3-Benzyl-4-ethyl-1H-1,2,4-triazole-5(4H)-thione.

The title compound, C(11)H(13)N(3)S, exists in the 5-thioxo tautomeric form. The benzene ring exhibits disorder with a refined ratio of 0.77 (2):0.23 (2) for components A and B with a common bridgehead C atom. The 1,2,4-triazole ring is essentially planar, with a maximum deviation of 0.002 (3) Å for the benzyl-substituted C atom, and forms dihedral angles of 88.94 (18) and 86.56 (49)° with the benzene rings of components A and B, respectively. The angle between the plane of the ethyl chain and the mean plane of 1,2,4-triazole ring is 88.55 (15)° and this conformation is stabilized by an intra-molecular C-H⋯S contact. In the crystal, pairs of N-H⋯S hydrogen bonds link mol-ecules into inversion dimers. π-π inter-actions are observed between the triazole and benzene rings, with centroid-centroid separations of 3.547 (4) and 3.544 (12) Å for components A and B, and slippages of 0.49 (6) and 0.58 (15) Å, respectively.

Related literature

For background information on 1,2,4-triazole-5-thio­nes, see: Saadeh et al. (2010 ▶); Akhtar et al. (2008 ▶); Al-Omar et al. (2010 ▶). For their biological activity, see: Pitucha et al. (2010 ▶). For the synthesis, see: Dobosz & Pachuta-Stec (1996 ▶). For related structures, see: Karczmarzyk et al. (2012 ▶); Kruszynski et al. (2007 ▶); Siwek et al. (2008 ▶). For graph-set motifs, see Bernstein et al. (1995 ▶).

Experimental

Crystal data

C11H13N3S

M = 219.30

Monoclinic,

a = 7.3731 (5) Å

b = 8.9408 (19) Å

c = 16.9936 (8) Å

β = 91.892 (4)°

V = 1119.6 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.26 mm−1

T = 296 K

0.55 × 0.20 × 0.20 mm

Data collection

Kuma KM-4 four-circle diffractometer

Absorption correction: ψ scan (North et al., 1968 ▶) T min = 0.834, T max = 0.852

3392 measured reflections

3289 independent reflections

1385 reflections with I > 2σ(I)

R int = 0.039

2 standard reflections every 100 reflections intensity decay: 1%

Refinement

R[F 2 > 2σ(F 2)] = 0.047

wR(F 2) = 0.156

S = 0.98

3289 reflections

187 parameters

6 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.23 e Å−3

Δρmin = −0.20 e Å−3

Data collection: KM4B8 (Gałdecki et al., 1996 ▶); cell refinement: KM4B8; data reduction: DATAPROC (Gałdecki et al., 1995 ▶); 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 ▶); software used to prepare material for publication: SHELXL97 and WinGX (Farrugia, 2012 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812051276/fy2077sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812051276/fy2077Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536812051276/fy2077Isup3.cml

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

C11H13N3S	F(000) = 464
Mr = 219.30	Dx = 1.301 Mg m−3
Monoclinic, P21/c	Melting point: 425 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 7.3731 (5) Å	Cell parameters from 67 reflections
b = 8.9408 (19) Å	θ = 3.6–11.2°
c = 16.9936 (8) Å	µ = 0.26 mm−1
β = 91.892 (4)°	T = 296 K
V = 1119.6 (3) Å3	Prism, colourless
Z = 4	0.55 × 0.20 × 0.20 mm

Kuma KM-4 four-circle diffractometer	1385 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.039
Graphite monochromator	θmax = 30.1°, θmin = 2.4°
ω–2θ scans	h = −10→10
Absorption correction: ψ scan (North et al., 1968)	k = 0→12
Tmin = 0.834, Tmax = 0.852	l = 0→23
3392 measured reflections	2 standard reflections every 100 reflections
3289 independent reflections	intensity decay: 1%

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.047	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.156	w = 1/[σ2(Fo2) + (0.062P)2 + 0.2203P] where P = (Fo2 + 2Fc2)/3
S = 0.98	(Δ/σ)max < 0.001
3289 reflections	Δρmax = 0.23 e Å−3
187 parameters	Δρmin = −0.20 e Å−3
6 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: 0.012 (3)

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.

