H1C	0.5046	0.5967	0.6688	0.153*
H1D	0.4422	0.4970	0.7654	0.153*
C2A	0.5735 (6)	0.3366 (11)	0.6984 (5)	0.0719 (19)
C3A	0.5524 (9)	0.1754 (12)	0.6397 (6)	0.089 (3)
H3C	0.4748	0.1541	0.5997	0.107*
C4A	0.6461 (11)	0.0427 (13)	0.6393 (7)	0.101 (3)
H4A	0.6297	−0.0665	0.6008	0.121*
C5A	0.7622 (10)	0.0745 (13)	0.6961 (6)	0.099 (3)
H5A	0.8256	−0.0109	0.6943	0.118*
C6A	0.7826 (8)	0.2317 (11)	0.7545 (5)	0.078 (2)
H6A	0.8605	0.2506	0.7943	0.094*
C7A	0.6914 (6)	0.3683 (10)	0.7579 (4)	0.0584 (15)
C8A	0.7246 (5)	0.5356 (9)	0.8216 (4)	0.0498 (14)
C9A	0.8294 (5)	0.7902 (9)	0.9137 (4)	0.0480 (13)
S1B	0.37988 (11)	0.8934 (2)	0.83030 (11)	0.0573 (5)
N1B	0.1506 (4)	0.8716 (9)	0.8594 (4)	0.0568 (13)
N2B	0.2089 (4)	0.7424 (9)	0.9293 (4)	0.0584 (13)
N3B	0.4089 (4)	0.6193 (10)	0.9831 (4)	0.0746 (18)
H6B	0.3816	0.5427	1.0295	0.090*
H6C	0.4870	0.6226	0.9745	0.090*
C1B	0.2175 (8)	0.8875 (11)	0.5560 (5)	0.082 (2)
H10A	0.2077	0.8889	0.4744	0.124*
H10B	0.1631	0.7973	0.5827	0.124*
H10C	0.3023	0.8586	0.5829	0.124*
C2B	0.1846 (5)	1.0742 (9)	0.6006 (4)	0.0532 (13)
C3B	0.1501 (6)	1.2157 (11)	0.5268 (5)	0.0688 (17)
H12A	0.1477	1.1966	0.4489	0.083*
C4B	0.1192 (5)	1.3853 (10)	0.5666 (5)	0.0660 (16)
H13A	0.0960	1.4783	0.5152	0.079*
C5B	0.1226 (6)	1.4175 (13)	0.6825 (6)	0.076 (2)
H14A	0.1014	1.5312	0.7093	0.092*
C6B	0.1574 (6)	1.2795 (9)	0.7564 (5)	0.0616 (16)
H15A	0.1616	1.3012	0.8342	0.074*
C7B	0.1866 (4)	1.1078 (9)	0.7184 (4)	0.0466 (12)
C8B	0.2252 (5)	0.9641 (9)	0.8013 (4)	0.0469 (13)
C9B	0.3289 (5)	0.7347 (9)	0.9235 (4)	0.0496 (14)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1A	0.0373 (7)	0.0732 (9)	0.0484 (7)	0.0080 (7)	0.0115 (5)	−0.0080 (7)
N1A	0.040 (2)	0.066 (3)	0.048 (2)	−0.007 (2)	0.0155 (18)	−0.010 (2)
N2A	0.038 (2)	0.065 (3)	0.051 (3)	−0.005 (2)	0.012 (2)	−0.018 (2)
N3A	0.039 (2)	0.075 (3)	0.060 (3)	0.002 (3)	0.014 (2)	−0.021 (3)
C1A	0.057 (4)	0.148 (8)	0.098 (5)	−0.003 (5)	−0.004 (4)	−0.041 (6)
C2A	0.063 (4)	0.097 (5)	0.060 (3)	−0.016 (4)	0.022 (3)	−0.019 (4)
C3A	0.106 (6)	0.094 (6)	0.072 (5)	−0.041 (5)	0.031 (4)	−0.025 (4)
C4A	0.165 (9)	0.081 (5)	0.062 (4)	−0.044 (6)	0.042 (6)	−0.003 (4)
C5A	0.159 (9)	0.086 (5)	0.051 (4)	0.022 (6)	0.016 (5)	0.003 (4)
C6A	0.104 (5)	0.083 (5)	0.048 (3)	0.013 (4)	0.008 (3)	0.007 (4)
C7A	0.061 (3)	0.076 (4)	0.039 (3)	−0.005 (3)	0.015 (2)	0.006 (3)
C8A	0.039 (3)	0.078 (4)	0.032 (2)	−0.006 (3)	0.002 (2)	0.001 (3)
C9A	0.039 (3)	0.069 (3)	0.036 (2)	0.003 (3)	0.007 (2)	−0.001 (3)
S1B	0.0337 (7)	0.0842 (11)	0.0549 (8)	−0.0021 (8)	0.0086 (6)	0.0203 (9)
N1B	0.038 (2)	0.086 (4)	0.048 (2)	0.002 (3)	0.0128 (18)	0.018 (3)
N2B	0.036 (2)	0.089 (4)	0.053 (3)	0.000 (3)	0.017 (2)	0.013 (3)
N3B	0.035 (2)	0.115 (5)	0.075 (3)	0.013 (3)	0.012 (2)	0.047 (4)
C1B	0.114 (6)	0.085 (5)	0.047 (3)	−0.002 (5)	0.004 (3)	−0.023 (4)
C2B	0.053 (3)	0.066 (3)	0.040 (2)	−0.011 (3)	0.002 (2)	−0.005 (3)
C3B	0.073 (4)	0.092 (5)	0.041 (3)	−0.014 (4)	0.002 (3)	0.005 (3)
C4B	0.053 (3)	0.081 (4)	0.065 (4)	0.005 (3)	0.009 (3)	0.021 (4)
C5B	0.071 (4)	0.091 (5)	0.071 (4)	0.005 (4)	0.029 (3)	0.000 (4)
C6B	0.064 (4)	0.072 (4)	0.052 (3)	0.014 (3)	0.023 (3)	0.000 (3)
C7B	0.037 (2)	0.062 (3)	0.041 (3)	−0.008 (3)	0.006 (2)	0.005 (3)
C8B	0.037 (3)	0.066 (3)	0.039 (3)	−0.006 (3)	0.010 (2)	−0.001 (3)
C9B	0.037 (3)	0.073 (4)	0.040 (3)	−0.002 (3)	0.012 (2)	0.010 (3)

