4-Bromo­benzoic acid–6-(4-bromo­phen­yl)-3-methyl-1,2,4-triazolo[3,4-b][1,3,4]thia­diazole (1/1)

Kamini Kapoor; Vivek K Gupta; Satya Paul; Seema Sahi; Rajni Kant

doi:10.1107/S1600536812012184

. 2012 Mar 24;68(Pt 4):o1185–o1186. doi: 10.1107/S1600536812012184

4-Bromobenzoic acid–6-(4-bromophenyl)-3-methyl-1,2,4-triazolo[3,4-b][1,3,4]thiadiazole (1/1)

Kamini Kapoor ^a, Vivek K Gupta ^a, Satya Paul ^b, Seema Sahi ^b, Rajni Kant ^a,^*

PMCID: PMC3344123 PMID: 22606126

Abstract

In the title 1:1 co-crystal, C₁₀H₇BrN₄S·C₇H₅BrO₂, the triazolothiadiazole system is approximately planar [with a maximum deviation of 0.030 (4) Å] and forms a dihedral angle of 8.6 (1)° with the bromophenyl ring. In the carboxylic acid molecule, the carboxyl group is rotated by 6.4 (3)° out of the benzene ring plane. The crystal structure features O—H⋯N and C—H⋯O hydrogen bonds, π–π stacking interactions [centroid–centroid distances = 3.713 (2), 3.670 (2) and 3.859 (3) Å] and short S⋯N [2.883 (4) Å] contacts.

Related literature

For the biological activity of triazole derivatives, thiadiazoles and triazolothiadiazole compounds, see: Chaturvedi et al. (1988 ▶); Holla et al. (2003 ▶); Bhat et al. (2004 ▶); Bekircan & Bektas (2006 ▶); Shawali & Sayed (2006 ▶); Mathew et al. (2007 ▶); Karthikeyan et al. (2007 ▶); Zhou et al. (2007 ▶). For related structures, see: Dinçer et al. (2005 ▶); Arshad et al. (2009 ▶); Jia et al. (2011 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₁₀H₇BrN₄S·C₇H₅BrO₂
M _r = 496.19
Triclinic,
a = 7.7592 (3) Å
b = 8.0634 (4) Å
c = 14.9076 (7) Å
α = 94.090 (4)°
β = 92.961 (3)°
γ = 99.326 (4)°
V = 916.13 (7) Å³
Z = 2
Mo Kα radiation
μ = 4.56 mm⁻¹
T = 293 K
0.3 × 0.2 × 0.2 mm

Data collection

Oxford Diffraction Xcalibur Sapphire3 diffractometer
Absorption correction: multi-scan (CrysAlis PRO RED; Oxford Diffraction, 2010 ▶) T _min = 0.581, T _max = 1.000
8264 measured reflections
3594 independent reflections
2254 reflections with I > 2σ(I)
R _int = 0.036

Refinement

R[F ² > 2σ(F ²)] = 0.048
wR(F ²) = 0.116
S = 1.01
3594 reflections
236 parameters
H-atom parameters constrained
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.51 e Å⁻³

Data collection: CrysAlis PRO CCD (Oxford Diffraction, 2010 ▶); cell refinement: CrysAlis PRO CCD; data reduction: CrysAlis PRO RED (Oxford Diffraction, 2010 ▶); 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: PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812012184/bh2421sup1.cif

e-68-o1185-sup1.cif^{(23.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812012184/bh2421Isup2.hkl

e-68-o1185-Isup2.hkl^{(172.6KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812012184/bh2421Isup3.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
O24—H24⋯N2ⁱ	0.82	1.87	2.674 (4)	169
C9—H9A⋯O23ⁱ	0.96	2.48	3.393 (6)	159

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Symmetry code: (i) Inline graphic .

Acknowledgments

RK acknowledges the Department of Science & Technology for the single-crystal X-ray diffractometer sanctioned as a National Facility under project No. SR/S2/CMP-47/2003. He is also thankful to the University of Jammu, Jammu, India, for financial support.

supplementary crystallographic information

Comment

Derivatives of 1,2,4-triazole possess a wide spectrum of biological activity, such as anticancer, anticonvulsant, analgesic, antibacterial, anthelmintic, antitubercular and anti-inflammatory activities (Holla et al., 2003; Bekircan & Bektas, 2006; Zhou et al., 2007). Similarly 1,3,4-thiadiazoles were also found to possess antitumor, anti-inflammatory, antibacterial, antifungal, anticonvulsant and antitubercular properties (Bhat et al., 2004; Mathew et al., 2007). Thus triazolothiadiazole systems may be viewed as cyclic analogues of two very important components, which often display diverse pharmacological properties. Triazolothiadiazoles obtained by fusing the 1,2,4-trizole and 1,3,4-thiadiazole rings together have been reported to possess similar biological properties (Chaturvedi et al., 1988; Shawali & Sayed, 2006; Karthikeyan et al., 2007). Here we report the crystal structure of the 1:1 cocrystal of a triazolothiadiazole derivative and 4-bromobenzoic acid.

Bond lengths (Allen et al., 1987) and angles in the title compound (Fig. 1) have normal values and also correspond to those observed in related structures (Dinçer et al., 2005; Arshad et al., 2009; Jia et al., 2011). The triazolothiadiazole ring is planar with a maximum deviation of 0.030 (4) Å for atom C6. The plane through the benzene ring forms dihedral angle of 8.6 (1)° with the triazolothiadiazole unit. In the molecular structure, an intramolecular C15—H15···S7 contact leads to the formation of a five-membered ring which is fused with the phenyl ring (Fig. 1).

In the crystal structure of the title compound, intermolecular O—H···N and C—H···O hydrogen bonds (Table 2) link the triazolothiadiazole molecule with 4-bromobenzoic acid (Fig. 2). In addition to these interactions, the crystal structure contains three π–π stacking interactions. The first of these is between the thiadiazole ring and its symmetry-related partner at (-x, 1-y, -z), with a distance of 3.713 (2) Å between the ring centroids, and a perpendicular distance between the rings of 3.468 Å. The second is between the triazole ring and the benzene ring at (-x, 1-y, -z), with a distance of 3.670 (2) Å between the ring centroids and a perpendicular distance between the rings of 3.427 Å. The third is between the benzene rings (C10···C15) and (C16···C21) in the asymmetric unit, with a distance of 3.859 (3) Å between the ring centroids and a perpendicular distance between the rings of 3.599 Å. A short contact distance not listed in tables, yet noteworthy, is S7···N1 with N1 at position (-x-1, -y+1, -z+2), the S···N separation being 2.883 (4) Å, which may cause steric hindrance.

Experimental

4-Amino-5-mercapto-3-methyl-1,2,4-triazole (0.130 g, 1 mmol) and 4-bromo-β-chlorocinnamic acid (0.261 g, 1 mmol) were stirred in POCl₃ (3 ml) at 80 °C for 30 min. 6-(4-Bromophenyl)-3-methyl-1,2,4-triazolo[3,4-b][1,3,4]thiadiazole was obtained along with 4-bromobenzoic acid after pouring the reaction mixture in crushed ice followed by washing with dilute NaOH. Finally, it was crystallized from methanol, affording white crystals.