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 > 2sigma(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)
S6	−0.22230 (10)	0.33538 (8)	0.53097 (4)	0.0567 (3)
N1	0.0496 (3)	0.3323 (3)	0.42647 (13)	0.0473 (6)
H1	0.101 (4)	0.412 (4)	0.4446 (18)	0.071*
N2	0.1063 (3)	0.2595 (3)	0.36067 (13)	0.0525 (6)
N4	−0.1519 (3)	0.1693 (2)	0.40086 (12)	0.0445 (5)
C3	−0.0184 (4)	0.1613 (3)	0.34683 (16)	0.0516 (7)
C5	−0.1070 (3)	0.2807 (3)	0.45287 (15)	0.0412 (6)
C7	−0.3151 (4)	0.0780 (3)	0.40482 (17)	0.0563 (8)
H7A	−0.3527	0.0466	0.3521	0.084*
H7B	−0.4122	0.1375	0.4259	0.084*
C8	−0.2841 (5)	−0.0576 (4)	0.4557 (2)	0.0776 (11)
H8A	−0.2561	−0.0268	0.5088	0.116*
H8B	−0.1847	−0.1146	0.4362	0.116*
H8C	−0.3917	−0.1182	0.4545	0.116*
C9	−0.0260 (4)	0.0531 (4)	0.2795 (2)	0.0834 (12)
H91	−0.1034	0.0942	0.2376	0.125*
H92	−0.0813	−0.0391	0.2969	0.125*
C10	0.1561 (3)	0.0173 (3)	0.24685 (16)	0.0456 (6)
C11A	0.1986 (18)	0.0849 (15)	0.1776 (6)	0.0499 (18)	0.77 (2)
H11A	0.1175	0.1531	0.1547	0.075*	0.77 (2)
C12A	0.3582 (15)	0.0546 (11)	0.1410 (6)	0.062 (2)	0.77 (2)
H12A	0.3837	0.1027	0.0941	0.093*	0.77 (2)
C13A	0.4806 (9)	−0.0468 (11)	0.1733 (7)	0.066 (2)	0.77 (2)
H13A	0.5890	−0.0673	0.1490	0.100*	0.77 (2)
C14A	0.4388 (12)	−0.1159 (11)	0.2417 (7)	0.071 (3)	0.77 (2)
H14A	0.5179	−0.1870	0.2633	0.107*	0.77 (2)
C15A	0.2833 (14)	−0.0828 (10)	0.2790 (5)	0.068 (2)	0.77 (2)
H15A	0.2613	−0.1279	0.3270	0.102*	0.77 (2)
C11B	0.240 (5)	0.060 (6)	0.179 (2)	0.069 (11)	0.23 (2)
H11B	0.1873	0.1316	0.1463	0.103*	0.23 (2)
C12B	0.403 (3)	−0.004 (4)	0.1598 (16)	0.052 (8)	0.23 (2)
H12B	0.4608	0.0185	0.1134	0.077*	0.23 (2)
C13B	0.475 (3)	−0.104 (4)	0.214 (2)	0.074 (12)	0.23 (2)
H13B	0.5909	−0.1414	0.2053	0.112*	0.23 (2)
C14B	0.391 (3)	−0.154 (3)	0.280 (2)	0.072 (7)	0.23 (2)
H14B	0.4437	−0.2272	0.3126	0.108*	0.23 (2)
C15B	0.225 (3)	−0.093 (3)	0.2963 (16)	0.053 (6)	0.23 (2)
H15B	0.1608	−0.1244	0.3395	0.079*	0.23 (2)