Geometric parameters (Å, º) top

S1A—C9A	1.734 (6)	S1B—C9B	1.733 (6)
S1A—C8A	1.736 (5)	S1B—C8B	1.747 (5)
N1A—C8A	1.300 (7)	N1B—C8B	1.304 (7)
N1A—N2A	1.387 (7)	N1B—N2B	1.366 (8)
N2A—C9A	1.299 (6)	N2B—C9B	1.306 (6)
N3A—C9A	1.326 (7)	N3B—C9B	1.352 (8)
N3A—H3A	0.8600	N3B—H6B	0.8600
N3A—H3B	0.8600	N3B—H6C	0.8600
C1A—C2A	1.536 (11)	C1B—C2B	1.524 (9)
C1A—H1B	0.9600	C1B—H10A	0.9600
C1A—H1C	0.9600	C1B—H10B	0.9600
C1A—H1D	0.9600	C1B—H10C	0.9600
C2A—C3A	1.379 (10)	C2B—C3B	1.382 (9)
C2A—C7A	1.406 (9)	C2B—C7B	1.413 (7)
C3A—C4A	1.404 (13)	C3B—C4B	1.384 (10)
C3A—H3C	0.9300	C3B—H12A	0.9300
C4A—C5A	1.377 (12)	C4B—C5B	1.388 (9)
C4A—H4A	0.9300	C4B—H13A	0.9300
C5A—C6A	1.351 (12)	C5B—C6B	1.365 (10)
C5A—H5A	0.9300	C5B—H14A	0.9300
C6A—C7A	1.408 (10)	C6B—C7B	1.386 (8)
C6A—H6A	0.9300	C6B—H15A	0.9300
C7A—C8A	1.465 (9)	C7B—C8B	1.470 (8)

