4-Benzyl-3-(thio-phen-2-yl)-4,5-di-hydro-1H-1,2,4-triazole-5-thione.

In the title compound, C13H11N3S2, the triazole and thio-phene rings are coplanar [dihedral angle = 6.22 (13)°]. By contrast, the phenyl ring is perpendicular to the triazole ring [dihedral angle = 85.58 (13)°], so that the mol-ecule has an L-shape. The thio-phene S atom is syn with the ring imine N atom. In the crystal, eight-membered {⋯HNCS}2 synthons form between centrosymmetrically related mol-ecules, leading to dimeric aggregates that are connected into a supra-molecular layer parallel to (101) by π-π inter-actions between centrosymmetrically related triazole rings [centroid-centroid distance = 3.6091 (15) Å] and C-H⋯π inter-actions.

Related literature

For the pharmacological properties (anti-inflammatory, anti-microbial and anti-cancer) of 1,2,4-triazole derivatives, see: El-Emam & Ibrahim (1991 ▶); Navidpour et al. (2006 ▶); Kumar et al. (2010 ▶); Wang et al. (2011 ▶). For a related structure, see: Zareef et al. (2008 ▶).

Experimental

Crystal data

C13H11N3S2

M = 273.37

Monoclinic,

a = 13.422 (2) Å

b = 6.1670 (7) Å

c = 16.596 (2) Å

β = 111.972 (15)°

V = 1273.9 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.40 mm−1

T = 295 K

0.30 × 0.05 × 0.05 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ▶) T min = 0.806, T max = 1.000

6460 measured reflections

2937 independent reflections

2088 reflections with I > 2σ(I)

R int = 0.036

Refinement

R[F 2 > 2σ(F 2)] = 0.045

wR(F 2) = 0.109

S = 1.02

2937 reflections

167 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.24 e Å−3

Δρmin = −0.27 e Å−3

Data collection: CrysAlis PRO (Agilent, 2011 ▶); 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 DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813009501/hg5308sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813009501/hg5308Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813009501/hg5308Isup3.cml

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

C13H11N3S2	F(000) = 568
Mr = 273.37	Dx = 1.425 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1615 reflections
a = 13.422 (2) Å	θ = 3.0–27.5°
b = 6.1670 (7) Å	µ = 0.40 mm−1
c = 16.596 (2) Å	T = 295 K
β = 111.972 (15)°	Prism, colourless
V = 1273.9 (3) Å3	0.30 × 0.05 × 0.05 mm
Z = 4

Agilent SuperNova Dual diffractometer with an Atlas detector	2937 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	2088 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.036
Detector resolution: 10.4041 pixels mm-1	θmax = 27.6°, θmin = 3.3°
ω scan	h = −12→17
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −8→5
Tmin = 0.806, Tmax = 1.000	l = −21→19
6460 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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.109	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ2(Fo2) + (0.0415P)2 + 0.2539P] where P = (Fo2 + 2Fc2)/3
2937 reflections	(Δ/σ)max < 0.001
167 parameters	Δρmax = 0.24 e Å−3
1 restraint	Δρmin = −0.27 e Å−3

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	0.21756 (5)	0.78528 (13)	0.30574 (4)	0.0548 (2)
S2	0.47823 (5)	0.12218 (10)	0.62298 (3)	0.03891 (18)
N1	0.34574 (15)	0.4060 (3)	0.39839 (11)	0.0395 (5)
N2	0.40554 (15)	0.2515 (3)	0.45408 (12)	0.0383 (5)
H2	0.4302 (18)	0.138 (3)	0.4349 (15)	0.052 (8)*
N3	0.35676 (13)	0.4651 (3)	0.53331 (10)	0.0304 (4)
C1	0.14130 (18)	0.9997 (4)	0.31144 (16)	0.0475 (6)
H1	0.1054	1.0904	0.2648	0.057*
C2	0.1387 (2)	1.0233 (4)	0.39097 (16)	0.0492 (6)
H2A	0.1008	1.1330	0.4054	0.059*
C3	0.19944 (19)	0.8647 (4)	0.45051 (14)	0.0426 (6)
H3	0.2054	0.8574	0.5081	0.051*
C4	0.24840 (16)	0.7233 (4)	0.41373 (13)	0.0346 (5)
C5	0.31583 (17)	0.5357 (4)	0.44809 (13)	0.0323 (5)
C6	0.41379 (16)	0.2783 (3)	0.53621 (13)	0.0315 (5)
C7	0.34971 (17)	0.5686 (4)	0.61041 (13)	0.0344 (5)
H7A	0.3586	0.7238	0.6065	0.041*
H7B	0.4085	0.5168	0.6614	0.041*
C8	0.24552 (17)	0.5271 (4)	0.62246 (12)	0.0344 (5)
C9	0.1871 (2)	0.3419 (5)	0.59316 (17)	0.0534 (7)
H9	0.2110	0.2391	0.5635	0.064*
C10	0.0931 (2)	0.3049 (5)	0.6069 (2)	0.0708 (9)
H10	0.0540	0.1787	0.5863	0.085*
C11	0.0579 (2)	0.4550 (6)	0.65120 (19)	0.0665 (8)
H11	−0.0056	0.4316	0.6602	0.080*
C12	0.1160 (2)	0.6383 (5)	0.68195 (17)	0.0595 (8)
H12	0.0928	0.7387	0.7129	0.071*
C13	0.2092 (2)	0.6763 (4)	0.66753 (15)	0.0474 (6)
H13	0.2479	0.8029	0.6882	0.057*