	U11	U22	U33	U12	U13	U23
S6	0.0669 (5)	0.0494 (4)	0.0553 (4)	−0.0142 (4)	0.0264 (3)	−0.0107 (4)
N1	0.0485 (13)	0.0404 (12)	0.0538 (13)	−0.0110 (11)	0.0150 (10)	−0.0100 (11)
N2	0.0480 (13)	0.0527 (13)	0.0577 (15)	−0.0092 (11)	0.0180 (11)	−0.0129 (12)
N4	0.0407 (11)	0.0443 (12)	0.0491 (12)	−0.0089 (10)	0.0113 (9)	−0.0094 (11)
C3	0.0438 (14)	0.0560 (16)	0.0558 (16)	−0.0092 (14)	0.0160 (12)	−0.0166 (14)
C5	0.0429 (14)	0.0345 (12)	0.0465 (15)	−0.0038 (11)	0.0069 (11)	0.0005 (11)
C7	0.0447 (15)	0.0585 (18)	0.0665 (19)	−0.0148 (14)	0.0138 (13)	−0.0140 (15)
C8	0.080 (2)	0.0522 (18)	0.102 (3)	−0.0176 (17)	0.031 (2)	−0.0055 (18)
C9	0.0629 (19)	0.101 (3)	0.089 (2)	−0.0244 (19)	0.0288 (17)	−0.054 (2)
C10	0.0451 (15)	0.0458 (15)	0.0465 (15)	−0.0063 (12)	0.0078 (12)	−0.0113 (13)
C11A	0.052 (4)	0.043 (4)	0.055 (4)	0.004 (3)	0.006 (3)	−0.004 (2)
C12A	0.062 (5)	0.063 (5)	0.062 (4)	0.001 (3)	0.024 (3)	−0.004 (3)
C13A	0.043 (4)	0.077 (5)	0.080 (5)	0.008 (3)	0.014 (4)	−0.027 (4)
C14A	0.063 (6)	0.063 (5)	0.087 (8)	0.018 (4)	−0.015 (5)	0.002 (4)
C15A	0.091 (6)	0.063 (4)	0.050 (4)	−0.020 (5)	−0.003 (4)	0.007 (3)
C11B	0.054 (19)	0.06 (2)	0.09 (2)	0.006 (12)	−0.022 (13)	−0.003 (13)
C12B	0.032 (14)	0.07 (2)	0.052 (16)	−0.003 (12)	0.015 (12)	−0.019 (14)
C13B	0.051 (12)	0.10 (2)	0.07 (2)	−0.041 (13)	0.029 (13)	−0.041 (18)
C14B	0.074 (15)	0.049 (11)	0.094 (19)	0.016 (10)	−0.004 (13)	0.003 (11)
C15B	0.033 (10)	0.059 (12)	0.067 (15)	0.008 (9)	0.003 (7)	0.008 (8)

