4-(4-Chloro­benzyl­ideneamino)-3-(1H-1,2,4-triazol-1-ylmeth­yl)-1H-1,2,4-triazole-5(4H)-thione

In the title compound, C₁₂H₁₀ClN₇S, the dihedral angles made by the plane of the thione-substituted triazole ring with the planes of the other triazole ring and the benzene ring are 73.57 (3) and 46.65 (2)°, respectively. Inter- and intra­molcular hydrogen bonds and π-π stacking inter­actions stabilize the structure.

Key indicators

• Single-crystal X-ray study
• T = 294 K
• Mean [sigma](C-C)= 0.003 Å
• R factor = 0.041
• wR factor = 0.113
• Data-to-parameter ratio = 15.3

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S1. Comment

Recently, compounds containing a 1H-1,2,4-triazole group have attracted much interest because compounds containing this ring system are well known as efficient fungicides in pesticides and they exhibit good plant-growth regulatory activity for a wide variety of crops (Xu et al., 2002). In addition, amine- and thione-substituted triazoles have been studied as anti-inflammatory and antimicrobial agents (Eweiss et al.,1986; Awad et al., 1991). In a search for new triazole compounds with better biological activity, the title compound, (I), was synthesized. We report here the crystal structure of (I).

Bond lengths and angles in the thione-substituted triazole ring and the other triazole ring (Table 1) are in agreement with the values quotes in previous reports (Li et al., 2005; Xu et al., 2005). The molecule exists in the thione tautomeric form, with an S=C distance of 1.662 (2) Å, which indicates substantial double-bond character for this bond (Allen et al., 1987). The planes C10–C12/N5/N6/N7 and C1–C7/N1/Cl1 make angles of 73.57 (3) and 46.65 (2)°, respectively, with the thione-substituted triazole plane C8/C9/N2/N3/N4/S1. The crystal structure of (I) is stabilized by weak intra- and intermolecular hydrogen bonds and π-π stacking interactions. The π-π stacking interactions involve the thione-substituted triazole ring (C8/C9/N2/N3/N4/S1) R1 and the benzene ring (C2–C7) R2. The distance between the centroids of rings R1 and R2 is 3.532 (3) Å (1 − x,1/2 + y,1/2 − z).

S2. Experimental

A mixture of 4-amino-3-(1,2,4-triazol-1-yl)-1H-1,2,4-triazole-5(4H)-thione (0.02 mol) and 4-chlorobenzaldehyde (0.02 mol) was refluxed at 391 K for 15–20 min in glacial acetic acid. Then, the mixture was filtered and crystallized from ethanol to afford the compound (5.87 g, yield 92%). Single crystals suitable for X-ray measurements were obtained by recrystallization from ethanol at room temperature.

S3. Refinement

All H atoms were placed in calculated positions, with C—H = 0.93–0.97 Å, and refined using a riding model, with U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SAINT; data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1999); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. View of the title compound (I), with displacement ellipsoids drawn at the 40% probability level.
	Fig. 2. The packing of the title compound, viewed down the b axis. Hydrogen bonds are shown as dashed lines.

5-((1H-1,2,4-triazol-1-yl)methyl)-4-(4-chlorobenzylideneamino)-2H −1,2,4-triazole-3(4H)-thione

Crystal data

C12H10ClN7S	F(000) = 656
Mr = 319.78	Dx = 1.464 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yb c	Cell parameters from 2083 reflections
a = 11.090 (2) Å	θ = 2.3–25.2°
b = 7.4421 (15) Å	µ = 0.41 mm^−1
c = 17.734 (4) Å	T = 294 K
β = 97.693 (3)°	Block, yellow
V = 1450.6 (5) Å^3	0.22 × 0.20 × 0.18 mm
Z = 4

