5-Ethyl-5-methyl-4-phenyl-5H-1,2,4-triazol-3(4H)-thione.

The five-membered ring of the title compound Δ(1)-1,2,4-triazoline-5-thione, C(11)H(13)N(3)S, is almost planar (r.m.s. deviation = 0.009 Å); the phenyl ring is aligned at 84.6 (2)° with respect to the five-membered ring. The crystal studied was a racemic twin with an approximate 20% minor twin component. Weak inter-molecular C-H⋯N hydrogen bonding is present in the crystal structure.

Related literature

For the synthesis of this and other Δ1-[1,2,4]-triazoline-5-thio­nes, see: Kabashima et al. (1991 ▶); Landquist (1970 ▶); Tripathi & Dhar (1986 ▶). For the crystal structure of the related compound 5,5-dimethyl-4-phenyl-1,2,4-triazol-3-thione, see: Katritzky et al. (1984 ▶).

Experimental

Crystal data

C11H13N3S

M = 219.30

Tetragonal,

a = 17.962 (4) Å

c = 6.9992 (14) Å

V = 2258.2 (6) Å3

Z = 8

Mo Kα radiation

μ = 0.26 mm−1

T = 100 K

0.30 × 0.05 × 0.05 mm

Data collection

Bruker SMART APEX diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.927, T max = 0.987

10418 measured reflections

1987 independent reflections

1546 reflections with I > 2σ(I)

R int = 0.087

Refinement

R[F 2 > 2σ(F 2)] = 0.065

wR(F 2) = 0.186

S = 1.07

1987 reflections

136 parameters

H-atom parameters constrained

Δρmax = 0.69 e Å−3

Δρmin = −0.31 e Å−3

Absolute structure: Flack (1983 ▶), 837 Friedel pairs

Flack parameter: −0.2 (2)

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: X-SEED (Barbour, 2001 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810030503/xu5008sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810030503/xu5008Isup2.hkl

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

C11H13N3S	Dx = 1.290 Mg m−3
Mr = 219.30	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P421c	Cell parameters from 926 reflections
Hall symbol: P -4 2n	θ = 2.5–18.5°
a = 17.962 (4) Å	µ = 0.26 mm−1
c = 6.9992 (14) Å	T = 100 K
V = 2258.2 (6) Å3	Prism, orange
Z = 8	0.30 × 0.05 × 0.05 mm
F(000) = 928

Bruker SMART APEX diffractometer	1987 independent reflections
Radiation source: fine-focus sealed tube	1546 reflections with I > 2σ(I)
graphite	Rint = 0.087
ω scans	θmax = 25.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −21→20
Tmin = 0.927, Tmax = 0.987	k = −21→21
10418 measured reflections	l = −8→5

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)] = 0.065	H-atom parameters constrained
wR(F2) = 0.186	w = 1/[σ2(Fo2) + (0.0992P)2 + 1.8759P] where P = (Fo2 + 2Fc2)/3
S = 1.07	(Δ/σ)max = 0.001
1987 reflections	Δρmax = 0.69 e Å−3
136 parameters	Δρmin = −0.31 e Å−3
0 restraints	Absolute structure: Flack (1983), 837 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: −0.2 (2)

