3-Ethyl-4-[(E)-2-methyl-benzyl-idene-amino]-1H-1,2,4-triazole-5(4H)-thione.

Crystals of the title compound, C(12)H(14)N(4)S, were obtained from a condensation reaction of 4-amino-3-ethyl-1H-1,2,4-triazole-5(4H)-thione and 2-methyl-benzaldehyde. In the mol-ecular structure, there is a short N=C double bond [1.255 (2) Å], and the benzene and triazole rings are located on opposite sites of this double bond. The two rings are approximately parallel to each other, the dihedral angle being 1.75 (11)°. A partially overlapped arrangement is observed between the nearly parallel triazole and benzene rings of adjacent mol-ecules; the perpendicular distance of the centroid of the triazole ring from the benzene ring is 3.482 Å, indicating the existence of π-π stacking in the crystal structure.

Related literature

For general background, see: Okabe et al. (1993 ▶); Shan et al. (2003 ▶). For related structures, see: Fan et al. (2008 ▶); Shan et al. (2004 ▶, 2008 ▶). For the thickness of the aromatic ring, see: Cotton & Wilkinson (1972 ▶).

Experimental

Crystal data

C12H14N4S

M = 246.33

Monoclinic,

a = 7.7255 (15) Å

b = 15.411 (3) Å

c = 10.685 (2) Å

β = 101.032 (12)°

V = 1248.7 (4) Å3

Z = 4

Mo Kα radiation

μ = 0.24 mm−1

T = 295 (2) K

0.32 × 0.28 × 0.24 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer

Absorption correction: none

12354 measured reflections

2860 independent reflections

1777 reflections with I > 2σ(I)

R int = 0.061

Refinement

R[F 2 > 2σ(F 2)] = 0.047

wR(F 2) = 0.120

S = 1.03

2860 reflections

156 parameters

H-atom parameters constrained

Δρmax = 0.18 e Å−3

Δρmin = −0.21 e Å−3

Data collection: PROCESS-AUTO (Rigaku, 1998 ▶); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ▶); program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808019867/xu2434sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808019867/xu2434Isup2.hkl

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

C12H14N4S	F000 = 520
Mr = 246.33	Dx = 1.310 Mg m−3
Monoclinic, P21/n	Mo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4278 reflections
a = 7.7255 (15) Å	θ = 2.8–24.5º
b = 15.411 (3) Å	µ = 0.24 mm−1
c = 10.685 (2) Å	T = 295 (2) K
β = 101.032 (12)º	Prism, yellow
V = 1248.7 (4) Å3	0.32 × 0.28 × 0.24 mm
Z = 4

Rigaku R-AXIS RAPID IP diffractometer	2860 independent reflections
Radiation source: fine-focus sealed tube	1777 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.061
Detector resolution: 10.00 pixels mm-1	θmax = 27.6º
T = 295(2) K	θmin = 2.6º
ω scans	h = −9→10
Absorption correction: none	k = −20→16
12354 measured reflections	l = −13→13

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)] = 0.047	H-atom parameters constrained
wR(F2) = 0.121	w = 1/[σ2(Fo2) + (0.0463P)2 + 0.2633P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max < 0.001
2860 reflections	Δρmax = 0.18 e Å−3
156 parameters	Δρmin = −0.21 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