Data collection

Bruker SMART CCD area detector diffractometer	2972 independent reflections
Radiation source: fine-focus sealed tube	1855 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
ϕ and ω scans	θmax = 26.4°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→13
Tmin = 0.910, Tmax = 0.929	k = −9→8
7928 measured reflections	l = −22→22

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.113	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.050P)^2 + 0.2972P] where P = (Fo^2 + 2Fc^2)/3
2972 reflections	(Δ/σ)max = 0.001
194 parameters	Δρmax = 0.16 e Å^−3
0 restraints	Δρmin = −0.27 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
S1	0.49163 (7)	0.24628 (10)	0.08460 (4)	0.0740 (3)
Cl1	0.92839 (6)	0.28322 (11)	0.52370 (4)	0.0807 (3)
N1	0.43747 (17)	0.3488 (3)	0.26156 (9)	0.0471 (5)
N2	0.35753 (17)	0.3716 (2)	0.19453 (9)	0.0432 (4)
N3	0.17593 (17)	0.4106 (3)	0.12972 (9)	0.0514 (5)
N4	0.2582 (2)	0.3470 (3)	0.08457 (11)	0.0537 (5)
H4A	0.235 (2)	0.345 (3)	0.0380 (14)	0.060 (8)*
N5	0.18102 (16)	0.3565 (2)	0.32196 (9)	0.0435 (4)
N6	0.09677 (18)	0.2247 (3)	0.30803 (10)	0.0573 (5)
N7	0.1991 (2)	0.1986 (3)	0.42552 (11)	0.0656 (6)
C1	0.5480 (2)	0.3908 (3)	0.25843 (13)	0.0504 (6)
H1	0.5702	0.4380	0.2137	0.061*
C2	0.6395 (2)	0.3657 (3)	0.32412 (12)	0.0460 (5)
C3	0.6126 (2)	0.2829 (3)	0.39062 (13)	0.0514 (6)
H3	0.5338	0.2428	0.3933	0.062*
C4	0.7002 (2)	0.2601 (3)	0.45168 (14)	0.0536 (6)
H4	0.6816	0.2043	0.4956	0.064*
C5	0.8169 (2)	0.3209 (3)	0.44742 (13)	0.0534 (6)
C6	0.8461 (2)	0.4038 (3)	0.38286 (14)	0.0587 (6)
H6	0.9248	0.4448	0.3807	0.070*
C7	0.7571 (2)	0.4250 (3)	0.32145 (13)	0.0540 (6)
H7	0.7764	0.4801	0.2775	0.065*
C8	0.3702 (2)	0.3211 (3)	0.12057 (12)	0.0493 (6)
C9	0.2391 (2)	0.4213 (3)	0.19627 (11)	0.0414 (5)
C10	0.1940 (2)	0.4942 (3)	0.26547 (10)	0.0475 (6)
H10A	0.2502	0.5853	0.2880	0.057*