	x	y	z	Uiso*/Ueq
S1	0.47452 (8)	0.23341 (7)	1.2411 (2)	0.0351 (4)
N1	0.4463 (3)	0.2810 (3)	0.8841 (6)	0.0351 (11)
N2	0.4094 (3)	0.3589 (3)	1.1143 (7)	0.0531 (15)
N3	0.3934 (3)	0.3924 (3)	0.9623 (8)	0.0511 (14)
C1	0.4778 (3)	0.2198 (2)	0.7806 (6)	0.0237 (10)
C2	0.5518 (3)	0.2275 (3)	0.7230 (8)	0.0353 (13)
H2	0.5801	0.2706	0.7530	0.042*
C3	0.5823 (3)	0.1677 (3)	0.6175 (9)	0.0441 (15)
H3	0.6323	0.1704	0.5738	0.053*
C4	0.5409 (4)	0.1065 (3)	0.5785 (8)	0.0480 (17)
H4	0.5623	0.0671	0.5066	0.058*
C5	0.4687 (4)	0.1003 (3)	0.6404 (8)	0.0435 (15)
H5	0.4406	0.0568	0.6136	0.052*
C6	0.4381 (3)	0.1576 (3)	0.7413 (9)	0.0351 (12)
H6	0.3881	0.1537	0.7846	0.042*
C7	0.4431 (3)	0.2869 (3)	1.0741 (7)	0.0371 (14)
C8	0.4127 (3)	0.3477 (3)	0.7940 (8)	0.0398 (14)
C9	0.4652 (4)	0.3911 (3)	0.6695 (9)	0.0525 (17)
H9A	0.5098	0.4041	0.7429	0.079*
H9B	0.4407	0.4367	0.6254	0.079*
H9C	0.4794	0.3607	0.5590	0.079*
C10	0.3418 (3)	0.3257 (4)	0.6851 (9)	0.0528 (18)
H10A	0.3210	0.3707	0.6231	0.063*
H10B	0.3554	0.2902	0.5828	0.063*
C11	0.2824 (4)	0.2911 (5)	0.8070 (11)	0.073 (2)
H11A	0.2391	0.2789	0.7276	0.109*
H11B	0.2675	0.3262	0.9072	0.109*
H11C	0.3017	0.2455	0.8659	0.109*

	U11	U22	U33	U12	U13	U23
S1	0.0531 (8)	0.0347 (6)	0.0174 (6)	−0.0009 (6)	−0.0038 (7)	0.0016 (7)
N1	0.051 (3)	0.033 (2)	0.021 (2)	0.014 (2)	−0.004 (2)	−0.001 (2)
N2	0.069 (4)	0.058 (3)	0.033 (3)	0.025 (3)	−0.008 (3)	−0.007 (3)
N3	0.058 (3)	0.048 (3)	0.047 (3)	0.010 (3)	−0.015 (3)	−0.009 (3)
C1	0.035 (2)	0.024 (2)	0.012 (2)	0.0085 (19)	−0.006 (2)	0.000 (2)
C2	0.042 (3)	0.031 (3)	0.032 (3)	−0.009 (2)	−0.009 (3)	0.000 (3)
C3	0.036 (3)	0.055 (4)	0.041 (4)	0.012 (3)	0.015 (3)	0.008 (3)
C4	0.088 (5)	0.034 (3)	0.022 (3)	0.023 (3)	0.001 (3)	0.002 (3)
C5	0.072 (4)	0.029 (3)	0.029 (3)	−0.006 (3)	−0.010 (3)	−0.003 (2)
C6	0.038 (3)	0.038 (3)	0.030 (3)	−0.001 (2)	0.006 (3)	0.001 (3)
C7	0.053 (4)	0.042 (3)	0.016 (3)	0.019 (2)	−0.002 (2)	−0.008 (2)
C8	0.044 (3)	0.039 (3)	0.037 (4)	0.006 (2)	−0.001 (3)	−0.001 (3)
C9	0.059 (4)	0.048 (3)	0.051 (4)	−0.006 (3)	−0.019 (3)	0.021 (3)
C10	0.047 (4)	0.066 (4)	0.046 (4)	0.004 (3)	−0.003 (3)	−0.009 (3)
C11	0.045 (4)	0.101 (6)	0.072 (6)	−0.004 (4)	−0.009 (4)	−0.012 (5)