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
S	0.70986 (7)	−0.00644 (3)	0.39484 (6)	0.0542 (2)
N1	0.9437 (2)	0.12184 (11)	0.47565 (18)	0.0453 (5)
H1N	1.0320	0.0826	0.5095	0.068*
N2	0.9697 (2)	0.20996 (11)	0.47450 (18)	0.0449 (5)
N3	0.70093 (19)	0.17368 (10)	0.37970 (15)	0.0356 (4)
N4	0.5343 (2)	0.19429 (11)	0.31007 (17)	0.0424 (5)
C1	0.7829 (3)	0.09601 (13)	0.4175 (2)	0.0388 (5)
C2	0.8200 (3)	0.24045 (13)	0.4152 (2)	0.0387 (5)
C3	0.7750 (3)	0.33278 (13)	0.3886 (2)	0.0486 (6)
H3A	0.6760	0.3482	0.4279	0.058*
H3B	0.7391	0.3408	0.2973	0.058*
C4	0.9288 (3)	0.39305 (14)	0.4383 (3)	0.0627 (7)
H4A	0.9624	0.3868	0.5291	0.094*
H4B	0.8942	0.4520	0.4180	0.094*
H4C	1.0270	0.3784	0.3991	0.094*
C5	0.4118 (3)	0.13985 (14)	0.3022 (2)	0.0443 (6)
H5	0.4330	0.0856	0.3402	0.053*
C6	0.2346 (3)	0.16241 (14)	0.2325 (2)	0.0412 (5)
C7	0.1079 (3)	0.09783 (15)	0.1958 (2)	0.0484 (6)
C8	−0.0589 (3)	0.1238 (2)	0.1313 (2)	0.0631 (7)
H8	−0.1454	0.0820	0.1064	0.076*
C9	−0.0980 (3)	0.2091 (2)	0.1040 (3)	0.0688 (8)
H9	−0.2105	0.2245	0.0618	0.083*
C10	0.0279 (3)	0.27235 (18)	0.1386 (2)	0.0621 (7)
H10	0.0019	0.3302	0.1182	0.074*
C11	0.1935 (3)	0.24901 (15)	0.2038 (2)	0.0502 (6)
H11	0.2783	0.2916	0.2288	0.060*
C12	0.1452 (3)	0.00349 (16)	0.2212 (3)	0.0700 (8)
H12A	0.2246	−0.0169	0.1687	0.105*
H12B	0.0369	−0.0287	0.2019	0.105*
H12C	0.1978	−0.0045	0.3094	0.105*

	U11	U22	U33	U12	U13	U23
S	0.0374 (3)	0.0352 (3)	0.0829 (5)	−0.0002 (2)	−0.0066 (3)	−0.0011 (3)
N1	0.0309 (9)	0.0361 (9)	0.0641 (12)	0.0015 (7)	−0.0027 (8)	0.0017 (9)
N2	0.0339 (9)	0.0374 (10)	0.0598 (12)	−0.0031 (7)	−0.0003 (8)	0.0001 (9)
N3	0.0273 (8)	0.0326 (8)	0.0443 (10)	0.0001 (7)	0.0000 (7)	0.0000 (7)
N4	0.0305 (9)	0.0416 (10)	0.0507 (11)	0.0016 (8)	−0.0031 (8)	0.0013 (8)
C1	0.0304 (10)	0.0400 (11)	0.0444 (12)	0.0025 (8)	0.0028 (9)	0.0000 (9)
C2	0.0333 (11)	0.0368 (11)	0.0449 (12)	−0.0042 (8)	0.0042 (9)	−0.0016 (9)
C3	0.0468 (12)	0.0380 (12)	0.0586 (14)	−0.0010 (10)	0.0044 (11)	0.0004 (11)
C4	0.0662 (16)	0.0398 (13)	0.0762 (18)	−0.0139 (11)	−0.0015 (14)	0.0007 (12)
C5	0.0336 (11)	0.0393 (11)	0.0568 (14)	0.0026 (9)	0.0011 (10)	0.0017 (10)
C6	0.0297 (10)	0.0505 (12)	0.0423 (12)	0.0011 (9)	0.0042 (9)	0.0005 (10)
C7	0.0349 (11)	0.0594 (15)	0.0493 (14)	−0.0029 (10)	0.0042 (10)	−0.0021 (11)
C8	0.0336 (12)	0.090 (2)	0.0625 (17)	−0.0080 (13)	0.0014 (12)	−0.0046 (15)
C9	0.0353 (13)	0.104 (2)	0.0637 (17)	0.0157 (15)	−0.0003 (12)	0.0089 (16)
C10	0.0513 (14)	0.0725 (17)	0.0615 (16)	0.0261 (13)	0.0086 (13)	0.0125 (14)
C11	0.0413 (12)	0.0545 (14)	0.0538 (14)	0.0100 (10)	0.0069 (11)	0.0033 (11)
C12	0.0550 (15)	0.0620 (17)	0.089 (2)	−0.0124 (13)	0.0029 (14)	−0.0045 (15)