H10B	0.1158	0.5514	0.2508	0.057*
C11	0.2410 (2)	0.3384 (4)	0.39150 (12)	0.0566 (6)
H11	0.3033	0.4133	0.4131	0.068*
C12	0.1116 (3)	0.1355 (4)	0.37213 (14)	0.0676 (7)
H12	0.0649	0.0353	0.3803	0.081*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0968 (6)	0.0698 (5)	0.0658 (4)	0.0040 (4)	0.0490 (4)	−0.0056 (3)
Cl1	0.0675 (5)	0.0857 (6)	0.0834 (5)	−0.0059 (4)	−0.0104 (4)	0.0131 (4)
N1	0.0543 (12)	0.0504 (12)	0.0377 (10)	0.0030 (9)	0.0097 (9)	0.0007 (8)
N2	0.0568 (11)	0.0436 (11)	0.0311 (9)	0.0001 (8)	0.0131 (8)	0.0017 (8)
N3	0.0688 (13)	0.0563 (12)	0.0298 (9)	−0.0025 (10)	0.0099 (9)	0.0015 (8)
N4	0.0803 (16)	0.0561 (13)	0.0268 (10)	−0.0071 (11)	0.0148 (10)	−0.0023 (9)
N5	0.0493 (11)	0.0558 (12)	0.0265 (8)	0.0033 (9)	0.0095 (7)	0.0008 (8)
N6	0.0621 (13)	0.0697 (14)	0.0409 (11)	−0.0108 (11)	0.0104 (9)	0.0039 (10)
N7	0.0759 (15)	0.0864 (16)	0.0354 (10)	0.0034 (12)	0.0110 (10)	0.0150 (11)
C1	0.0617 (16)	0.0403 (13)	0.0521 (13)	−0.0006 (11)	0.0178 (12)	0.0036 (11)
C2	0.0474 (13)	0.0390 (12)	0.0535 (13)	0.0029 (10)	0.0131 (11)	−0.0020 (10)
C3	0.0474 (13)	0.0539 (14)	0.0558 (14)	0.0025 (11)	0.0170 (11)	0.0010 (11)
C4	0.0553 (15)	0.0550 (15)	0.0533 (14)	0.0071 (12)	0.0170 (12)	0.0014 (12)
C5	0.0536 (15)	0.0463 (14)	0.0601 (15)	0.0045 (11)	0.0071 (12)	−0.0045 (12)
C6	0.0490 (15)	0.0518 (15)	0.0772 (18)	−0.0067 (12)	0.0161 (13)	−0.0011 (13)
C7	0.0579 (16)	0.0485 (14)	0.0587 (15)	−0.0027 (12)	0.0190 (12)	0.0026 (12)
C8	0.0759 (17)	0.0412 (13)	0.0352 (11)	−0.0072 (12)	0.0232 (12)	0.0005 (10)
C9	0.0534 (14)	0.0423 (12)	0.0297 (11)	0.0004 (10)	0.0100 (9)	0.0030 (9)
C10	0.0629 (15)	0.0480 (13)	0.0334 (11)	0.0074 (11)	0.0132 (10)	0.0034 (10)
C11	0.0590 (15)	0.0791 (18)	0.0314 (11)	−0.0006 (13)	0.0047 (10)	0.0016 (12)
C12	0.0824 (19)	0.0733 (19)	0.0500 (15)	−0.0109 (15)	0.0190 (14)	0.0105 (14)

