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

The mol-ecule of the title compound, C(4)H(7)N(3)S, exists as the thione tautomer in the solid state. The asymmetric unit consits of one mol-ecule in which all atoms are located on a crystallographic mirror plane. In the crystal, adjacent mol-ecules are linked by N-H⋯N and N-H⋯S hydrogen bonds into chains running along the a axis. π-π stacking inter-actions between the triazole rings [centroid-centroid distance = 3.740 (1) Å and inter-planar distance = 3.376 Å] may further stabilize the structure.

Related literature

For applications of thione-substituted triazoles and its derivatives in coordination chemistry, see: Shivarama et al. (2006 ▶); Wujec et al. (2007 ▶); Ghassemzadeh et al. (2008 ▶); Zhang et al. (2008 ▶). For crystal structure reports of 3-(alkyl or ar­yl)-1,2,4-triazole-5-thione compounds, see: Buzykin et al. (2008 ▶); Pachuta-Stec et al. (2009 ▶). For related structures of thione-substituted 1,2,4-triazole compounds, see: Kajdan et al. (2000 ▶). For the previous synthesis of the title compound, see: Jones & Ainsworth (1955 ▶).

Experimental

Crystal data

C4H7N3S

M = 129.19

Monoclinic,

a = 5.0922 (10) Å

b = 6.7526 (14) Å

c = 8.6578 (17) Å

β = 90.17 (3)°

V = 297.70 (10) Å3

Z = 2

Mo Kα radiation

μ = 0.43 mm−1

T = 293 K

0.26 × 0.21 × 0.11 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer

Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T min = 0.896, T max = 0.954

2467 measured reflections

637 independent reflections

590 reflections with I > 2σ(I)

R int = 0.034

Refinement

R[F 2 > 2σ(F 2)] = 0.042

wR(F 2) = 0.116

S = 1.09

637 reflections

49 parameters

H-atom parameters constrained

Δρmax = 0.50 e Å−3

Δρmin = −0.30 e Å−3

Data collection: RAPID-AUTO (Rigaku, 1998 ▶); cell refinement: RAPID-AUTO; data reduction: CrystalClear (Rigaku/MSC, 2002 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 1999 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812021927/nc2279sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812021927/nc2279Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812021927/nc2279Isup3.cdx

Supplementary material file. DOI: 10.1107/S1600536812021927/nc2279Isup4.cml

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

C4H7N3S	Z = 2
Mr = 129.19	F(000) = 136
Monoclinic, P21/m	Dx = 1.441 Mg m−3
Hall symbol: -P 2yb	Mo Kα radiation, λ = 0.71073 Å
a = 5.0922 (10) Å	µ = 0.43 mm−1
b = 6.7526 (14) Å	T = 293 K
c = 8.6578 (17) Å	Rod, colorless
β = 90.17 (3)°	0.26 × 0.21 × 0.11 mm
V = 297.70 (10) Å3

Rigaku R-AXIS RAPID IP diffractometer	637 independent reflections
Radiation source: fine-focus sealed tube	590 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.034
ω scans	θmax = 26.0°, θmin = 3.8°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −6→6
Tmin = 0.896, Tmax = 0.954	k = −8→7
2467 measured reflections	l = −10→9

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.116	H-atom parameters constrained
S = 1.09	w = 1/[σ2(Fo2) + (0.0332P)2 + 0.4796P] where P = (Fo2 + 2Fc2)/3
637 reflections	(Δ/σ)max < 0.001
49 parameters	Δρmax = 0.50 e Å−3
0 restraints	Δρmin = −0.30 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)
S1	0.45391 (12)	0.2500	0.74979 (7)	0.03824 (18)
N1	0.0168 (4)	0.2500	0.5691 (3)	0.0384 (6)
H1D	−0.0890	0.2500	0.6464	0.046*
N2	−0.0665 (4)	0.2500	0.4165 (2)	0.0344 (5)
N3	0.3624 (4)	0.2500	0.4359 (2)	0.0347 (5)
H3A	0.5244	0.2500	0.4082	0.042*
C1	−0.0885 (5)	0.2500	0.0845 (3)	0.0447 (8)
H1A	−0.0616	0.2500	−0.0252	0.067*
H1B	−0.1855	0.3661	0.1135	0.067*	0.50
H1C	−0.1855	0.1339	0.1135	0.067*	0.50
C2	0.1729 (5)	0.2500	0.1657 (3)	0.0377 (7)
H2A	0.2710	0.1340	0.1336	0.045*	0.50
H2B	0.2710	0.3660	0.1336	0.045*	0.50
C3	0.1532 (5)	0.2500	0.3376 (3)	0.0311 (6)
C4	0.2769 (5)	0.2500	0.5841 (3)	0.0345 (6)

	U11	U22	U33	U12	U13	U23
S1	0.0270 (3)	0.0578 (4)	0.0299 (3)	0.000	−0.0018 (2)	0.000
N1	0.0287 (10)	0.0526 (14)	0.0338 (11)	0.000	0.0008 (9)	0.000
N2	0.0258 (9)	0.0435 (12)	0.0339 (11)	0.000	−0.0006 (8)	0.000
N3	0.0204 (9)	0.0486 (13)	0.0349 (11)	0.000	0.0017 (8)	0.000
C1	0.0332 (13)	0.0639 (19)	0.0368 (14)	0.000	−0.0086 (11)	0.000
C2	0.0276 (11)	0.0535 (16)	0.0321 (12)	0.000	−0.0014 (10)	0.000
C3	0.0229 (10)	0.0334 (13)	0.0368 (12)	0.000	−0.0025 (9)	0.000
C4	0.0274 (11)	0.0368 (13)	0.0393 (13)	0.000	0.0003 (10)	0.000

S1—C4	1.692 (3)	C1—C2	1.504 (4)
N1—C4	1.330 (3)	C1—H1A	0.9600
N1—N2	1.386 (3)	C1—H1B	0.9600
N1—H1D	0.8600	C1—H1C	0.9600
N2—C3	1.312 (3)	C2—C3	1.492 (4)
N3—C4	1.356 (3)	C2—H2A	0.9700
N3—C3	1.362 (3)	C2—H2B	0.9700
N3—H3A	0.8600
C4—N1—N2	113.2 (2)	C3—C2—C1	113.8 (2)
C4—N1—H1D	123.4	C3—C2—H2A	108.8
N2—N1—H1D	123.4	C1—C2—H2A	108.8
C3—N2—N1	103.7 (2)	C3—C2—H2B	108.8
C4—N3—C3	109.8 (2)	C1—C2—H2B	108.8
C4—N3—H3A	125.1	H2A—C2—H2B	107.7
C3—N3—H3A	125.1	N2—C3—N3	109.9 (2)
C2—C1—H1A	109.5	N2—C3—C2	125.4 (2)
C2—C1—H1B	109.5	N3—C3—C2	124.6 (2)
H1A—C1—H1B	109.5	N1—C4—N3	103.3 (2)
C2—C1—H1C	109.5	N1—C4—S1	127.6 (2)
H1A—C1—H1C	109.5	N3—C4—S1	129.07 (19)
H1B—C1—H1C	109.5

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1D···S1i	0.86	2.50	3.270 (2)	150
N3—H3A···N2ii	0.86	2.08	2.914 (3)	162

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1D⋯S1i	0.86	2.50	3.270 (2)	150
N3—H3A⋯N2ii	0.86	2.08	2.914 (3)	162

Symmetry codes: (i) ; (ii) .