3-Methyl-4-{(E)-[4-(methyl-sulfan-yl)benzyl-idene]amino}-1H-1,2,4-triazole-5(4H)-thione.

In the title mol-ecule, C11H12N4S2, the dihedral angle between the triazole and benzene rings is 21.31 (5)°. A weak intra-molecular C-H⋯S hydrogen bond generates an S(6) ring motif. In the crystal, pairs of N-H⋯S hydrogen bonds form inversion dimers. In addition, π-π inter-actions are observed between the benzene rings, with a centroid-centroid separation of 3.7599 (11) Å.

Related literature

For background to Schiff base compounds, see: Dubey & Vaid (1991 ▶); Yadav et al. (1994 ▶); Galic et al. (2001 ▶). For biological applications of sulfur- and nitro­gen-containing compounds, see: Wei et al. (1981 ▶, 1982 ▶); Thieme et al. (1973a ▶,b ▶); Dornow et al. (1964 ▶); Barrera et al. (1985 ▶); Malik et al., (2011 ▶). For related structures, see: Devarajegowda et al. (2012 ▶); Fun et al. (2008 ▶); Wang et al. (2008 ▶). For standard bond-length data, see: Allen et al. (1987 ▶). For hydrogen-bond graph-set motifs, see: Bernstein et al.(1995 ▶).

Experimental

Crystal data

C11H12N4S2

M = 264.37

Triclinic,

a = 7.7873 (2) Å

b = 9.5982 (2) Å

c = 9.6041 (2) Å

α = 76.608 (2)°

β = 70.602 (2)°

γ = 68.570 (2)°

V = 625.30 (2) Å3

Z = 2

Mo Kα radiation

μ = 0.41 mm−1

T = 293 K

0.3 × 0.2 × 0.1 mm

Data collection

Oxford Diffraction Xcalibur Sapphire3 diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 ▶) T min = 0.866, T max = 1.000

30316 measured reflections

2449 independent reflections

2121 reflections with I > 2σ(I)

R int = 0.041

Refinement

R[F 2 > 2σ(F 2)] = 0.032

wR(F 2) = 0.088

S = 1.03

2449 reflections

156 parameters

H-atom parameters constrained

Δρmax = 0.26 e Å−3

Δρmin = −0.17 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: PLATON.

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813009690/lh5604sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813009690/lh5604Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813009690/lh5604Isup3.cml

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

C11H12N4S2	Z = 2
Mr = 264.37	F(000) = 276
Triclinic, P1	Dx = 1.404 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.7873 (2) Å	Cell parameters from 15170 reflections
b = 9.5982 (2) Å	θ = 3.4–29.1°
c = 9.6041 (2) Å	µ = 0.41 mm−1
α = 76.608 (2)°	T = 293 K
β = 70.602 (2)°	Block, white
γ = 68.570 (2)°	0.3 × 0.2 × 0.1 mm
V = 625.30 (2) Å3

Oxford Diffraction Xcalibur Sapphire3 diffractometer	2449 independent reflections
Radiation source: fine-focus sealed tube	2121 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.041
Detector resolution: 16.1049 pixels mm-1	θmax = 26.0°, θmin = 3.4°
ω scan	h = −9→9
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	k = −11→11
Tmin = 0.866, Tmax = 1.000	l = −11→11
30316 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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.088	H-atom parameters constrained
S = 1.03	w = 1/[σ2(Fo2) + (0.0446P)2 + 0.2502P] where P = (Fo2 + 2Fc2)/3
2449 reflections	(Δ/σ)max = 0.001
156 parameters	Δρmax = 0.26 e Å−3
0 restraints	Δρmin = −0.17 e Å−3