S—C1	1.679 (2)	C5—C6	1.469 (3)
N1—C1	1.338 (2)	C5—H5	0.9300
N1—N2	1.373 (2)	C6—C11	1.393 (3)
N1—H1N	0.9314	C6—C7	1.399 (3)
N2—C2	1.296 (2)	C7—C8	1.398 (3)
N3—C1	1.378 (2)	C7—C12	1.497 (3)
N3—C2	1.384 (2)	C8—C9	1.369 (4)
N3—N4	1.395 (2)	C8—H8	0.9300
N4—C5	1.255 (2)	C9—C10	1.376 (4)
C2—C3	1.479 (3)	C9—H9	0.9300
C3—C4	1.522 (3)	C10—C11	1.382 (3)
C3—H3A	0.9700	C10—H10	0.9300
C3—H3B	0.9700	C11—H11	0.9300
C4—H4A	0.9600	C12—H12A	0.9600
C4—H4B	0.9600	C12—H12B	0.9600
C4—H4C	0.9600	C12—H12C	0.9600
C1—N1—N2	114.48 (16)	N4—C5—H5	120.2
C1—N1—H1N	122.2	C6—C5—H5	120.2
N2—N1—H1N	123.2	C11—C6—C7	120.14 (19)
C2—N2—N1	104.15 (15)	C11—C6—C5	119.32 (19)
C1—N3—C2	108.74 (15)	C7—C6—C5	120.53 (19)
C1—N3—N4	132.83 (15)	C8—C7—C6	117.7 (2)
C2—N3—N4	118.30 (15)	C8—C7—C12	119.6 (2)
C5—N4—N3	119.38 (17)	C6—C7—C12	122.71 (19)
N1—C1—N3	102.21 (16)	C9—C8—C7	121.7 (2)
N1—C1—S	127.10 (15)	C9—C8—H8	119.2
N3—C1—S	130.66 (14)	C7—C8—H8	119.2
N2—C2—N3	110.40 (17)	C8—C9—C10	120.5 (2)
N2—C2—C3	126.69 (18)	C8—C9—H9	119.8
N3—C2—C3	122.91 (17)	C10—C9—H9	119.8
C2—C3—C4	112.41 (18)	C9—C10—C11	119.3 (2)
C2—C3—H3A	109.1	C9—C10—H10	120.3
C4—C3—H3A	109.1	C11—C10—H10	120.3
C2—C3—H3B	109.1	C10—C11—C6	120.7 (2)
C4—C3—H3B	109.1	C10—C11—H11	119.6
H3A—C3—H3B	107.9	C6—C11—H11	119.6
C3—C4—H4A	109.5	C7—C12—H12A	109.5
C3—C4—H4B	109.5	C7—C12—H12B	109.5
H4A—C4—H4B	109.5	H12A—C12—H12B	109.5
C3—C4—H4C	109.5	C7—C12—H12C	109.5
H4A—C4—H4C	109.5	H12A—C12—H12C	109.5
H4B—C4—H4C	109.5	H12B—C12—H12C	109.5
N4—C5—C6	119.54 (19)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···Si	0.93	2.37	3.2899 (19)	169
C5—H5···S	0.93	2.54	3.239 (2)	132

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯Si	0.93	2.37	3.2899 (19)	169
C5—H5⋯S	0.93	2.54	3.239 (2)	132

Symmetry code: (i) .