4-(5-Bromo-2-hydroxy­benzyl­idene­amino)-3-methyl-1H-1,2,4-triazole-5(4H)-thione

Min Wang; Minna Cao; Bo Hu; CuiXia Cheng; XueGang Song

doi:10.1107/S1600536807062149

. 2008 Jan 4;64(Pt 2):o374. doi: 10.1107/S1600536807062149

4-(5-Bromo-2-hydroxybenzylideneamino)-3-methyl-1H-1,2,4-triazole-5(4H)-thione

Min Wang ^a, Minna Cao ^a, Bo Hu ^a, CuiXia Cheng ^a, XueGang Song ^a,^*

PMCID: PMC2960248 PMID: 21201405

Abstract

In the title compound, C₁₀H₉BrN₄OS, the triazole ring forms a dihedral angle of 72.05 (14)° with the benzene ring. The conformation of the molecule is stabilized by intramolecular O—H⋯·N hydrogen bonding. The crystal packing is determined by intermolecular N—H⋯S interactions, a short Br⋯S contact of 3.4464 (13) Å and π–π stacking of the triazole rings and of the benzene rings (centroid–centroid distances of 3.4109 and 3.569 Å, respectively).

Related literature

For related literature, see: Allen et al. (1987 ▶); Awad et al. (1991 ▶); Eweiss et al. (1986 ▶); Ji et al. (2002 ▶); Mohan (1983 ▶); Xu et al. (2002 ▶).

Experimental

Crystal data

C₁₀H₉BrN₄OS
M _r = 313.18
Triclinic,
a = 6.9780 (8) Å
b = 7.1529 (8) Å
c = 12.3119 (14) Å
α = 83.561 (2)°
β = 88.820 (2)°
γ = 79.987 (2)°
V = 601.35 (12) Å³
Z = 2
Mo Kα radiation
μ = 3.58 mm⁻¹
T = 293 (2) K
0.30 × 0.28 × 0.26 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (Blessing; 1995 ▶) T _min = 0.404, T _max = 0.519 (expected range = 0.307–0.394)
4340 measured reflections
2560 independent reflections
1977 reflections with I > 2σ(I)
R _int = 0.038

Refinement

R[F ² > 2σ(F ²)] = 0.040
wR(F ²) = 0.111
S = 1.10
2560 reflections
161 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.59 e Å⁻³

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); 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, 2001 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807062149/gk2112sup1.cif

e-64-0o374-sup1.cif^{(16.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807062149/gk2112Isup2.hkl

e-64-0o374-Isup2.hkl^{(123.2KB, hkl)}

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—H2⋯S1ⁱ	0.862 (19)	2.44 (2)	3.295 (3)	173 (5)
O1—H1⋯N4	0.821 (19)	1.97 (4)	2.676 (4)	144 (5)
O1—H1⋯N1ⁱⁱ	0.821 (19)	2.69 (5)	3.178 (5)	120 (5)

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

Acknowledgments

We thank Xianggao Meng for assistance with refinement of the crystal structure.

supplementary crystallographic information

Comment

Recently, compounds containing 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-inflamatory 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 and we report here its crystal structure.

The molecule of (I) exists in the thione tautomeric form, with the S==C distance of 1.681 (4) Å, which indicates a substantial double-bond character (Allen et al., 1987). The dihedral angle between the thione-substituted triazole ring and the benzene ring is 72.05 (14)°. The crystal packing is determined by intermolecular N–H···S interaction (Table 1), short Br···S contact of 3.4464 (13) Å and π-π stacking of the triazole rings (centroid-to-centrod distance of 3.410 Å) and π-π stacking of the benzene rings (centroid-to-centrod distance of 3.569 Å).

Experimental

4-Amino-5-methyl-1,2,4-triazole-3-thione (0.02 mol in 15 ml e thanol), synthesized according to a reported method (Mohan, 1983), was added to a solution of 5-bromosalicylaldehyde (0.02 mol in 20 ml). Then several drops of concentrated sulfuric acid were added to the solution, which was then refluxed for 1 h. The mixture was filtered and crystallized from ethanol to afford the title compound (I). Yellow plates of (I) were obtained by recrystallization from ethanol at room temperature.