Ethyl 2-(3-methyl-5-sulfanyl-idene-4,5-dihydro-1H-1,2,4-triazol-4-yl)acetate.

The title compound, C7H11N3O2S, exists in the 5-thioxo tautomeric form. The 1,2,4-triazoline ring is essentially planar, with a maximum deviation of 0.010 (2) Å for the substituted N atom. The ethyl acetate substituent is almost planar, with a maximum deviation of 0.061 (4) Å for the methyl-ene C atom of the eth-oxy group. The angle between the mean plane of this substituent and the mean plane of the 1,2,4-triazoline ring is 89.74 (8)°. In the crystal, mol-ecules are linked by a combination of N-H⋯S, C-H⋯N and C-H⋯O hydrogen bonds into chains parallel to [100].

Related literature

For background information on the title compound, see: Saadeh et al. (2010 ▶); Akhtar et al. (2008 ▶); Al-Omar et al. (2010 ▶). For the biological activity of 1,2,4-triazoline-thio­nes, see: Pitucha et al. (2010 ▶). For their synthesis, see: Bany & Dobosz (1972 ▶). For related structures, see: Kruszynski et al. (2007 ▶); Siwek et al. (2008 ▶). For graph-set motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C7H11N3O2S

M = 201.25

Monoclinic,

a = 6.4438 (19) Å

b = 15.2328 (15) Å

c = 9.9672 (8) Å

β = 98.416 (19)°

V = 967.8 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.31 mm−1

T = 293 K

0.60 × 0.30 × 0.30 mm

Data collection

Kuma KM-4 four-circle diffractometer

Absorption correction: ψ scan (North et al., 1968 ▶) T min = 0.754, T max = 0.869

2979 measured reflections

2837 independent reflections

1571 reflections with I > 2σ(I)

R int = 0.069

2 standard reflections every 100 reflections intensity decay: 8.9%

Refinement

R[F 2 > 2σ(F 2)] = 0.062

wR(F 2) = 0.198

S = 0.93

2837 reflections

123 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.64 e Å−3

Δρmin = −0.48 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/S1600536812044716/fj2601sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812044716/fj2601Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536812044716/fj2601Isup3.cml

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

C7H11N3O2S	F(000) = 424
Mr = 201.25	Dx = 1.381 Mg m−3
Monoclinic, P21/c	Melting point = 446–447 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 6.4438 (19) Å	Cell parameters from 70 reflections
b = 15.2328 (15) Å	θ = 2.7–11.9°
c = 9.9672 (8) Å	µ = 0.31 mm−1
β = 98.416 (19)°	T = 293 K
V = 967.8 (3) Å3	Prism, colourless
Z = 4	0.60 × 0.30 × 0.30 mm

Kuma KM-4 four-circle diffractometer	1571 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.069
Graphite monochromator	θmax = 30.1°, θmin = 2.5°
ω–2θ scans	h = −9→8
Absorption correction: ψ scan (North et al., 1968)	k = 0→21
Tmin = 0.754, Tmax = 0.869	l = 0→14
2979 measured reflections	2 standard reflections every 100 reflections
2837 independent reflections	intensity decay: 8.9%

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)] = 0.062	Hydrogen site location: difference Fourier map
wR(F2) = 0.198	H atoms treated by a mixture of independent and constrained refinement
S = 0.93	w = 1/[σ2(Fo2) + (0.1344P)2] where P = (Fo2 + 2Fc2)/3
2837 reflections	(Δ/σ)max < 0.001
123 parameters	Δρmax = 0.64 e Å−3
0 restraints	Δρmin = −0.48 e Å−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
S6	0.29109 (11)	0.08274 (5)	0.48884 (8)	0.0493 (3)
O10	0.2086 (3)	0.33096 (15)	0.4137 (2)	0.0553 (6)
O11	0.5003 (3)	0.34124 (13)	0.31670 (19)	0.0423 (5)
N1	−0.1100 (3)	0.08964 (16)	0.3569 (2)	0.0384 (5)
H1	−0.152 (6)	0.053 (3)	0.402 (4)	0.058*
N2	−0.2330 (3)	0.13342 (15)	0.2554 (2)	0.0400 (5)
N4	0.0940 (3)	0.17783 (14)	0.2764 (2)	0.0324 (4)
C3	−0.1054 (4)	0.18780 (18)	0.2086 (2)	0.0348 (5)
C5	0.0896 (4)	0.11528 (17)	0.3742 (2)	0.0338 (5)
C7	−0.1642 (4)	0.2523 (2)	0.0993 (3)	0.0449 (6)
H7A	−0.1073	0.2345	0.0198	0.067*
H7B	−0.1093	0.3089	0.1282	0.067*
H7C	−0.3143	0.2555	0.0788	0.067*
C8	0.2820 (4)	0.22340 (18)	0.2511 (2)	0.0348 (5)
H8A	0.2677	0.2399	0.1562	0.052*
H8B	0.4014	0.1842	0.2700	0.052*
C9	0.3210 (4)	0.30402 (17)	0.3374 (2)	0.0347 (5)
C12	0.5476 (5)	0.4245 (2)	0.3862 (4)	0.0553 (8)
H12A	0.5543	0.4166	0.4833	0.083*
H12B	0.4386	0.4670	0.3561	0.083*
C13	0.7523 (7)	0.4562 (3)	0.3544 (5)	0.0743 (11)
H13A	0.8607	0.4158	0.3902	0.111*
H13B	0.7818	0.5130	0.3944	0.111*
H13C	0.7469	0.4604	0.2578	0.111*

