4-[(2-Bromo­benzyl­idene)amino]-3-(pyridin-4-yl)-1H-1,2,4-triazole-5(4H)-thione

Wei Gao; Xian Li; Xin-Ling Wang; Jing Yang; Xue-Fen Wu

doi:10.1107/S1600536812024439

. 2012 Jun 2;68(Pt 7):o1996. doi: 10.1107/S1600536812024439

4-[(2-Bromobenzylidene)amino]-3-(pyridin-4-yl)-1H-1,2,4-triazole-5(4H)-thione

Wei Gao ^a,^*, Xian Li ^a, Xin-Ling Wang ^a, Jing Yang ^a, Xue-Fen Wu ^a

PMCID: PMC3393270 PMID: 22807827

Abstract

In the title compound, C₁₄H₁₀BrN₅S, the dihedral angle between the triazole ring and the pyridine and bromobenzene rings are 26.42 (13) and 6.28 (13)°, respectively. The molecule exists as a thione in the solid state. In the crystal, molecules are linked by N—H⋯N hydrogen bonds, generating [010] C(8) chains.

Related literature

For related structures, see: Zou et al. (2008 ▶); Kashaev et al. (2010 ▶); Liu & Liu (2011 ▶); Liu, Pan, Weng, Tan et al. (2012 ▶); Liu, Tan, Weng & Liu (2012 ▶); Tan et al. (2012 ▶).

Experimental

Crystal data

C₁₄H₁₀BrN₅S
M _r = 360.24
Monoclinic,
a = 10.406 (3) Å
b = 17.299 (5) Å
c = 15.858 (4) Å
β = 103.719 (5)°
V = 2773.3 (13) Å³
Z = 8
Mo Kα radiation
μ = 3.12 mm⁻¹
T = 113 K
0.20 × 0.18 × 0.12 mm

Data collection

Rigaku Saturn CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 ▶) T _min = 0.575, T _max = 0.706
14119 measured reflections
3293 independent reflections
2565 reflections with I > 2σ(I)
R _int = 0.036

Refinement

R[F ² > 2σ(F ²)] = 0.030
wR(F ²) = 0.087
S = 1.08
3293 reflections
194 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.54 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Data collection: CrystalClear (Rigaku/MSC, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812024439/hb6820sup1.cif

e-68-o1996-sup1.cif^{(17.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812024439/hb6820Isup2.hkl

e-68-o1996-Isup2.hkl^{(161.6KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812024439/hb6820Isup3.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
N3—H3⋯N1ⁱ	0.90 (1)	1.95 (1)	2.821 (3)	163 (3)

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Symmetry code: (i) Inline graphic .

Acknowledgments

We gratefully acknowledge financial support by the Doctoral Research Fund of Henan University of Traditional Chinese Medicine.

supplementary crystallographic information

Comment

Single-crystal X-ray diffraction analysis reveals that the title compound crystallizes in the monoclinic space group C2/c. As shown in Fig. 1, the dihedral angle between the pyridyl and triazole rings is 153.6 °. As shown in Fig. 2, the crystal structure is stabilized by intermolecular hydrogen bonds N—H···N.

Experimental

In round bottom flask, 4-pyridine carboxylic acid (0.01 mol) and hydrazine hydrate 99% (0.01 mol) were taken along with alcohol and the mixture was refluxed for 4 h. Then from the reaction mixture alcohol was removed under reduced pressure. Solid residue was obtained, recrystallized from ethanol. In a 250 ml round bottom flask, 4-pyridine hydrazide (0.075 mol) was taken. To this a solution of potassium hydroxide (0.075 mol) in 100 ml of absolute alcohol and carbon disulfide were added agitated for overnight. The reaction mixture was diluted with 200 ml of dry ether. The solid obtained was 15.05 g (80%). It was filtered and washed with dry ether. A mixture of potassium-pyridine-dithiocarbazate (0.1 mol) and hydrazine hydrate 5 ml (0.1 mol) was refluxed for 2 h with occasional shaking and the solution was poured into the cold water. The mixture was acidified with hydrochloric acid. The precipitate obtained was filtered, dried and recrystallized by using alcohol. A mixture of 5-pyridine-4-amino-3-mercapto-4(H)-1,2,4-triazole (0.01 mol) taken with 2-bromobenzaldehyde (0.01 mol) and concentrated sulfuric acid (0.5 ml) in ethanol 100 ml. The mixture was refluxed on water bath for several hours with TLC monitoring. The solid was obtained on cooling the mixture and poured in cold water was afforded the the title compound. Colourless prisms were grown from ethanol solution.