4-Amino-3-(4-chloro-phen-yl)-1H-1,2,4-triazole-5(4H)-thione.

In the title compound, C(8)H(7)ClN(4)S, the benzene ring is statistically disordered over two conformations rotated about the Cl-C⋯C-C axis, which subtend dihedral angles of 24.7 (3) and 9.9 (2) ° with respect to the triazole ring. An intra-molecular C-H⋯N close contact occurs. In the crystal, N-H⋯N and N-H⋯S hydrogen bonds link the mol-ecules into (001) sheets: R(2) (2)(8) and R(2) (2)(10) graph-set motifs result. Weak C-H⋯N hydrogen bonds and aromatic π-π stacking inter-actions [shortest centroid-centroid separation = 3.681 (7) Å] complete the structure.

Related literature

For a related structure and background references, see: Natarajan & Mathews (2011 ▶). For a related structure, see: Ambalavanan et al. (2003 ▶).

Experimental

Crystal data

C8H7ClN4S

M = 226.69

Triclinic,

a = 6.0765 (9) Å

b = 8.0268 (7) Å

c = 10.9873 (16) Å

α = 72.501 (10)°

β = 87.597 (10)°

γ = 67.88 (2)°

V = 471.94 (12) Å3

Z = 2

Cu Kα radiation

μ = 5.35 mm−1

T = 293 K

0.24 × 0.18 × 0.12 mm

Data collection

Enraf–Nonius CAD-4 diffractometer

Absorption correction: part of the refinement model (ΔF) (SHELXA; Sheldrick, 2008) ▶ T min = 0.146, T max = 0.618

1912 measured reflections

1818 independent reflections

1670 reflections with I > 2σ(I)

R int = 0.054

3 standard reflections every 60 min intensity decay: none

Refinement

R[F 2 > 2σ(F 2)] = 0.080

wR(F 2) = 0.236

S = 1.09

1818 reflections

173 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.62 e Å−3

Δρmin = −0.51 e Å−3

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ▶); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms, 1996 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97 and PLATON.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812000785/hb6583sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812000785/hb6583Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812000785/hb6583Isup3.cml

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

C8H7ClN4S	Z = 2
Mr = 226.69	F(000) = 232
Triclinic, P1	Dx = 1.595 Mg m−3
a = 6.0765 (9) Å	Cu Kα radiation, λ = 1.54184 Å
b = 8.0268 (7) Å	Cell parameters from 25 reflections
c = 10.9873 (16) Å	θ = 1–60°
α = 72.501 (10)°	µ = 5.35 mm−1
β = 87.597 (10)°	T = 293 K
γ = 67.88 (2)°	Needle, yellow
V = 471.94 (12) Å3	0.24 × 0.18 × 0.12 mm

Enraf–Nonius CAD-4 diffractometer	1670 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.054
graphite	θmax = 72.5°, θmin = 4.2°
ω scans	h = −6→7
Absorption correction: part of the refinement model (ΔF) (SHELXA; Sheldrick, 2008)	k = −9→9
Tmin = 0.146, Tmax = 0.618	l = −9→13
1912 measured reflections	3 standard reflections every 60 min
1818 independent reflections	intensity decay: none

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)] = 0.080	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.236	w = 1/[σ2(Fo2) + (0.1913P)2 + 0.1469P] where P = (Fo2 + 2Fc2)/3
S = 1.09	(Δ/σ)max < 0.001
1818 reflections	Δρmax = 0.62 e Å−3
173 parameters	Δρmin = −0.51 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.031 (8)

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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cl1	0.91511 (17)	0.68117 (13)	−0.30339 (8)	0.0585 (5)
S1	0.31850 (16)	0.79307 (13)	0.50686 (8)	0.0534 (5)
N1	0.5022 (5)	0.7466 (4)	0.2844 (2)	0.0404 (7)
N2	0.7683 (6)	0.8756 (5)	0.2550 (3)	0.0569 (9)
N3	0.6640 (6)	0.8820 (5)	0.3677 (3)	0.0596 (9)
H3	0.7032	0.9292	0.4196	0.072*
N4	0.3603 (7)	0.6528 (5)	0.2662 (3)	0.0541 (8)
C1	0.4998 (6)	0.8091 (5)	0.3885 (3)	0.0453 (8)
C2	0.6627 (5)	0.7938 (4)	0.2044 (3)	0.0407 (7)
C3	0.7171 (5)	0.7637 (4)	0.0791 (3)	0.0395 (7)
C4A	0.5509 (19)	0.7474 (19)	0.0004 (9)	0.0404 (19)	0.50 (2)
H4A	0.4041	0.7494	0.0291	0.048*	0.50 (2)
C5A	0.6105 (19)	0.7284 (18)	−0.1214 (9)	0.048 (2)	0.50 (2)
H5A	0.5020	0.7227	−0.1757	0.057*	0.50 (2)
C4B	0.631 (2)	0.661 (2)	0.0331 (10)	0.041 (2)	0.50 (2)
H4B	0.5303	0.6072	0.0799	0.050*	0.50 (2)
C5B	0.694 (2)	0.636 (2)	−0.0856 (10)	0.047 (3)	0.50 (2)
H5B	0.6401	0.5606	−0.1156	0.056*	0.50 (2)
C6	0.8321 (6)	0.7185 (4)	−0.1578 (3)	0.0437 (8)
C7A	0.9891 (19)	0.737 (2)	−0.0863 (8)	0.047 (2)	0.50 (2)
H7A	1.1338	0.7384	−0.1168	0.057*	0.50 (2)
C8A	0.9324 (19)	0.755 (2)	0.0335 (8)	0.047 (2)	0.50 (2)
H8A	1.0451	0.7608	0.0850	0.057*	0.50 (2)
C7B	0.9186 (19)	0.831 (2)	−0.1110 (9)	0.046 (2)	0.50 (2)
H7B	1.0154	0.8880	−0.1592	0.056*	0.50 (2)
C8B	0.8574 (18)	0.856 (2)	0.0063 (8)	0.041 (2)	0.50 (2)
H8B	0.9085	0.9321	0.0371	0.050*	0.50 (2)
H4C	0.394 (11)	0.538 (9)	0.327 (6)	0.095 (19)*
H4D	0.198 (12)	0.724 (9)	0.277 (6)	0.096 (18)*

	U11	U22	U33	U12	U13	U23
Cl1	0.0650 (7)	0.0717 (7)	0.0365 (6)	−0.0151 (5)	0.0119 (4)	−0.0289 (4)
S1	0.0548 (7)	0.0735 (7)	0.0408 (6)	−0.0209 (5)	0.0126 (4)	−0.0356 (5)
N1	0.0407 (14)	0.0474 (13)	0.0337 (13)	−0.0068 (10)	0.0014 (10)	−0.0258 (11)
N2	0.0591 (18)	0.090 (2)	0.0414 (16)	−0.0351 (16)	0.0129 (13)	−0.0406 (15)
N3	0.0627 (19)	0.098 (2)	0.0446 (16)	−0.0400 (17)	0.0151 (14)	−0.0490 (17)
N4	0.0587 (19)	0.073 (2)	0.0469 (17)	−0.0299 (15)	0.0138 (14)	−0.0360 (15)
C1	0.0451 (17)	0.0584 (17)	0.0326 (15)	−0.0081 (14)	0.0023 (12)	−0.0295 (13)
C2	0.0359 (15)	0.0500 (16)	0.0358 (15)	−0.0072 (12)	−0.0010 (11)	−0.0238 (12)
C3	0.0373 (15)	0.0435 (14)	0.0330 (14)	−0.0024 (11)	0.0001 (11)	−0.0213 (11)
C4A	0.033 (4)	0.049 (5)	0.035 (4)	−0.003 (4)	0.001 (3)	−0.023 (3)
C5A	0.050 (4)	0.051 (5)	0.033 (4)	−0.005 (4)	−0.003 (3)	−0.018 (4)
C4B	0.041 (4)	0.053 (6)	0.034 (4)	−0.012 (4)	0.008 (3)	−0.027 (4)
C5B	0.052 (5)	0.057 (6)	0.038 (4)	−0.016 (5)	0.004 (4)	−0.030 (4)
C6	0.0419 (16)	0.0468 (15)	0.0338 (16)	−0.0026 (13)	0.0028 (12)	−0.0188 (12)
C7A	0.047 (4)	0.054 (6)	0.040 (4)	−0.014 (4)	0.003 (3)	−0.020 (4)
C8A	0.045 (4)	0.055 (6)	0.045 (4)	−0.012 (4)	−0.004 (3)	−0.028 (4)
C7B	0.045 (4)	0.048 (6)	0.040 (4)	−0.011 (4)	0.010 (3)	−0.016 (4)
C8B	0.041 (4)	0.048 (6)	0.042 (4)	−0.012 (4)	0.006 (3)	−0.030 (4)

