4-Ethyl-3-(2-thienylmeth-yl)-Δ-1,2,4-triazoline-5-thione.

The title compound, C(9)H(11)N(3)S(2), exists in the thione form in the crystal structure. The central triazole ring is almost perpendicular to the thio-phene ring which is disordered over two orientations [dihedral angles of 88.5 (7) and 85.7 (8)° for the two orientations]. The crystal structure is stabilized by strong inter-molecular N-H⋯S hydrogen bonds, forming centrosymmetric dimers, and by some weak C-H⋯S inter-actions.

Related literature

For background on the applications of 1,2,4-triazole and its derivatives, see: Ünver et al. (2006 ▶); Dobosz et al. (2002 ▶); Jian et al. (2005 ▶); Maliszewska-Guz et al. (2005 ▶); Al-Soud et al. (2004 ▶); Amir & Shikha (2004 ▶); Collin et al. (2003 ▶); Demirayak et al. (2000 ▶); Palaska et al. (2002 ▶); Shivarama et al. (2006 ▶). For details of the synthesis, see: Wujec et al. (2004 ▶, 2007 ▶). For related structures, see: Yilmaz et al. (2005 ▶).

Experimental

Crystal data

C9H11N3S2

M = 225.33

Monoclinic,

a = 6.813 (1) Å

b = 17.119 (2) Å

c = 9.846 (1) Å

β = 100.88 (1)°

V = 1127.7 (2) Å3

Z = 4

Mo Kα radiation

μ = 0.44 mm−1

T = 295 (2) K

0.47 × 0.30 × 0.16 mm

Data collection

Oxford Diffraction Xcalibur diffractometer

Absorption correction: none

2735 measured reflections

2592 independent reflections

1130 reflections with I > 2σ(I)

R int = 0.026

Refinement

R[F 2 > 2σ(F 2)] = 0.052

wR(F 2) = 0.111

S = 0.98

2592 reflections

147 parameters

H-atom parameters constrained

Δρmax = 0.16 e Å−3

Δρmin = −0.17 e Å−3

Data collection: CrysAlis CCD (Oxford Diffraction, 2005 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2005 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL/PC (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97 and enCIFer (Allen et al., 2004 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809000440/at2696sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809000440/at2696Isup2.hkl

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

C9H11N3S2	F(000) = 472
Mr = 225.33	Dx = 1.327 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 69 reflections
a = 6.813 (1) Å	θ = 6–14°
b = 17.119 (2) Å	µ = 0.44 mm−1
c = 9.846 (1) Å	T = 295 K
β = 100.88 (1)°	Prism, colourless
V = 1127.7 (2) Å3	0.47 × 0.30 × 0.16 mm
Z = 4

Oxford Diffraction Xcalibur diffractometer	Rint = 0.026
Radiation source: fine-focus sealed tube	θmax = 27.6°, θmin = 3.9°
graphite	h = −8→8
ω–2θ scans	k = 0→22
2735 measured reflections	l = 0→12
2592 independent reflections	3 standard reflections every 100 reflections
1130 reflections with I > 2σ(I)	intensity decay: 0.1%

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.111	H-atom parameters constrained
S = 0.98	w = 1/[σ2(Fo2) + (0.0395P)2 + 0.2245P] where P = (Fo2 + 2Fc2)/3
2592 reflections	(Δ/σ)max = 0.002
147 parameters	Δρmax = 0.16 e Å−3
0 restraints	Δρmin = −0.16 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	Occ. (<1)
N1	0.2725 (3)	0.49647 (12)	0.6098 (2)	0.0563 (6)
H1	0.1684	0.4675	0.5868	0.068*
N2	0.4538 (3)	0.46832 (13)	0.6760 (2)	0.0598 (6)
C3	0.5669 (4)	0.52970 (16)	0.6930 (3)	0.0547 (7)
N4	0.4644 (3)	0.59498 (12)	0.6394 (2)	0.0504 (5)
C5	0.2730 (3)	0.57271 (16)	0.5846 (2)	0.0501 (6)
S1	0.08621 (10)	0.62899 (4)	0.50362 (7)	0.0654 (3)
C6	0.7818 (4)	0.52769 (17)	0.7589 (3)	0.0703 (8)
H6A	0.8601	0.5469	0.6933	0.084*
H6B	0.8205	0.4739	0.7799	0.084*
S2	0.7156 (9)	0.5621 (3)	1.0253 (6)	0.0683 (11)	0.538 (6)
C8	0.982 (3)	0.6272 (12)	0.921 (2)	0.123 (10)	0.538 (6)
H8	1.0760	0.6381	0.8662	0.148*	0.538 (6)
C8'	0.757 (3)	0.5727 (13)	1.003 (2)	0.079 (9)	0.462 (6)
H8'	0.6549	0.5383	1.0138	0.094*	0.462 (6)
S2'	1.0016 (7)	0.6482 (5)	0.9087 (7)	0.0949 (14)	0.462 (6)
C7	0.8316 (5)	0.57473 (19)	0.8885 (3)	0.0588 (8)
C9	0.9766 (6)	0.6655 (2)	1.0589 (5)	0.1017 (13)
H9	1.0536	0.7077	1.0974	0.122*
C10	0.8435 (6)	0.6283 (2)	1.1134 (3)	0.0885 (10)
H10	0.8241	0.6403	1.2020	0.106*
C11	0.5372 (4)	0.67518 (16)	0.6362 (3)	0.0670 (8)
H11A	0.4782	0.6990	0.5485	0.080*
H11B	0.6810	0.6744	0.6425	0.080*
C12	0.4875 (5)	0.72417 (17)	0.7527 (3)	0.0815 (9)
H12A	0.5369	0.7763	0.7462	0.098*
H12B	0.5488	0.7017	0.8397	0.098*
H12C	0.3452	0.7257	0.7463	0.098*