	U11	U22	U33	U12	U13	U23
S1	0.0569 (4)	0.0694 (5)	0.0403 (3)	0.0206 (4)	0.0206 (3)	0.0166 (3)
S2	0.0448 (3)	0.0349 (3)	0.0365 (3)	0.0064 (3)	0.0146 (2)	0.0030 (3)
N1	0.0467 (11)	0.0384 (11)	0.0365 (10)	0.0075 (9)	0.0190 (8)	0.0045 (9)
N2	0.0453 (11)	0.0369 (11)	0.0369 (10)	0.0088 (9)	0.0204 (9)	0.0021 (9)
N3	0.0335 (9)	0.0279 (9)	0.0318 (9)	0.0017 (8)	0.0145 (7)	−0.0002 (8)
C1	0.0385 (13)	0.0476 (15)	0.0501 (14)	0.0047 (12)	0.0095 (10)	0.0177 (12)
C2	0.0478 (14)	0.0404 (14)	0.0561 (15)	0.0098 (12)	0.0155 (12)	0.0040 (12)
C3	0.0500 (14)	0.0378 (13)	0.0386 (12)	0.0104 (12)	0.0148 (10)	0.0046 (11)
C4	0.0328 (11)	0.0346 (12)	0.0355 (11)	−0.0007 (10)	0.0117 (9)	0.0036 (10)
C5	0.0345 (11)	0.0308 (11)	0.0313 (10)	−0.0024 (10)	0.0120 (9)	0.0009 (10)
C6	0.0309 (11)	0.0301 (11)	0.0355 (11)	−0.0029 (9)	0.0148 (9)	−0.0015 (9)
C7	0.0371 (12)	0.0337 (12)	0.0314 (10)	0.0001 (10)	0.0116 (9)	−0.0031 (9)
C8	0.0371 (12)	0.0363 (12)	0.0307 (10)	0.0035 (10)	0.0137 (9)	0.0008 (10)
C9	0.0547 (16)	0.0503 (16)	0.0651 (16)	−0.0097 (13)	0.0339 (13)	−0.0164 (13)
C10	0.0595 (18)	0.073 (2)	0.092 (2)	−0.0239 (17)	0.0418 (17)	−0.0182 (19)
C11	0.0493 (16)	0.089 (2)	0.0722 (18)	0.0006 (17)	0.0350 (14)	0.0030 (18)
C12	0.0588 (17)	0.073 (2)	0.0550 (15)	0.0159 (16)	0.0313 (13)	−0.0069 (15)
C13	0.0531 (15)	0.0455 (15)	0.0458 (13)	0.0023 (12)	0.0211 (11)	−0.0120 (12)