Geometric parameters (Å, º)

S1—C8	1.662 (2)	C1—H1	0.9300
Cl1—C5	1.729 (2)	C2—C7	1.384 (3)
N1—C1	1.273 (3)	C2—C3	1.398 (3)
N1—N2	1.395 (2)	C3—C4	1.365 (3)
N2—C9	1.369 (3)	C3—H3	0.9300
N2—C8	1.389 (3)	C4—C5	1.382 (3)
N3—C9	1.292 (2)	C4—H4	0.9300
N3—N4	1.376 (2)	C5—C6	1.377 (3)
N4—C8	1.332 (3)	C6—C7	1.377 (3)
N4—H4A	0.83 (2)	C6—H6	0.9300
N5—C11	1.327 (3)	C7—H7	0.9300
N5—N6	1.354 (3)	C9—C10	1.488 (3)
N5—C10	1.454 (3)	C10—H10A	0.9700
N6—C12	1.308 (3)	C10—H10B	0.9700
N7—C11	1.318 (3)	C11—H11	0.9300
N7—C12	1.347 (3)	C12—H12	0.9300
C1—C2	1.451 (3)
C1—N1—N2	116.02 (18)	C6—C5—Cl1	119.97 (19)
C9—N2—C8	108.23 (18)	C4—C5—Cl1	118.74 (19)
C9—N2—N1	121.05 (16)	C5—C6—C7	119.0 (2)
C8—N2—N1	129.70 (19)	C5—C6—H6	120.5
C9—N3—N4	103.41 (19)	C7—C6—H6	120.5
C8—N4—N3	114.79 (18)	C6—C7—C2	121.0 (2)
C8—N4—H4A	128.6 (17)	C6—C7—H7	119.5
N3—N4—H4A	115.8 (17)	C2—C7—H7	119.5
C11—N5—N6	110.08 (18)	N4—C8—N2	102.00 (19)
C11—N5—C10	128.9 (2)	N4—C8—S1	128.03 (17)
N6—N5—C10	120.96 (17)	N2—C8—S1	130.0 (2)
C12—N6—N5	101.89 (19)	N3—C9—N2	111.55 (17)
C11—N7—C12	102.61 (19)	N3—C9—C10	125.1 (2)
N1—C1—C2	120.5 (2)	N2—C9—C10	123.13 (19)
N1—C1—H1	119.8	N5—C10—C9	112.72 (18)
C2—C1—H1	119.8	N5—C10—H10A	109.0
C7—C2—C3	118.6 (2)	C9—C10—H10A	109.0
C7—C2—C1	119.5 (2)	N5—C10—H10B	109.0
C3—C2—C1	121.9 (2)	C9—C10—H10B	109.0
C4—C3—C2	120.9 (2)	H10A—C10—H10B	107.8
C4—C3—H3	119.5	N7—C11—N5	110.0 (2)
C2—C3—H3	119.5	N7—C11—H11	125.0
C3—C4—C5	119.2 (2)	N5—C11—H11	125.0
C3—C4—H4	120.4	N6—C12—N7	115.4 (2)
C5—C4—H4	120.4	N6—C12—H12	122.3
C6—C5—C4	121.2 (2)	N7—C12—H12	122.3
C1—N1—N2—C9	−146.3 (2)	C9—N2—C8—N4	0.6 (2)
C1—N1—N2—C8	46.7 (3)	N1—N2—C8—N4	168.9 (2)
C9—N3—N4—C8	−1.1 (3)	C9—N2—C8—S1	−179.09 (18)
C11—N5—N6—C12	0.6 (3)	N1—N2—C8—S1	−10.8 (3)
C10—N5—N6—C12	−177.9 (2)	N4—N3—C9—N2	1.4 (2)
N2—N1—C1—C2	−177.58 (18)	N4—N3—C9—C10	176.1 (2)
N1—C1—C2—C7	−175.0 (2)	C8—N2—C9—N3	−1.4 (2)
N1—C1—C2—C3	4.9 (3)	N1—N2—C9—N3	−170.89 (18)
C7—C2—C3—C4	−0.3 (3)	C8—N2—C9—C10	−176.12 (19)
C1—C2—C3—C4	179.8 (2)	N1—N2—C9—C10	14.4 (3)
C2—C3—C4—C5	0.3 (3)	C11—N5—C10—C9	115.1 (2)
C3—C4—C5—C6	0.0 (3)	N6—N5—C10—C9	−66.7 (3)
C3—C4—C5—Cl1	−177.45 (17)	N3—C9—C10—N5	111.2 (2)
C4—C5—C6—C7	−0.4 (4)	N2—C9—C10—N5	−74.8 (3)
Cl1—C5—C6—C7	177.02 (18)	C12—N7—C11—N5	0.1 (3)
C5—C6—C7—C2	0.5 (3)	N6—N5—C11—N7	−0.5 (3)
C3—C2—C7—C6	−0.1 (3)	C10—N5—C11—N7	177.9 (2)
C1—C2—C7—C6	179.8 (2)	N5—N6—C12—N7	−0.6 (3)
N3—N4—C8—N2	0.3 (2)	C11—N7—C12—N6	0.3 (3)
N3—N4—C8—S1	179.98 (16)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···N7^i	0.83 (2)	2.01 (3)	2.830 (3)	169 (2)
C4—H4···S1^ii	0.93	2.82	3.517 (2)	133
C1—H1···S1	0.93	2.74	3.246 (2)	115

Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) x, −y+1/2, z+1/2.