4-[(E)-(4-Chloro-benzyl-idene)amino]-3-methyl-1H-1,2,4-triazole-5(4H)-thione.

In the title compound, C10H9ClN4S, the dihedral angle between the mean planes of the phenyl and 1H-1,2,4-triazole-5(4H)-thione rings is 25.3 (9)°. The latter ring is essentially planar, with maximum deviations of 0.010 and -0.010 Å for the ring N atom in the 4-position and ring C atom bearing the methyl group, respectively. An intra-molecular C-H⋯S contact occurs. In the crystal, pairs of weak N-H⋯S inter-actions link the mol-ecules into inversion dimers in the ac plane, forming R 2 (2)(8) graph-set motifs. In addition, weak π-π inter-actions [centroid-centroid distances = 3.3463 (14) and 3.6127 (13)Å] are observed.

Related literature

For the chemistry of Schiff base compounds, see: Dubey & Vaid (1991 ▶); Yadav et al. (1994 ▶). For the use of Schiff bases containing different donor atoms in analytical applications and metal coordination, see: Galic et al. (2001 ▶); Wyrzykiewicz & Prukah (1998 ▶); Reddy & Lirgappa (1994 ▶). Many compounds containing S and N atoms are anti­hypertensive (Wei et al., 1981 ▶,1982 ▶), analgesic (Thieme et al., 1973a ▶,b ▶), anti­inflammatory (Dornow et al., 1964 ▶), sedative (Barrera et al.,1985 ▶), or fungicidal (Malik et al., 2011 ▶). For the crystal structures of related Schiff bases, see: Jeyaseelan et al. (2012 ▶); Devarajegowda et al. (2012 ▶); Vinduvahini et al. (2011 ▶); Almutairi et al. (2012 ▶); Kubicki et al. (2012 ▶); Praveen et al. (2012 ▶); Kant et al. (2012 ▶); Ding et al. (2009 ▶). For the crystal structures of Schiff bases reported by our group, see: Sarojini et al. (2007a ▶,b ▶). For standard bond lengths, see: Allen et al. (1987 ▶). For π–π stacking, see: Grimme (2008 ▶).

Experimental

Crystal data

C10H9ClN4S

M = 252.72

Triclinic,

a = 7.0718 (8) Å

b = 7.2901 (8) Å

c = 11.8434 (7) Å

α = 92.778 (7)°

β = 94.986 (7)°

γ = 109.752 (10)°

V = 570.50 (10) Å3

Z = 2

Cu Kα radiation

μ = 4.49 mm−1

T = 173 K

0.42 × 0.08 × 0.06 mm

Data collection

Agilent Gemini EOS diffractometer

Absorption correction: multi-scan (CrysAlis PRO and CrysAlis RED; Agilent, 2012 ▶) T min = 0.544, T max = 1.000

3413 measured reflections

2195 independent reflections

1860 reflections with I > 2σ(I)

R int = 0.030

Refinement

R[F 2 > 2σ(F 2)] = 0.043

wR(F 2) = 0.120

S = 1.02

2195 reflections

146 parameters

H-atom parameters constrained

Δρmax = 0.34 e Å−3

Δρmin = −0.39 e Å−3

Data collection: CrysAlis PRO (Agilent, 2012 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED (Agilent, 2012 ▶); program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007 ▶); program(s) used to refine structure: SHELXL2012 (Sheldrick, 2008 ▶); molecular graphics: OLEX2 (Dolomanov et al., 2009 ▶); software used to prepare material for publication: OLEX2.

Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536813033527/qm2102sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813033527/qm2102Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536813033527/qm2102Isup3.cml

Additional supporting information: crystallographic information; 3D view; checkCIF report

C10H9ClN4S	Z = 2
Mr = 252.72	F(000) = 260
Triclinic, P1	Dx = 1.471 Mg m−3
a = 7.0718 (8) Å	Cu Kα radiation, λ = 1.54184 Å
b = 7.2901 (8) Å	Cell parameters from 1400 reflections
c = 11.8434 (7) Å	θ = 3.8–72.2°
α = 92.778 (7)°	µ = 4.49 mm−1
β = 94.986 (7)°	T = 173 K
γ = 109.752 (10)°	Irregular, colourless
V = 570.50 (10) Å3	0.42 × 0.08 × 0.06 mm

Agilent Gemini EOS diffractometer	2195 independent reflections
Radiation source: Enhance (Cu) X-ray Source	1860 reflections with I > 2σ(I)
Detector resolution: 16.0416 pixels mm-1	Rint = 0.030
ω scans	θmax = 72.3°, θmin = 3.8°
Absorption correction: multi-scan (CrysAlis PRO and CrysAlis RED; Agilent, 2012)	h = −8→8
Tmin = 0.544, Tmax = 1.000	k = −8→8
3413 measured reflections	l = −10→14