Experimental. CrysAlis PRO, Oxford Diffraction Ltd., Version 1.171.34.40 (release 27–08-2010 CrysAlis171. NET) (compiled Aug 27 2010,11:50:40) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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
S1	0.15017 (7)	0.32917 (5)	0.84285 (5)	0.04691 (16)
S2	0.40556 (6)	−0.40134 (5)	0.33254 (5)	0.03932 (14)
N1	−0.3639 (2)	0.35160 (17)	1.09693 (16)	0.0409 (4)
N2	−0.2053 (2)	0.39804 (16)	1.03276 (16)	0.0389 (3)
H2	−0.1954	0.4764	1.0542	0.047*
N4	−0.14673 (19)	0.20528 (14)	0.93293 (14)	0.0308 (3)
N7	−0.0745 (2)	0.07943 (15)	0.85714 (15)	0.0356 (3)
C3	−0.0676 (2)	0.31151 (18)	0.93426 (18)	0.0322 (3)
C5	−0.3237 (2)	0.23338 (19)	1.03460 (18)	0.0351 (4)
C6	−0.4492 (3)	0.1392 (2)	1.0656 (2)	0.0530 (5)
H6A	−0.5573	0.1702	1.1492	0.079*
H6B	−0.3784	0.0353	1.0876	0.079*
H6C	−0.4932	0.1511	0.9800	0.079*
C8	0.0461 (2)	0.08739 (18)	0.73055 (19)	0.0359 (4)
H8	0.0818	0.1743	0.6941	0.043*
C9	0.1295 (2)	−0.03748 (18)	0.64155 (18)	0.0332 (3)
C10	0.2741 (3)	−0.0280 (2)	0.5103 (2)	0.0411 (4)
H10	0.3162	0.0561	0.4831	0.049*
C11	0.3554 (3)	−0.1409 (2)	0.4205 (2)	0.0413 (4)
H11	0.4527	−0.1331	0.3339	0.050*
C12	0.2930 (2)	−0.26694 (18)	0.45838 (18)	0.0324 (3)
C13	0.1500 (2)	−0.27788 (19)	0.58982 (18)	0.0367 (4)
H13	0.1084	−0.3622	0.6172	0.044*
C14	0.0695 (2)	−0.16417 (19)	0.67990 (18)	0.0364 (4)
H14	−0.0262	−0.1727	0.7674	0.044*
C15	0.2776 (3)	−0.5350 (2)	0.4030 (2)	0.0513 (5)
H15A	0.2824	−0.5749	0.5035	0.077*
H15B	0.3350	−0.6157	0.3423	0.077*
H15C	0.1464	−0.4864	0.4011	0.077*

	U11	U22	U33	U12	U13	U23
S1	0.0418 (3)	0.0503 (3)	0.0534 (3)	−0.0245 (2)	0.0056 (2)	−0.0266 (2)
S2	0.0395 (2)	0.0369 (2)	0.0370 (2)	−0.00991 (18)	0.00102 (18)	−0.01659 (18)
N1	0.0374 (8)	0.0447 (8)	0.0427 (8)	−0.0163 (7)	−0.0004 (6)	−0.0192 (7)
N2	0.0401 (8)	0.0359 (7)	0.0437 (8)	−0.0157 (6)	−0.0011 (6)	−0.0196 (6)
N4	0.0360 (7)	0.0278 (6)	0.0321 (7)	−0.0115 (5)	−0.0071 (6)	−0.0110 (5)
N7	0.0419 (8)	0.0298 (7)	0.0387 (8)	−0.0102 (6)	−0.0094 (6)	−0.0152 (6)
C3	0.0369 (8)	0.0293 (8)	0.0321 (8)	−0.0110 (7)	−0.0065 (7)	−0.0102 (6)
C5	0.0363 (8)	0.0378 (9)	0.0333 (8)	−0.0134 (7)	−0.0062 (7)	−0.0106 (7)
C6	0.0496 (11)	0.0582 (12)	0.0599 (12)	−0.0311 (10)	−0.0024 (9)	−0.0191 (10)
C8	0.0431 (9)	0.0310 (8)	0.0377 (9)	−0.0113 (7)	−0.0117 (7)	−0.0114 (7)
C9	0.0353 (8)	0.0314 (8)	0.0344 (8)	−0.0057 (7)	−0.0112 (7)	−0.0121 (7)
C10	0.0419 (9)	0.0377 (9)	0.0456 (10)	−0.0163 (8)	−0.0056 (8)	−0.0123 (8)
C11	0.0386 (9)	0.0414 (9)	0.0398 (9)	−0.0139 (8)	0.0018 (7)	−0.0135 (7)
C12	0.0310 (8)	0.0312 (8)	0.0331 (8)	−0.0038 (6)	−0.0087 (7)	−0.0103 (6)
C13	0.0414 (9)	0.0304 (8)	0.0369 (9)	−0.0112 (7)	−0.0049 (7)	−0.0104 (7)
C14	0.0389 (9)	0.0356 (9)	0.0316 (8)	−0.0098 (7)	−0.0034 (7)	−0.0107 (7)
C15	0.0498 (11)	0.0516 (11)	0.0546 (12)	−0.0224 (9)	0.0052 (9)	−0.0285 (9)