	U11	U22	U33	U12	U13	U23
N1	0.0502 (12)	0.0529 (14)	0.0614 (14)	−0.0035 (10)	−0.0008 (10)	−0.0031 (11)
N2	0.0522 (13)	0.0619 (14)	0.0620 (15)	0.0057 (11)	0.0022 (11)	−0.0059 (12)
C3	0.0486 (15)	0.0655 (17)	0.0495 (16)	0.0044 (14)	0.0081 (12)	−0.0053 (15)
N4	0.0448 (12)	0.0561 (13)	0.0489 (12)	−0.0051 (11)	0.0056 (9)	−0.0040 (10)
C5	0.0512 (15)	0.0537 (16)	0.0441 (14)	−0.0029 (12)	0.0056 (12)	−0.0055 (13)
S1	0.0578 (4)	0.0571 (4)	0.0739 (5)	−0.0009 (3)	−0.0067 (3)	0.0003 (4)
C6	0.0456 (16)	0.088 (2)	0.075 (2)	0.0055 (15)	0.0052 (14)	−0.0120 (17)
S2	0.070 (2)	0.0744 (16)	0.0589 (15)	−0.0131 (15)	0.0081 (15)	−0.0015 (13)
C8	0.159 (19)	0.120 (15)	0.102 (10)	0.015 (11)	0.056 (10)	0.031 (9)
C8'	0.057 (9)	0.096 (10)	0.084 (15)	−0.022 (6)	0.015 (6)	0.018 (7)
S2'	0.0717 (17)	0.110 (3)	0.097 (3)	−0.0346 (17)	−0.0010 (15)	0.010 (2)
C7	0.0398 (15)	0.0610 (19)	0.071 (2)	−0.0056 (14)	−0.0015 (15)	0.0057 (17)
C9	0.104 (3)	0.072 (2)	0.109 (3)	−0.029 (2)	−0.033 (2)	0.008 (2)
C10	0.116 (3)	0.081 (2)	0.061 (2)	0.006 (2)	−0.002 (2)	−0.002 (2)
C11	0.0566 (17)	0.0687 (19)	0.0731 (19)	−0.0165 (14)	0.0055 (14)	0.0078 (17)
C12	0.079 (2)	0.0605 (18)	0.098 (2)	−0.0082 (15)	−0.0005 (17)	−0.0105 (18)