	U11	U22	U33	U12	U13	U23
S6	0.0354 (4)	0.0521 (4)	0.0567 (5)	−0.0037 (3)	−0.0051 (3)	0.0156 (3)
O10	0.0513 (12)	0.0536 (13)	0.0663 (13)	−0.0048 (10)	0.0263 (10)	−0.0162 (10)
O11	0.0342 (9)	0.0406 (10)	0.0530 (11)	−0.0086 (8)	0.0094 (7)	−0.0052 (8)
N1	0.0306 (10)	0.0387 (12)	0.0460 (12)	−0.0034 (9)	0.0064 (8)	0.0086 (10)
N2	0.0278 (10)	0.0463 (12)	0.0457 (12)	−0.0014 (9)	0.0046 (8)	0.0046 (10)
N4	0.0247 (9)	0.0336 (10)	0.0392 (10)	−0.0001 (8)	0.0061 (7)	0.0002 (8)
C3	0.0280 (11)	0.0398 (13)	0.0367 (12)	0.0024 (10)	0.0052 (9)	0.0003 (10)
C5	0.0300 (11)	0.0302 (11)	0.0411 (13)	−0.0001 (9)	0.0051 (9)	0.0001 (10)
C7	0.0352 (14)	0.0523 (16)	0.0467 (15)	0.0049 (12)	0.0045 (11)	0.0091 (12)
C8	0.0268 (11)	0.0411 (13)	0.0384 (12)	−0.0036 (10)	0.0115 (9)	−0.0008 (10)
C9	0.0329 (12)	0.0355 (12)	0.0360 (12)	0.0001 (10)	0.0062 (9)	0.0038 (10)
C12	0.0517 (17)	0.0402 (15)	0.072 (2)	−0.0077 (13)	0.0029 (15)	−0.0088 (15)
C13	0.063 (2)	0.057 (2)	0.105 (3)	−0.0248 (18)	0.019 (2)	−0.007 (2)

S6—C5	1.674 (3)	C7—H7A	0.9600
O10—C9	1.197 (3)	C7—H7B	0.9600
O11—C9	1.330 (3)	C7—H7C	0.9600
O11—C12	1.455 (4)	C8—C9	1.499 (4)
N1—C5	1.331 (3)	C8—H8A	0.9700
N1—N2	1.364 (3)	C8—H8B	0.9700
N1—H1	0.79 (4)	C12—C13	1.482 (5)
N2—C3	1.301 (3)	C12—H12A	0.9700
N4—C5	1.367 (3)	C12—H12B	0.9700
N4—C3	1.369 (3)	C13—H13A	0.9600
N4—C8	1.450 (3)	C13—H13B	0.9600
C3—C7	1.475 (4)	C13—H13C	0.9600
C9—O11—C12	115.0 (2)	N4—C8—H8A	109.3
C5—N1—N2	113.5 (2)	C9—C8—H8A	109.3
C5—N1—H1	123 (3)	N4—C8—H8B	109.3
N2—N1—H1	124 (3)	C9—C8—H8B	109.3
C3—N2—N1	104.3 (2)	H8A—C8—H8B	108.0
C5—N4—C3	108.3 (2)	O10—C9—O11	124.9 (3)
C5—N4—C8	124.3 (2)	O10—C9—C8	125.4 (2)
C3—N4—C8	127.5 (2)	O11—C9—C8	109.7 (2)
N2—C3—N4	110.5 (2)	O11—C12—C13	108.2 (3)
N2—C3—C7	125.5 (2)	O11—C12—H12A	110.1
N4—C3—C7	124.0 (2)	C13—C12—H12A	110.1
N1—C5—N4	103.4 (2)	O11—C12—H12B	110.1
N1—C5—S6	129.8 (2)	C13—C12—H12B	110.1
N4—C5—S6	126.74 (19)	H12A—C12—H12B	108.4
C3—C7—H7A	109.5	C12—C13—H13A	109.5
C3—C7—H7B	109.5	C12—C13—H13B	109.5
H7A—C7—H7B	109.5	H13A—C13—H13B	109.5
C3—C7—H7C	109.5	C12—C13—H13C	109.5
H7A—C7—H7C	109.5	H13A—C13—H13C	109.5
H7B—C7—H7C	109.5	H13B—C13—H13C	109.5
N4—C8—C9	111.52 (19)
C5—N1—N2—C3	0.0 (3)	C8—N4—C5—N1	−177.5 (2)
N1—N2—C3—N4	1.2 (3)	C3—N4—C5—S6	−176.9 (2)
N1—N2—C3—C7	−178.1 (3)	C8—N4—C5—S6	3.8 (4)
C5—N4—C3—N2	−1.9 (3)	C5—N4—C8—C9	−88.1 (3)
C8—N4—C3—N2	177.3 (2)	C3—N4—C8—C9	92.7 (3)
C5—N4—C3—C7	177.4 (2)	C12—O11—C9—O10	−5.1 (4)
C8—N4—C3—C7	−3.3 (4)	C12—O11—C9—C8	175.1 (2)
N2—N1—C5—N4	−1.1 (3)	N4—C8—C9—O10	−3.2 (4)
N2—N1—C5—S6	177.5 (2)	N4—C8—C9—O11	176.7 (2)
C3—N4—C5—N1	1.8 (3)	C9—O11—C12—C13	179.2 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S6i	0.79 (4)	2.56 (4)	3.339 (3)	170 (4)
C8—H8B···N2ii	0.97	2.50	3.407 (3)	155
C13—H13A···O10ii	0.96	2.57	3.482 (5)	159

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯S6i	0.79 (4)	2.56 (4)	3.339 (3)	170 (4)
C8—H8B⋯N2ii	0.97	2.50	3.407 (3)	155
C13—H13A⋯O10ii	0.96	2.57	3.482 (5)	159

Symmetry codes: (i) ; (ii) .