S1—C1	1.696 (3)	C4—C5	1.448 (3)
S1—C4	1.725 (2)	C7—C8	1.507 (3)
S2—C6	1.678 (2)	C7—H7A	0.9700
N1—C5	1.315 (3)	C7—H7B	0.9700
N1—N2	1.361 (3)	C8—C9	1.368 (3)
N2—C6	1.336 (3)	C8—C13	1.384 (3)
N2—H2	0.881 (10)	C9—C10	1.382 (4)
N3—C6	1.374 (3)	C9—H9	0.9300
N3—C5	1.382 (2)	C10—C11	1.372 (4)
N3—C7	1.464 (2)	C10—H10	0.9300
C1—C2	1.341 (3)	C11—C12	1.359 (4)
C1—H1	0.9300	C11—H11	0.9300
C2—C3	1.412 (3)	C12—C13	1.379 (4)
C2—H2A	0.9300	C12—H12	0.9300
C3—C4	1.366 (3)	C13—H13	0.9300
C3—H3	0.9300
C1—S1—C4	91.71 (11)	N3—C6—S2	127.78 (15)
C5—N1—N2	103.94 (17)	N3—C7—C8	114.11 (17)
C6—N2—N1	114.13 (18)	N3—C7—H7A	108.7
C6—N2—H2	124.6 (16)	C8—C7—H7A	108.7
N1—N2—H2	121.0 (16)	N3—C7—H7B	108.7
C6—N3—C5	107.63 (16)	C8—C7—H7B	108.7
C6—N3—C7	123.51 (17)	H7A—C7—H7B	107.6
C5—N3—C7	128.77 (18)	C9—C8—C13	118.4 (2)
C2—C1—S1	112.20 (18)	C9—C8—C7	122.1 (2)
C2—C1—H1	123.9	C13—C8—C7	119.4 (2)
S1—C1—H1	123.9	C8—C9—C10	121.1 (3)
C1—C2—C3	113.1 (2)	C8—C9—H9	119.5
C1—C2—H2A	123.4	C10—C9—H9	119.5
C3—C2—H2A	123.4	C11—C10—C9	119.7 (3)
C4—C3—C2	112.2 (2)	C11—C10—H10	120.1
C4—C3—H3	123.9	C9—C10—H10	120.1
C2—C3—H3	123.9	C12—C11—C10	119.9 (3)
C3—C4—C5	131.97 (19)	C12—C11—H11	120.1
C3—C4—S1	110.76 (16)	C10—C11—H11	120.1
C5—C4—S1	117.24 (16)	C11—C12—C13	120.4 (3)
N1—C5—N3	110.66 (19)	C11—C12—H12	119.8
N1—C5—C4	122.11 (18)	C13—C12—H12	119.8
N3—C5—C4	127.23 (19)	C12—C13—C8	120.4 (3)
N2—C6—N3	103.62 (17)	C12—C13—H13	119.8
N2—C6—S2	128.59 (17)	C8—C13—H13	119.8
C5—N1—N2—C6	0.3 (3)	N1—N2—C6—N3	−1.0 (2)
C4—S1—C1—C2	−0.2 (2)	N1—N2—C6—S2	178.98 (16)
S1—C1—C2—C3	−0.2 (3)	C5—N3—C6—N2	1.3 (2)
C1—C2—C3—C4	0.7 (3)	C7—N3—C6—N2	−175.41 (18)
C2—C3—C4—C5	−178.7 (2)	C5—N3—C6—S2	−178.73 (16)
C2—C3—C4—S1	−0.8 (3)	C7—N3—C6—S2	4.6 (3)
C1—S1—C4—C3	0.61 (19)	C6—N3—C7—C8	−102.1 (2)
C1—S1—C4—C5	178.87 (18)	C5—N3—C7—C8	81.9 (3)
N2—N1—C5—N3	0.5 (2)	N3—C7—C8—C9	29.0 (3)
N2—N1—C5—C4	−179.08 (19)	N3—C7—C8—C13	−153.6 (2)
C6—N3—C5—N1	−1.2 (2)	C13—C8—C9—C10	0.9 (4)
C7—N3—C5—N1	175.28 (19)	C7—C8—C9—C10	178.3 (2)
C6—N3—C5—C4	178.4 (2)	C8—C9—C10—C11	−0.5 (5)
C7—N3—C5—C4	−5.1 (3)	C9—C10—C11—C12	−0.6 (5)
C3—C4—C5—N1	172.4 (2)	C10—C11—C12—C13	1.2 (5)
S1—C4—C5—N1	−5.4 (3)	C11—C12—C13—C8	−0.8 (4)
C3—C4—C5—N3	−7.2 (4)	C9—C8—C13—C12	−0.3 (3)
S1—C4—C5—N3	175.03 (17)	C7—C8—C13—C12	−177.8 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···S2i	0.88 (1)	2.43 (1)	3.297 (2)	169 (2)
C13—H13···Cg1ii	0.93	2.94	3.636 (3)	133

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C8–C13 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯S2i	0.88 (1)	2.43 (1)	3.297 (2)	169 (2)
C13—H13⋯Cg1ii	0.93	2.94	3.636 (3)	133

Symmetry codes: (i) ; (ii) .