Cl1—C6	1.735 (3)	C4A—C5A	1.410 (9)
S1—C1	1.675 (3)	C4A—H4A	0.9300
N1—C2	1.368 (4)	C5A—C6	1.368 (9)
N1—C1	1.378 (4)	C5A—H5A	0.9300
N1—N4	1.394 (4)	C4B—C5B	1.395 (9)
N2—C2	1.311 (4)	C4B—H4B	0.9300
N2—N3	1.373 (4)	C5B—C6	1.346 (9)
N3—C1	1.315 (5)	C5B—H5B	0.9300
N3—H3	0.8572	C6—C7A	1.339 (9)
N4—H4C	0.91 (6)	C6—C7B	1.421 (10)
N4—H4D	0.96 (7)	C7A—C8A	1.381 (10)
C2—C3	1.471 (4)	C7A—H7A	0.9300
C3—C4B	1.344 (8)	C8A—H8A	0.9300
C3—C8A	1.365 (9)	C7B—C8B	1.377 (10)
C3—C8B	1.405 (9)	C7B—H7B	0.9300
C3—C4A	1.423 (8)	C8B—H8B	0.9300
C2—N1—C1	108.7 (3)	C6—C5A—H5A	120.8
C2—N1—N4	127.1 (3)	C4A—C5A—H5A	120.8
C1—N1—N4	124.3 (3)	C3—C4B—C5B	119.3 (7)
C2—N2—N3	104.2 (3)	C3—C4B—H4B	120.4
C1—N3—N2	114.0 (3)	C5B—C4B—H4B	120.4
C1—N3—H3	123.3	C6—C5B—C4B	121.7 (6)
N2—N3—H3	122.7	C6—C5B—H5B	119.1
N1—N4—H4C	113 (4)	C4B—C5B—H5B	119.1
N1—N4—H4D	109 (4)	C7A—C6—C5B	112.0 (5)
H4C—N4—H4D	104 (5)	C7A—C6—C5A	123.0 (5)
N3—C1—N1	103.3 (3)	C5B—C6—C5A	30.8 (4)
N3—C1—S1	131.5 (3)	C7A—C6—C7B	28.6 (3)
N1—C1—S1	125.2 (3)	C5B—C6—C7B	119.2 (5)
N2—C2—N1	109.8 (3)	C5A—C6—C7B	113.4 (5)
N2—C2—C3	122.3 (3)	C7A—C6—Cl1	118.0 (4)
N1—C2—C3	127.9 (3)	C5B—C6—Cl1	121.1 (4)
C4B—C3—C8A	110.6 (5)	C5A—C6—Cl1	119.0 (4)
C4B—C3—C8B	121.1 (5)	C7B—C6—Cl1	119.7 (4)
C8A—C3—C8B	30.7 (3)	C6—C7A—C8A	118.8 (7)
C4B—C3—C4A	28.1 (3)	C6—C7A—H7A	120.6
C8A—C3—C4A	117.7 (5)	C8A—C7A—H7A	120.6
C8B—C3—C4A	111.9 (5)	C3—C8A—C7A	122.4 (6)
C4B—C3—C2	122.7 (4)	C3—C8A—H8A	118.8
C8A—C3—C2	119.7 (4)	C7A—C8A—H8A	118.8
C8B—C3—C2	116.1 (4)	C8B—C7B—C6	119.3 (7)
C4A—C3—C2	122.6 (4)	C8B—C7B—H7B	120.3
C5A—C4A—C3	119.5 (6)	C6—C7B—H7B	120.3
C5A—C4A—H4A	120.2	C7B—C8B—C3	119.3 (6)
C3—C4A—H4A	120.2	C7B—C8B—H8B	120.4
C6—C5A—C4A	118.3 (6)	C3—C8B—H8B	120.4
C2—N2—N3—C1	−0.2 (5)	C2—C3—C4B—C5B	−178.8 (6)
N2—N3—C1—N1	1.7 (4)	C3—C4B—C5B—C6	−2.7 (14)
N2—N3—C1—S1	−177.0 (3)	C4B—C5B—C6—C7A	31.8 (11)
C2—N1—C1—N3	−2.5 (3)	C4B—C5B—C6—C5A	−86.1 (12)