S6—C5	1.673 (3)	C10—C11B	1.379 (5)
N1—C5	1.335 (3)	C10—C15A	1.394 (7)
N1—N2	1.371 (3)	C11A—C12A	1.376 (9)
N1—H1	0.86 (3)	C11A—H11A	0.9300
N2—C3	1.288 (3)	C12A—C13A	1.381 (10)
N4—C5	1.365 (3)	C12A—H12A	0.9300
N4—C3	1.370 (3)	C13A—C14A	1.360 (11)
N4—C7	1.457 (3)	C13A—H13A	0.9300
C3—C9	1.498 (4)	C14A—C15A	1.361 (9)
C7—C8	1.502 (4)	C14A—H14A	0.9300
C7—H7A	0.9700	C15A—H15A	0.9300
C7—H7B	0.9700	C11B—C12B	1.380 (5)
C8—H8A	0.9600	C11B—H11B	0.9300
C8—H8B	0.9600	C12B—C13B	1.379 (5)
C8—H8C	0.9600	C12B—H12B	0.9300
C9—C10	1.504 (4)	C13B—C14B	1.377 (5)
C9—H91	0.9700	C13B—H13B	0.9300
C9—H92	0.9700	C14B—C15B	1.379 (5)
C10—C11A	1.369 (6)	C14B—H14B	0.9300
C10—C15B	1.379 (5)	C15B—H15B	0.9300
C5—N1—N2	113.6 (2)	C15B—C10—C9	103.9 (10)
C5—N1—H1	123 (2)	C11B—C10—C9	133.0 (12)
N2—N1—H1	123 (2)	C15A—C10—C9	126.1 (5)
C3—N2—N1	103.7 (2)	C10—C11A—C12A	121.7 (8)
C5—N4—C3	107.9 (2)	C10—C11A—H11A	119.2
C5—N4—C7	124.2 (2)	C12A—C11A—H11A	119.2
C3—N4—C7	127.9 (2)	C11A—C12A—C13A	120.5 (9)
N2—C3—N4	111.5 (2)	C11A—C12A—H12A	119.8
N2—C3—C9	126.0 (2)	C13A—C12A—H12A	119.8
N4—C3—C9	122.4 (2)	C14A—C13A—C12A	118.3 (8)
N1—C5—N4	103.2 (2)	C14A—C13A—H13A	120.8
N1—C5—S6	129.3 (2)	C12A—C13A—H13A	120.8
N4—C5—S6	127.47 (18)	C13A—C14A—C15A	121.1 (7)
N4—C7—C8	111.6 (2)	C13A—C14A—H14A	119.4
N4—C7—H7A	109.3	C15A—C14A—H14A	119.4
C8—C7—H7A	109.3	C14A—C15A—C10	121.6 (5)
N4—C7—H7B	109.3	C14A—C15A—H15A	119.2
C8—C7—H7B	109.3	C10—C15A—H15A	119.2
H7A—C7—H7B	108.0	C10—C11B—C12B	120.3 (17)
C7—C8—H8A	109.5	C10—C11B—H11B	119.8
C7—C8—H8B	109.5	C12B—C11B—H11B	119.8
H8A—C8—H8B	109.5	C13B—C12B—C11B	115 (2)
C7—C8—H8C	109.5	C13B—C12B—H12B	122.3
H8A—C8—H8C	109.5	C11B—C12B—H12B	122.3
H8B—C8—H8C	109.5	C14B—C13B—C12B	126 (2)
C3—C9—C10	114.1 (3)	C14B—C13B—H13B	117.2
C3—C9—H91	108.7	C12B—C13B—H13B	117.2
C10—C9—H91	108.7	C13B—C14B—C15B	117 (2)
C3—C9—H92	108.7	C13B—C14B—H14B	121.3
C10—C9—H92	108.7	C15B—C14B—H14B	121.3
H91—C9—H92	107.6	C14B—C15B—C10	118.3 (15)
C15B—C10—C11B	122.5 (12)	C14B—C15B—H15B	120.8
C11A—C10—C15A	116.8 (5)	C10—C15B—H15B	120.8
C11A—C10—C9	117.1 (5)
C5—N1—N2—C3	−0.1 (3)	C3—C9—C10—C11B	−105 (4)
N1—N2—C3—N4	0.3 (3)	C3—C9—C10—C15A	79.6 (7)
N1—N2—C3—C9	178.3 (3)	C15A—C10—C11A—C12A	0.7 (18)
C5—N4—C3—N2	−0.3 (3)	C9—C10—C11A—C12A	−177.0 (11)
C7—N4—C3—N2	179.7 (3)	C10—C11A—C12A—C13A	0 (2)
C5—N4—C3—C9	−178.5 (3)	C11A—C12A—C13A—C14A	0.4 (17)
C7—N4—C3—C9	1.6 (5)	C12A—C13A—C14A—C15A	−2.2 (16)
N2—N1—C5—N4	−0.1 (3)	C13A—C14A—C15A—C10	3.3 (16)
N2—N1—C5—S6	179.3 (2)	C11A—C10—C15A—C14A	−2.5 (14)
C3—N4—C5—N1	0.2 (3)	C9—C10—C15A—C14A	175.0 (7)
C7—N4—C5—N1	−179.8 (2)	C15B—C10—C11B—C12B	−2 (7)
C3—N4—C5—S6	−179.2 (2)	C9—C10—C11B—C12B	−173 (3)
C7—N4—C5—S6	0.8 (4)	C10—C11B—C12B—C13B	−3 (7)
C5—N4—C7—C8	−88.5 (3)	C11B—C12B—C13B—C14B	7 (5)
C3—N4—C7—C8	91.4 (3)	C12B—C13B—C14B—C15B	−4 (5)
N2—C3—C9—C10	25.1 (5)	C13B—C14B—C15B—C10	−2 (5)
N4—C3—C9—C10	−157.0 (3)	C11B—C10—C15B—C14B	5 (5)
C3—C9—C10—C11A	−102.9 (9)	C9—C10—C15B—C14B	178 (3)
C3—C9—C10—C15B	83.1 (16)

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7B···S6	0.97	2.85	3.204 (3)	103
N1—H1···S6i	0.86 (3)	2.46 (3)	3.303 (3)	167 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7B⋯S6	0.97	2.85	3.204 (3)	103
N1—H1⋯S6i	0.86 (3)	2.46 (3)	3.303 (3)	167 (3)

Symmetry code: (i) .