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.043	H-atom parameters constrained
wR(F2) = 0.120	w = 1/[σ2(Fo2) + (0.0694P)2] where P = (Fo2 + 2Fc2)/3
S = 1.02	(Δ/σ)max < 0.001
2195 reflections	Δρmax = 0.34 e Å−3
146 parameters	Δρmin = −0.39 e Å−3
0 restraints

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.

	x	y	z	Uiso*/Ueq
Cl1	0.50541 (9)	0.96033 (9)	0.77738 (5)	0.03752 (19)
S1	−0.33106 (9)	0.64930 (9)	0.16551 (5)	0.03564 (19)
N1	0.0401 (3)	0.4905 (3)	0.27296 (16)	0.0295 (4)
N2	−0.0729 (3)	0.4344 (3)	0.16664 (15)	0.0287 (4)
N3	−0.1813 (3)	0.2442 (3)	0.00660 (17)	0.0353 (4)
N4	−0.2891 (3)	0.3680 (3)	0.02140 (16)	0.0317 (4)
H4	−0.3862	0.3696	−0.0271	0.038*
C1	0.0775 (3)	0.6667 (3)	0.31206 (19)	0.0311 (5)
H1	0.0364	0.7520	0.2684	0.037*
C2	0.1852 (3)	0.7342 (3)	0.42579 (19)	0.0289 (5)
C3	0.2005 (3)	0.9179 (3)	0.4726 (2)	0.0320 (5)
H3	0.1460	0.9957	0.4301	0.038*
C4	0.2955 (3)	0.9876 (3)	0.5816 (2)	0.0318 (5)
H4A	0.3026	1.1095	0.6131	0.038*
C5	0.3788 (3)	0.8714 (3)	0.64183 (19)	0.0307 (5)
C6	0.3682 (3)	0.6889 (3)	0.5977 (2)	0.0329 (5)
H6	0.4265	0.6136	0.6400	0.039*
C7	0.2703 (3)	0.6195 (3)	0.4903 (2)	0.0333 (5)
H7	0.2606	0.4959	0.4605	0.040*
C8	−0.2301 (3)	0.4851 (3)	0.11732 (19)	0.0291 (5)
C9	−0.0524 (3)	0.2861 (3)	0.0975 (2)	0.0322 (5)
C10	0.1023 (4)	0.1949 (4)	0.1262 (2)	0.0431 (6)
H10A	0.0590	0.1060	0.1837	0.065*
H10B	0.2284	0.2949	0.1541	0.065*
H10C	0.1195	0.1248	0.0594	0.065*

	U11	U22	U33	U12	U13	U23
Cl1	0.0398 (3)	0.0455 (3)	0.0282 (3)	0.0191 (3)	−0.0056 (2)	−0.0031 (2)
S1	0.0364 (3)	0.0421 (3)	0.0329 (3)	0.0242 (3)	−0.0099 (2)	−0.0080 (2)
N1	0.0255 (9)	0.0372 (10)	0.0263 (10)	0.0134 (7)	−0.0047 (7)	0.0010 (7)
N2	0.0270 (9)	0.0321 (9)	0.0274 (10)	0.0132 (7)	−0.0046 (7)	−0.0007 (7)
N3	0.0369 (10)	0.0397 (10)	0.0325 (11)	0.0212 (8)	−0.0063 (8)	−0.0057 (8)
N4	0.0318 (10)	0.0394 (10)	0.0272 (10)	0.0198 (8)	−0.0066 (8)	−0.0030 (8)
C1	0.0260 (10)	0.0337 (11)	0.0334 (12)	0.0113 (8)	−0.0029 (9)	0.0044 (9)
C2	0.0208 (10)	0.0344 (11)	0.0296 (12)	0.0087 (8)	−0.0020 (8)	0.0007 (9)
C3	0.0264 (10)	0.0364 (12)	0.0355 (12)	0.0153 (9)	−0.0017 (9)	0.0010 (9)
C4	0.0282 (10)	0.0353 (11)	0.0339 (12)	0.0152 (9)	−0.0004 (9)	−0.0041 (9)
C5	0.0248 (10)	0.0406 (12)	0.0260 (11)	0.0112 (9)	0.0007 (8)	−0.0001 (9)
C6	0.0331 (11)	0.0350 (11)	0.0328 (12)	0.0155 (9)	−0.0015 (9)	0.0064 (9)
C7	0.0346 (11)	0.0307 (11)	0.0342 (12)	0.0122 (9)	−0.0009 (10)	−0.0001 (9)
C8	0.0284 (10)	0.0330 (11)	0.0269 (11)	0.0138 (8)	−0.0036 (8)	0.0003 (9)
C9	0.0314 (11)	0.0350 (11)	0.0311 (12)	0.0148 (9)	−0.0021 (9)	−0.0024 (9)
C10	0.0420 (14)	0.0460 (14)	0.0481 (16)	0.0288 (12)	−0.0086 (12)	−0.0060 (12)