N4—N1—C1—N3	178.0 (3)	C4B—C5B—C6—C7B	1.1 (11)
C2—N1—C1—S1	176.3 (2)	C4B—C5B—C6—Cl1	178.4 (7)
N4—N1—C1—S1	−3.2 (4)	C4A—C5A—C6—C7A	−4.1 (11)
N3—N2—C2—N1	−1.4 (4)	C4A—C5A—C6—C5B	73.4 (10)
N3—N2—C2—C3	178.1 (3)	C4A—C5A—C6—C7B	−34.8 (9)
C1—N1—C2—N2	2.5 (4)	C4A—C5A—C6—Cl1	176.3 (5)
N4—N1—C2—N2	−178.0 (3)	C5B—C6—C7A—C8A	−28.2 (10)
C1—N1—C2—C3	−176.9 (3)	C5A—C6—C7A—C8A	4.5 (11)
N4—N1—C2—C3	2.5 (5)	C7B—C6—C7A—C8A	82.8 (12)
N2—C2—C3—C4B	172.1 (9)	Cl1—C6—C7A—C8A	−175.9 (6)
N1—C2—C3—C4B	−8.5 (9)	C4B—C3—C8A—C7A	32.1 (10)
N2—C2—C3—C8A	24.1 (9)	C8B—C3—C8A—C7A	−84.4 (11)
N1—C2—C3—C8A	−156.5 (8)	C4A—C3—C8A—C7A	2.2 (11)
N2—C2—C3—C8B	−10.5 (7)	C2—C3—C8A—C7A	−176.4 (7)
N1—C2—C3—C8B	168.9 (7)	C6—C7A—C8A—C3	−3.5 (13)
N2—C2—C3—C4A	−154.4 (7)	C7A—C6—C7B—C8B	−83.4 (12)
N1—C2—C3—C4A	25.0 (8)	C5B—C6—C7B—C8B	−0.8 (10)
C4B—C3—C4A—C5A	−83.7 (11)	C5A—C6—C7B—C8B	33.1 (9)
C8A—C3—C4A—C5A	−1.8 (10)	Cl1—C6—C7B—C8B	−178.1 (5)
C8B—C3—C4A—C5A	31.6 (9)	C6—C7B—C8B—C3	2.0 (11)
C2—C3—C4A—C5A	176.8 (6)	C4B—C3—C8B—C7B	−3.6 (10)
C3—C4A—C5A—C6	2.6 (11)	C8A—C3—C8B—C7B	74.2 (9)
C8A—C3—C4B—C5B	−28.3 (10)	C4A—C3—C8B—C7B	−33.5 (9)
C8B—C3—C4B—C5B	3.9 (11)	C2—C3—C8B—C7B	178.9 (6)
C4A—C3—C4B—C5B	82.2 (13)

D—H···A	D—H	H···A	D···A	D—H···A
C4B—H4B···N4	0.93	2.32	2.98	128
N3—H3···S1i	0.86	2.55	3.332 (3)	152
C5B—H5B···N4ii	0.93	2.72	3.582 (8)	155
C8A—H8A···N4iii	0.93	2.53	3.416 (9)	158
C7B—H7B···N2iv	0.93	2.64	3.541 (10)	162
N4—H4C···S1v	0.91 (6)	2.70 (6)	3.552 (4)	155 (5)
N4—H4D···N2vi	0.96 (7)	2.42 (7)	3.349 (5)	164 (5)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4B—H4B⋯N4	0.93	2.32	2.98	128
N3—H3⋯S1i	0.86	2.55	3.332 (3)	152
C5B—H5B⋯N4ii	0.93	2.72	3.582 (8)	155
C8A—H8A⋯N4iii	0.93	2.53	3.416 (9)	158
C7B—H7B⋯N2iv	0.93	2.64	3.541 (10)	162
N4—H4C⋯S1v	0.91 (6)	2.70 (6)	3.552 (4)	155 (5)
N4—H4D⋯N2vi	0.96 (7)	2.42 (7)	3.349 (5)	164 (5)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .