4-[(5-Bromo-2-hy­droxy­benzyl­idene)amino]-3-propyl-1H-1,2,4-triazole-5(4H)-thione

Xin Wu; Cai-Xia Yuan; Ling Ma; Kai-Lu Zhai; Miao-Li Zhu

doi:10.1107/S1600536812019745

. 2012 May 12;68(Pt 6):o1674. doi: 10.1107/S1600536812019745

4-[(5-Bromo-2-hydroxybenzylidene)amino]-3-propyl-1H-1,2,4-triazole-5(4H)-thione

Xin Wu ^a, Cai-Xia Yuan ^b,^*, Ling Ma ^c, Kai-Lu Zhai ^d, Miao-Li Zhu ^b

PMCID: PMC3379270 PMID: 22719468

Abstract

The asymmetric unit of the title compound, C₁₂H₁₃BrN₄OS, contains two independent molecules in which the dihedral angles between the triazole and benzene rings are 2.9 (3) and 7.5 (3)°. The thione group is of the form R ₂C=S. An intramolecular O—H⋯N hydrogen bond occurs in each molecule. The crystal structure features weak N—H⋯S interactions and π–π stacking of the benzene rings [centroid–centroid distance = 3.667 (3) Å].

Related literature

For the pharmacological activity of 1,2,4-triazole-substituted and Schiff base compounds, see: Isloor et al. (2009 ▶); Ma et al. (2011 ▶). For copper complexes containing 1,2,4-triazole Schiff base ligands, see: Wen et al. (2004 ▶).

Experimental

Crystal data

C₁₂H₁₃BrN₄OS
M _r = 341.23
Triclinic,
a = 8.042 (5) Å
b = 13.187 (8) Å
c = 13.408 (8) Å
α = 97.406 (9)°
β = 92.956 (10)°
γ = 95.916 (9)°
V = 1399.5 (15) Å³
Z = 4
Mo Kα radiation
μ = 3.08 mm⁻¹
T = 298 K
0.30 × 0.25 × 0.20 mm

Data collection

Bruker SMART 1K CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2000 ▶) T _min = 0.458, T _max = 0.578
14278 measured reflections
4939 independent reflections
3061 reflections with I > 2σ(I)
R _int = 0.055

Refinement

R[F ² > 2σ(F ²)] = 0.043
wR(F ²) = 0.102
S = 0.93
4939 reflections
347 parameters
H-atom parameters constrained
Δρ_max = 0.49 e Å⁻³
Δρ_min = −0.55 e Å⁻³

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812019745/jj2128sup1.cif

e-68-o1674-sup1.cif^{(31.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812019745/jj2128Isup2.hkl

e-68-o1674-Isup2.hkl^{(241.9KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812019745/jj2128Isup3.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
O1—H1⋯N4	0.82	1.93	2.644 (4)	145
O2—H2⋯N8	0.82	1.90	2.612 (4)	144
N1—H1A⋯S1ⁱ	0.86	2.46	3.300 (4)	164
N5—H5⋯S2ⁱⁱ	0.86	2.41	3.252 (4)	165

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

Acknowledgments

The authors acknowledge financial support from the National Natural Science Foundation of China for Youth (grant No. 21001070), the Specialized Research Fund for the Doctoral Program of Higher Education (grant No. 20111401110002) and the Natural Science Foundation of Shanxi Province of China (grant No. 2011021006–2).

supplementary crystallographic information

Comment

1,2,4-triazole and its derivatives possess a variety of pharmacological properties (Isloor et al., 2009). Schiff bases derived from substituted salicylaldehydes form numerous metal complexes (Wen et al., 2004). Also, copper complexes containing 1,2,4-triazole Schiff base ligands are potential inhibitors of PTP1B (protein tyrosine phosphatase 1B), TCPTP (T-cell protein tyrosine phosphatase), PTP-MEG2 (megakaryocyte protein tyrosine phosphatase) and SHP-1 (Src homology phosphatase 1) (Ma et al., 2011). In continuation of our work in this area, we report here the synthesis and crystal structure of the title compound, C₁₂H₁₃BrN₄OS, (I).

The title compound, (I), crystallizes with two independent molecules in the asymmetric unit (Fig. 1). The dihedral angles between the triazole and phenyl rings are 2.9 (3)° and 7.5 (3)°, respectively. The thione group is of the form R₂C=S with a Cdb\S distance of 1.673 (4)Å and 1.675 (4)Å indicating significant double bond character. Intramolecular O—H···N hydrogen bonds, weak N—H···S intermolecular interactions (Table 1) and π–π stacking of the benzene rings [centroid–centroid distance = 3.667 (3) Å] are observed that may influence crystal packing.

Experimental

0.5 mmol 5-Bromosalicylaldehyde in 10 ml of ethanol was added to a solution of 4-amino-5-propyl-1,2,4-triazole-3-thione (0.5 mmol) in 20 ml of ethanol, and then refluxed for 2 h. The resulting solution was filterd and recrystallized from ethanol. X-ray quality Yellow crystals of the title compound were formed upon slow evaporation of the resulting soluton.