S1—C7	1.614 (5)	C5—C6	1.364 (8)
N1—C7	1.335 (7)	C5—H5	0.9500
N1—C1	1.433 (6)	C6—H6	0.9500
N1—C8	1.483 (7)	C8—C9	1.502 (8)
N2—N3	1.255 (7)	C8—C10	1.535 (8)
N2—C7	1.456 (7)	C9—H9A	0.9800
N3—C8	1.466 (8)	C9—H9B	0.9800
C1—C6	1.355 (7)	C9—H9C	0.9800
C1—C2	1.396 (7)	C10—C11	1.502 (10)
C2—C3	1.415 (8)	C10—H10A	0.9900
C2—H2	0.9500	C10—H10B	0.9900
C3—C4	1.355 (9)	C11—H11A	0.9800
C3—H3	0.9500	C11—H11B	0.9800
C4—C5	1.372 (9)	C11—H11C	0.9800
C4—H4	0.9500
C7—N1—C1	125.5 (5)	N2—C7—S1	122.3 (4)
C7—N1—C8	110.0 (5)	N3—C8—N1	101.3 (4)
C1—N1—C8	124.5 (4)	N3—C8—C9	109.3 (5)
N3—N2—C7	110.9 (5)	N1—C8—C9	114.2 (5)
N2—N3—C8	111.4 (4)	N3—C8—C10	110.1 (5)
C6—C1—C2	121.7 (4)	N1—C8—C10	109.9 (5)
C6—C1—N1	121.8 (5)	C9—C8—C10	111.5 (5)
C2—C1—N1	116.5 (4)	C8—C9—H9A	109.5
C1—C2—C3	116.4 (5)	C8—C9—H9B	109.5
C1—C2—H2	121.8	H9A—C9—H9B	109.5
C3—C2—H2	121.8	C8—C9—H9C	109.5
C4—C3—C2	120.6 (5)	H9A—C9—H9C	109.5
C4—C3—H3	119.7	H9B—C9—H9C	109.5
C2—C3—H3	119.7	C11—C10—C8	114.4 (6)
C3—C4—C5	121.4 (5)	C11—C10—H10A	108.7
C3—C4—H4	119.3	C8—C10—H10A	108.7
C5—C4—H4	119.3	C11—C10—H10B	108.7
C6—C5—C4	119.0 (5)	C8—C10—H10B	108.7
C6—C5—H5	120.5	H10A—C10—H10B	107.6
C4—C5—H5	120.5	C10—C11—H11A	109.5
C1—C6—C5	121.0 (5)	C10—C11—H11B	109.5
C1—C6—H6	119.5	H11A—C11—H11B	109.5
C5—C6—H6	119.5	C10—C11—H11C	109.5
N1—C7—N2	106.3 (5)	H11A—C11—H11C	109.5
N1—C7—S1	131.2 (5)	H11B—C11—H11C	109.5
C7—N2—N3—C8	0.9 (7)	C8—N1—C7—S1	−176.6 (5)
C7—N1—C1—C6	85.0 (7)	N3—N2—C7—N1	0.5 (7)
C8—N1—C1—C6	−95.6 (6)	N3—N2—C7—S1	175.9 (5)
C7—N1—C1—C2	−94.8 (7)	N2—N3—C8—N1	−1.9 (6)
C8—N1—C1—C2	84.7 (6)	N2—N3—C8—C9	−122.7 (6)
C6—C1—C2—C3	1.5 (7)	N2—N3—C8—C10	114.5 (6)
N1—C1—C2—C3	−178.8 (4)	C7—N1—C8—N3	2.2 (6)
C1—C2—C3—C4	−0.7 (8)	C1—N1—C8—N3	−177.3 (5)
C2—C3—C4—C5	−0.5 (9)	C7—N1—C8—C9	119.6 (6)
C3—C4—C5—C6	0.9 (9)	C1—N1—C8—C9	−60.0 (7)
C2—C1—C6—C5	−1.1 (8)	C7—N1—C8—C10	−114.3 (5)
N1—C1—C6—C5	179.1 (5)	C1—N1—C8—C10	66.2 (7)
C4—C5—C6—C1	−0.1 (9)	N3—C8—C10—C11	−50.8 (8)
C1—N1—C7—N2	177.8 (5)	N1—C8—C10—C11	60.0 (7)
C8—N1—C7—N2	−1.8 (7)	C9—C8—C10—C11	−172.4 (6)
C1—N1—C7—S1	2.9 (10)

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9A···N2i	0.98	2.56	3.519 (9)	165

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9A⋯N2i	0.98	2.56	3.519 (9)	165

Symmetry code: (i) .