S1—C3	1.6818 (17)	C8—C9	1.458 (2)
S2—C12	1.7565 (16)	C8—H8	0.9300
S2—C15	1.7837 (19)	C9—C14	1.388 (2)
N1—C5	1.294 (2)	C9—C10	1.395 (2)
N1—N2	1.3688 (19)	C10—C11	1.374 (2)
N2—C3	1.332 (2)	C10—H10	0.9300
N2—H2	0.8600	C11—C12	1.393 (2)
N4—C5	1.372 (2)	C11—H11	0.9300
N4—C3	1.3744 (19)	C12—C13	1.391 (2)
N4—N7	1.3944 (18)	C13—C14	1.382 (2)
N7—C8	1.272 (2)	C13—H13	0.9300
C5—C6	1.479 (2)	C14—H14	0.9300
C6—H6A	0.9600	C15—H15A	0.9600
C6—H6B	0.9600	C15—H15B	0.9600
C6—H6C	0.9600	C15—H15C	0.9600
C12—S2—C15	104.35 (8)	C14—C9—C10	118.42 (15)
C5—N1—N2	103.74 (13)	C14—C9—C8	123.14 (15)
C3—N2—N1	114.29 (13)	C10—C9—C8	118.44 (15)
C3—N2—H2	122.9	C11—C10—C9	121.01 (16)
N1—N2—H2	122.9	C11—C10—H10	119.5
C5—N4—C3	108.19 (13)	C9—C10—H10	119.5
C5—N4—N7	119.83 (13)	C10—C11—C12	120.40 (16)
C3—N4—N7	131.85 (13)	C10—C11—H11	119.8
C8—N7—N4	116.65 (13)	C12—C11—H11	119.8
N2—C3—N4	102.66 (14)	C13—C12—C11	118.93 (15)
N2—C3—S1	126.93 (12)	C13—C12—S2	125.20 (13)
N4—C3—S1	130.36 (12)	C11—C12—S2	115.88 (13)
N1—C5—N4	111.08 (14)	C14—C13—C12	120.34 (16)
N1—C5—C6	125.65 (16)	C14—C13—H13	119.8
N4—C5—C6	123.27 (15)	C12—C13—H13	119.8
C5—C6—H6A	109.5	C13—C14—C9	120.90 (16)
C5—C6—H6B	109.5	C13—C14—H14	119.6
H6A—C6—H6B	109.5	C9—C14—H14	119.6
C5—C6—H6C	109.5	S2—C15—H15A	109.5
H6A—C6—H6C	109.5	S2—C15—H15B	109.5
H6B—C6—H6C	109.5	H15A—C15—H15B	109.5
N7—C8—C9	121.10 (15)	S2—C15—H15C	109.5
N7—C8—H8	119.4	H15A—C15—H15C	109.5
C9—C8—H8	119.5	H15B—C15—H15C	109.5
C5—N1—N2—C3	−0.8 (2)	N4—N7—C8—C9	−179.55 (14)
C5—N4—N7—C8	153.95 (16)	N7—C8—C9—C14	7.1 (3)
C3—N4—N7—C8	−30.8 (2)	N7—C8—C9—C10	−174.05 (16)
N1—N2—C3—N4	1.71 (19)	C14—C9—C10—C11	0.1 (3)
N1—N2—C3—S1	−176.03 (13)	C8—C9—C10—C11	−178.77 (17)
C5—N4—C3—N2	−1.95 (17)	C9—C10—C11—C12	0.7 (3)
N7—N4—C3—N2	−177.60 (15)	C10—C11—C12—C13	−1.3 (3)
C5—N4—C3—S1	175.68 (14)	C10—C11—C12—S2	178.86 (14)
N7—N4—C3—S1	0.0 (3)	C15—S2—C12—C13	5.91 (18)
N2—N1—C5—N4	−0.59 (19)	C15—S2—C12—C11	−174.23 (14)
N2—N1—C5—C6	179.81 (18)	C11—C12—C13—C14	1.0 (3)
C3—N4—C5—N1	1.67 (19)	S2—C12—C13—C14	−179.17 (13)
N7—N4—C5—N1	177.93 (14)	C12—C13—C14—C9	−0.1 (3)
C3—N4—C5—C6	−178.72 (16)	C10—C9—C14—C13	−0.4 (3)
N7—N4—C5—C6	−2.5 (2)	C8—C9—C14—C13	178.42 (16)

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···S1	0.93	2.57	3.212 (2)	126
N2—H2···S1i	0.86	2.48	3.328 (2)	169

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8⋯S1	0.93	2.57	3.212 (2)	126
N2—H2⋯S1i	0.86	2.48	3.328 (2)	169

Symmetry code: (i) .