Cl1—C5	1.748 (2)	C2—C7	1.402 (3)
S1—C8	1.689 (2)	C3—H3	0.9300
N1—N2	1.395 (2)	C3—C4	1.390 (3)
N1—C1	1.275 (3)	C4—H4A	0.9300
N2—C8	1.378 (3)	C4—C5	1.377 (3)
N2—C9	1.379 (3)	C5—C6	1.381 (3)
N3—N4	1.378 (2)	C6—H6	0.9300
N3—C9	1.301 (3)	C6—C7	1.379 (3)
N4—H4	0.8600	C7—H7	0.9300
N4—C8	1.333 (3)	C9—C10	1.484 (3)
C1—H1	0.9300	C10—H10A	0.9600
C1—C2	1.463 (3)	C10—H10B	0.9600
C2—C3	1.390 (3)	C10—H10C	0.9600
C1—N1—N2	116.28 (19)	C4—C5—C6	122.1 (2)
C8—N2—N1	131.27 (18)	C6—C5—Cl1	119.20 (18)
C8—N2—C9	108.25 (18)	C5—C6—H6	120.4
C9—N2—N1	119.99 (18)	C7—C6—C5	119.2 (2)
C9—N3—N4	103.61 (18)	C7—C6—H6	120.4
N3—N4—H4	122.9	C2—C7—H7	119.8
C8—N4—N3	114.29 (18)	C6—C7—C2	120.4 (2)
C8—N4—H4	122.9	C6—C7—H7	119.8
N1—C1—H1	120.1	N2—C8—S1	129.63 (17)
N1—C1—C2	119.8 (2)	N4—C8—S1	127.48 (17)
C2—C1—H1	120.1	N4—C8—N2	102.87 (18)
C3—C2—C1	118.6 (2)	N2—C9—C10	122.4 (2)
C3—C2—C7	118.7 (2)	N3—C9—N2	110.94 (19)
C7—C2—C1	122.6 (2)	N3—C9—C10	126.6 (2)
C2—C3—H3	119.3	C9—C10—H10A	109.5
C4—C3—C2	121.3 (2)	C9—C10—H10B	109.5
C4—C3—H3	119.3	C9—C10—H10C	109.5
C3—C4—H4A	120.9	H10A—C10—H10B	109.5
C5—C4—C3	118.2 (2)	H10A—C10—H10C	109.5
C5—C4—H4A	120.9	H10B—C10—H10C	109.5
C4—C5—Cl1	118.70 (18)
Cl1—C5—C6—C7	−179.28 (17)	C1—C2—C3—C4	178.0 (2)
N1—N2—C8—S1	5.3 (4)	C1—C2—C7—C6	−179.2 (2)
N1—N2—C8—N4	−173.2 (2)	C2—C3—C4—C5	1.4 (3)
N1—N2—C9—N3	174.80 (19)	C3—C2—C7—C6	−0.4 (3)
N1—N2—C9—C10	−6.5 (3)	C3—C4—C5—Cl1	178.09 (17)
N1—C1—C2—C3	−171.5 (2)	C3—C4—C5—C6	−0.8 (3)
N1—C1—C2—C7	7.2 (3)	C4—C5—C6—C7	−0.4 (4)
N2—N1—C1—C2	176.53 (18)	C5—C6—C7—C2	1.0 (3)
N3—N4—C8—S1	−177.92 (17)	C7—C2—C3—C4	−0.8 (3)
N3—N4—C8—N2	0.6 (3)	C8—N2—C9—N3	2.0 (3)
N4—N3—C9—N2	−1.5 (3)	C8—N2—C9—C10	−179.3 (2)
N4—N3—C9—C10	179.8 (2)	C9—N2—C8—S1	177.00 (18)
C1—N1—N2—C8	−35.9 (3)	C9—N2—C8—N4	−1.5 (2)
C1—N1—N2—C9	153.2 (2)	C9—N3—N4—C8	0.5 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4···S1i	0.86	2.43	3.2926 (19)	176
C1—H1···S1	0.93	2.62	3.199 (2)	121

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4⋯S1i	0.86	2.43	3.2926 (19)	176
C1—H1⋯S1	0.93	2.62	3.199 (2)	121

Symmetry code: (i) .