3-(2-Chloro­phen­yl)-4-(4-nitro­phen­yl)-1H-1,2,4-triazole-5(4H)-thione

Abbas Nikoo; Karim Akbari Dilmaghani; Ali Hassanzadeh; Behrouz Notash

doi:10.1107/S1600536811020459

. 2011 Jun 11;67(Pt 7):o1612. doi: 10.1107/S1600536811020459

3-(2-Chlorophenyl)-4-(4-nitrophenyl)-1H-1,2,4-triazole-5(4H)-thione

Abbas Nikoo ^a, Karim Akbari Dilmaghani ^a,^*, Ali Hassanzadeh ^a, Behrouz Notash ^b

PMCID: PMC3152097 PMID: 21837020

Abstract

In the crystal structure of the title triazole compound, C₁₄H₉ClN₄O₂S, molecules are connected into centrosymmetric dimers by pairs of N—H⋯S hydrogen bonds. In addition, there are weak C—H⋯N hydrogen bonds stabilizing the crystal structure. The dihedral angles between the triazole ring and the two benzene rings are 73.0 (4) and 72.9 (4)°.

Related literature

For related structures, see: Genç et al. (2004 ▶); Kumaran et al. (1999 ▶). For the synthesis of triazoles, see: Zamani et al. (2003 ▶).

Experimental

Crystal data

C₁₄H₉ClN₄O₂S
M _r = 332.77
Monoclinic,
a = 6.7262 (13) Å
b = 17.109 (3) Å
c = 13.101 (3) Å
β = 95.89 (3)°
V = 1499.7 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.41 mm⁻¹
T = 298 K
0.35 × 0.3 × 0.3 mm

Data collection

Stoe IPDS 2T diffractometer
16462 measured reflections
4038 independent reflections
2850 reflections with I > 2σ(I)
R _int = 0.060

Refinement

R[F ² > 2σ(F ²)] = 0.072
wR(F ²) = 0.174
S = 1.18
4038 reflections
203 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2005 ▶); cell refinement: X-AREA; data reduction: X-AREA; 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, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811020459/bt5548sup1.cif

e-67-o1612-sup1.cif^{(17.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811020459/bt5548Isup2.hkl

e-67-o1612-Isup2.hkl^{(197.9KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811020459/bt5548Isup3.cml

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1⋯S1ⁱ	0.86 (3)	2.48 (3)	3.328 (3)	172 (3)
C2—H2⋯N1ⁱⁱ	0.93	2.54	3.454 (5)	170

Open in a new tab

Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

The authors are grateful to Urmia University for financial support.

supplementary crystallographic information

Comment

In the medicinal chemistry, 1,2,4-triazoles are widely used. Cyclization of 1,4-disubstituted thiosemicarbazides produced 4,5-disubstituted 1,2,4-triazoles (Zamani et al., 2003). 4-nitro phenylisothiocyanate reacted with 2-chlorophenylcarboxylic acid hydrazide to yield the corresponding 1-(2-chlorobenzoyl)-4-(4-nitrophenyl)thiosemicarbazide (1), whereas cyclization of (1) with NaHCO₃ 10% solution gave the 3-(2-Chlorophenyl)-4-(4-nitrophenyl)-1H-1,2,4-triazole-5(4H)-thione (2) (Fig. 1).The structures of the compounds were assigned on the basis of IR, ¹H-NMR and ¹³C-NMR spectra.

The molecular structure of the title compound is shown in Fig. 2. In the crystal structure of the title compound, there are intermolecular N—H···S and weak C—H···N hydrogen bonding which play important role in the stabilization of the crystal structure (Table 1 and Fig. 3).

Experimental

Starting materials were obtained from Merck. For the synthesis of 1-(2-chlorobenzoyl)-4-(4-nitrophenyl)thiosemicarbazide (1), a mixture of 2-chlorophenylcarboxylic acid hydrazide (0.01 mol, 1.7 g) and 4-nitrophenyl isothiocynate (0.01 mol, 1.8 g) in absolute ethanol was refluxed for 6 h. The solid material obtained on cooling was filtered, washed with diethyl ether, dried and crystallized from ethanol (yield 82%; m.p. 170–172°C). IR (KBr, cm^-1): 3315, 3184 (N—H), 1643 (C═O), 1457, 1330 (NO₂), 1273 (C═S); ¹H NMR (300 MHz, DMSO-d₆): 7.42–7.53 (3H, m, 2-chlorophenyl), 7.74 (1H, s, 2-chlorophenyl), 7.90 (2H, d, J = 8.7, Ar—H), 8.21 (2H, d, J = 8.7, Ar—H), 9.99 (1H, br, –NH—Ar), 10.30 (1H, s, –CS—NH–), 10.56 (1H, br, –CO—NH–); ¹³C NMR (75 MHz, DMSO-d₆): 121.59, 124.66, 125.11, 127.43, 130.39, 131.22, 132.19, 146.25, 165.93 and 181.58. For the synthesis of (2), a stirred mixture of (1) (1 mmol, 0.35 g) and NaHCO₃ 10% (10 ml) was refluxed for 6 h. After cooling, the solution was acidified with hydrochloric acid and the precipitate was filtered. The precipitate was then crystallized from ethanol (yield 57%; m.p. 223–225°C). IR (KBr, cm^-1): 3286 (N—H), 1608 (C═N), 1465, 1336 (NO₂), 1529, 1177, 1071, 963 (N—═S, amide I, II, III and IV bands); ¹H NMR (300 MHz, CDCl₃): 7.37–7.53 (6H, m, Ar—H), 7.91 (1H, s, 2-chlorophenyl), 8.23 (2H, d, J = 8.7, Ar—H), 12.24 (1H, s, SH); ¹³C NMR (75 MHz, CDCl₃): 124.43, 127.26, 127.48, 128.74, 130.30, 130.50, 131.58, 132.23, 133, 133.07.