C9A—S1A—C8A	86.9 (3)	C9B—S1B—C8B	87.9 (3)
C8A—N1A—N2A	114.1 (4)	C8B—N1B—N2B	114.2 (4)
C9A—N2A—N1A	111.2 (5)	C9B—N2B—N1B	113.2 (5)
C9A—N3A—H3A	120.0	C9B—N3B—H6B	120.0
C9A—N3A—H3B	120.0	C9B—N3B—H6C	120.0
H3A—N3A—H3B	120.0	H6B—N3B—H6C	120.0
C2A—C1A—H1B	109.5	C2B—C1B—H10A	109.5
C2A—C1A—H1C	109.5	C2B—C1B—H10B	109.5
H1B—C1A—H1C	109.5	H10A—C1B—H10B	109.5
C2A—C1A—H1D	109.5	C2B—C1B—H10C	109.5
H1B—C1A—H1D	109.5	H10A—C1B—H10C	109.5
H1C—C1A—H1D	109.5	H10B—C1B—H10C	109.5
C3A—C2A—C7A	119.1 (8)	C3B—C2B—C7B	117.8 (6)
C3A—C2A—C1A	119.8 (7)	C3B—C2B—C1B	121.0 (5)
C7A—C2A—C1A	121.0 (6)	C7B—C2B—C1B	121.2 (5)
C2A—C3A—C4A	121.1 (8)	C2B—C3B—C4B	121.3 (6)
C2A—C3A—H3C	119.5	C2B—C3B—H12A	119.3
C4A—C3A—H3C	119.5	C4B—C3B—H12A	119.3
C5A—C4A—C3A	119.9 (8)	C3B—C4B—C5B	120.5 (7)
C5A—C4A—H4A	120.0	C3B—C4B—H13A	119.8
C3A—C4A—H4A	120.0	C5B—C4B—H13A	119.8
C6A—C5A—C4A	119.0 (9)	C6B—C5B—C4B	118.9 (7)
C6A—C5A—H5A	120.5	C6B—C5B—H14A	120.5
C4A—C5A—H5A	120.5	C4B—C5B—H14A	120.5
C5A—C6A—C7A	123.2 (8)	C5B—C6B—C7B	121.5 (5)
C5A—C6A—H6A	118.4	C5B—C6B—H15A	119.2
C7A—C6A—H6A	118.4	C7B—C6B—H15A	119.2
C2A—C7A—C6A	117.7 (7)	C6B—C7B—C2B	119.9 (5)
C2A—C7A—C8A	123.6 (6)	C6B—C7B—C8B	119.6 (5)
C6A—C7A—C8A	118.6 (6)	C2B—C7B—C8B	120.4 (6)
N1A—C8A—C7A	127.7 (5)	N1B—C8B—C7B	125.4 (5)
N1A—C8A—S1A	113.0 (5)	N1B—C8B—S1B	111.9 (4)
C7A—C8A—S1A	119.2 (4)	C7B—C8B—S1B	122.7 (4)
N2A—C9A—N3A	123.5 (5)	N2B—C9B—N3B	125.5 (5)
N2A—C9A—S1A	114.8 (5)	N2B—C9B—S1B	112.9 (4)
N3A—C9A—S1A	121.7 (4)	N3B—C9B—S1B	121.6 (4)

C8A—N1A—N2A—C9A	−1.8 (7)	C8B—N1B—N2B—C9B	−0.8 (8)
C7A—C2A—C3A—C4A	0.4 (10)	C7B—C2B—C3B—C4B	0.3 (9)
C1A—C2A—C3A—C4A	176.9 (7)	C1B—C2B—C3B—C4B	179.5 (6)
C2A—C3A—C4A—C5A	−1.5 (11)	C2B—C3B—C4B—C5B	0.3 (10)
C3A—C4A—C5A—C6A	2.1 (11)	C3B—C4B—C5B—C6B	0.3 (10)
C4A—C5A—C6A—C7A	−1.8 (11)	C4B—C5B—C6B—C7B	−1.4 (10)
C3A—C2A—C7A—C6A	−0.1 (9)	C5B—C6B—C7B—C2B	2.0 (9)
C1A—C2A—C7A—C6A	−176.4 (6)	C5B—C6B—C7B—C8B	179.2 (5)
C3A—C2A—C7A—C8A	179.1 (6)	C3B—C2B—C7B—C6B	−1.5 (8)
C1A—C2A—C7A—C8A	2.7 (9)	C1B—C2B—C7B—C6B	179.4 (6)
C5A—C6A—C7A—C2A	0.8 (10)	C3B—C2B—C7B—C8B	−178.6 (5)
C5A—C6A—C7A—C8A	−178.4 (6)	C1B—C2B—C7B—C8B	2.2 (8)
N2A—N1A—C8A—C7A	179.5 (5)	N2B—N1B—C8B—C7B	178.6 (6)
N2A—N1A—C8A—S1A	1.3 (6)	N2B—N1B—C8B—S1B	0.3 (7)
C2A—C7A—C8A—N1A	34.2 (9)	C6B—C7B—C8B—N1B	77.1 (8)
C6A—C7A—C8A—N1A	−146.6 (6)	C2B—C7B—C8B—N1B	−105.7 (7)
C2A—C7A—C8A—S1A	−147.7 (5)	C6B—C7B—C8B—S1B	−104.7 (6)
C6A—C7A—C8A—S1A	31.4 (7)	C2B—C7B—C8B—S1B	72.5 (7)
C9A—S1A—C8A—N1A	−0.4 (5)	C9B—S1B—C8B—N1B	0.2 (5)
C9A—S1A—C8A—C7A	−178.7 (5)	C9B—S1B—C8B—C7B	−178.2 (5)
N1A—N2A—C9A—N3A	−178.1 (5)	N1B—N2B—C9B—N3B	−179.8 (6)
N1A—N2A—C9A—S1A	1.4 (6)	N1B—N2B—C9B—S1B	1.0 (7)
C8A—S1A—C9A—N2A	−0.6 (5)	C8B—S1B—C9B—N2B	−0.7 (5)
C8A—S1A—C9A—N3A	178.9 (5)	C8B—S1B—C9B—N3B	−179.9 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3A—H3A···N2Bⁱ	0.86	2.23	3.079 (8)	167
N3A—H3B···N1Bⁱⁱ	0.86	2.16	2.990 (6)	162
N3B—H6B···N2Aⁱⁱⁱ	0.86	2.22	3.006 (8)	153
N3B—H6C···N1A	0.86	2.23	3.035 (6)	156
C6A—H6A···S1A	0.93	2.71	3.090 (8)	105
C1B—H10A···Cg3^iv	0.96	2.89	3.623 (3)	134

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

Experimental details

Crystal data
Chemical formula	C₉H₉N₃S
M_r	191.26
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	294
a, b, c (Å)	10.792 (2), 7.3400 (15), 11.831 (2)
β (°)	96.15 (3)
V (Å³)	931.8 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.30
Crystal size (mm)	0.20 × 0.10 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.942, 0.971
No. of measured, independent and observed [I > 2σ(I)] reflections	2190, 2190, 1620
R_int	0.000
(sin θ/λ)_max (Å⁻¹)	0.638

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.162, 1.00
No. of reflections	2190
No. of parameters	237
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.27
Absolute structure	Flack (1983), 113 Friedel pairs
Absolute structure parameter	0.04 (18)

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3A—H3A···N2Bⁱ	0.86	2.23	3.079 (8)	167
N3A—H3B···N1Bⁱⁱ	0.86	2.16	2.990 (6)	162
N3B—H6B···N2Aⁱⁱⁱ	0.86	2.22	3.006 (8)	153
N3B—H6C···N1A	0.86	2.23	3.035 (6)	156
C6A—H6A···S1A	0.93	2.71	3.090 (8)	105
C1B—H10A···Cg3^iv	0.96	2.89	3.623 (3)	134

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

Acknowledgements

The authors thank Professor Hua-qin Wang of the Analysis Centre, Nanjing University, for carrying out the X-ray crystallographic analysis.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Enraf–Nonius (1989). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Han, F., Wan, R., Wu, W.-Y., Zhang, J.-J. & Wang, J.-T. (2007). Acta Cryst. E63, o717–o718. Web of Science CSD CrossRef IUCr Journals Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
Nakagawa, Y., Nishimura, K., Izumi, K., Kinoshita, K., Kimura, T. & Kurihara, N. (1996). J. Pestic. Sci. 21, 195–201. CrossRef CAS Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wang, Y. G., Cao, L., Yan, J., Ye, W. F., Zhou, Q. C. & Lu, B. X. (1999). Chem. J. Chin. Univ. 20, 1903–1905. CAS Google Scholar