N1—C5	1.329 (3)	C8—H8	0.9300
N1—N2	1.370 (3)	C8'—C7	1.32 (2)
N1—H1	0.8600	C8'—C10	1.48 (2)
N2—C3	1.295 (3)	C8'—H8'	0.9300
C3—N4	1.370 (3)	S2'—C9	1.549 (10)
C3—C6	1.485 (3)	S2'—C7	1.695 (6)
N4—C5	1.368 (3)	C9—C10	1.304 (5)
N4—C11	1.462 (3)	C9—H9	0.9300
C5—S1	1.673 (2)	C10—H10	0.9300
C6—C7	1.493 (4)	C11—C12	1.510 (4)
C6—H6A	0.9700	C11—H11A	0.9700
C6—H6B	0.9700	C11—H11B	0.9700
S2—C10	1.584 (7)	C12—H12A	0.9600
S2—C7	1.699 (6)	C12—H12B	0.9600
C8—C7	1.355 (17)	C12—H12C	0.9600
C8—C9	1.51 (2)
C5—N1—N2	113.6 (2)	C8—C7—C6	126.8 (11)
C5—N1—H1	123.2	C8'—C7—S2'	106.5 (10)
N2—N1—H1	123.2	C6—C7—S2'	122.7 (4)
C3—N2—N1	103.7 (2)	C8—C7—S2	110.0 (11)
N2—C3—N4	111.4 (2)	C6—C7—S2	123.0 (3)
N2—C3—C6	123.4 (2)	S2'—C7—S2	114.3 (4)
N4—C3—C6	125.2 (3)	C10—C9—C8	107.1 (7)
C5—N4—C3	107.7 (2)	C10—C9—S2'	120.6 (4)
C5—N4—C11	123.7 (2)	C10—C9—H9	126.5
C3—N4—C11	128.6 (2)	C8—C9—H9	126.5
N1—C5—N4	103.6 (2)	S2'—C9—H9	112.5
N1—C5—S1	128.8 (2)	C9—C10—C8'	103.1 (8)
N4—C5—S1	127.6 (2)	C9—C10—S2	118.6 (4)
C3—C6—C7	114.1 (2)	C9—C10—H10	120.7
C3—C6—H6A	108.7	C8'—C10—H10	136.2
C7—C6—H6A	108.7	S2—C10—H10	120.7
C3—C6—H6B	108.7	N4—C11—C12	112.3 (2)
C7—C6—H6B	108.7	N4—C11—H11A	109.1
H6A—C6—H6B	107.6	C12—C11—H11A	109.1
C10—S2—C7	93.0 (4)	N4—C11—H11B	109.1
C7—C8—C9	110.7 (14)	C12—C11—H11B	109.1
C7—C8—H8	124.7	H11A—C11—H11B	107.9
C9—C8—H8	124.7	C11—C12—H12A	109.5
C7—C8'—C10	116.3 (13)	C11—C12—H12B	109.5
C7—C8'—H8'	121.9	H12A—C12—H12B	109.5
C10—C8'—H8'	121.9	C11—C12—H12C	109.5
C9—S2'—C7	93.4 (4)	H12A—C12—H12C	109.5
C8'—C7—C8	102.3 (15)	H12B—C12—H12C	109.5
C8'—C7—C6	130.7 (10)
C5—N1—N2—C3	0.8 (3)	C3—C6—C7—S2'	−122.1 (4)
N1—N2—C3—N4	−0.4 (3)	C3—C6—C7—S2	54.9 (4)
N1—N2—C3—C6	−178.8 (2)	C9—S2'—C7—C8'	3.9 (11)
N2—C3—N4—C5	−0.1 (3)	C9—S2'—C7—C8	−58 (9)
C6—C3—N4—C5	178.2 (2)	C9—S2'—C7—C6	−178.6 (3)
N2—C3—N4—C11	−179.4 (2)	C9—S2'—C7—S2	4.1 (5)
C6—C3—N4—C11	−1.0 (4)	C10—S2—C7—C8'	−2(9)
N2—N1—C5—N4	−0.9 (3)	C10—S2—C7—C8	5.2 (10)
N2—N1—C5—S1	178.5 (2)	C10—S2—C7—C6	179.8 (2)
C3—N4—C5—N1	0.6 (3)	C10—S2—C7—S2'	−2.9 (4)
C11—N4—C5—N1	179.9 (2)	C7—C8—C9—C10	8.5 (15)
C3—N4—C5—S1	−178.8 (2)	C7—C8—C9—S2'	−145 (4)
C11—N4—C5—S1	0.5 (3)	C7—S2'—C9—C10	−4.2 (5)
N2—C3—C6—C7	−117.9 (3)	C7—S2'—C9—C8	25 (3)
N4—C3—C6—C7	63.9 (4)	C8—C9—C10—C8'	−5.0 (13)
C10—C8'—C7—C8	5(2)	S2'—C9—C10—C8'	2.8 (11)
C10—C8'—C7—C6	179.6 (7)	C8—C9—C10—S2	−4.9 (9)
C10—C8'—C7—S2'	−3.2 (19)	S2'—C9—C10—S2	2.9 (6)
C10—C8'—C7—S2	178 (11)	C7—C8'—C10—C9	0.6 (19)
C9—C8—C7—C8'	−7.5 (18)	C7—C8'—C10—S2	−179 (6)
C9—C8—C7—C6	177.2 (6)	C7—S2—C10—C9	0.2 (4)
C9—C8—C7—S2'	113 (9)	C7—S2—C10—C8'	1(4)
C9—C8—C7—S2	−8.4 (15)	C5—N4—C11—C12	83.3 (3)
C3—C6—C7—C8'	54.7 (14)	C3—N4—C11—C12	−97.5 (3)
C3—C6—C7—C8	−131.4 (11)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S1i	0.86	2.44	3.287 (3)	169
C6—H6a···S1ii	0.97	2.99	3.949 (4)	172
C9—H9···S1iii	0.93	2.97	3.659 (4)	132
C8'—H8'···S2iv	0.93	3.02	3.928 (7)	166

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯S1i	0.86	2.44	3.287 (3)	169
C6—H6a⋯S1ii	0.97	2.99	3.949 (4)	172
C9—H9⋯S1iii	0.93	2.97	3.659 (4)	132
C8′—H8′⋯S2iv	0.93	3.02	3.928 (7)	166

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .