4-Bromo­thio­benzamide

Mahmood-ul-Hassan Khan; Shahid Hameed; Tashfeen Akhtar; Jason D Masuda

doi:10.1107/S1600536809018273

. 2009 May 20;65(Pt 6):o1333. doi: 10.1107/S1600536809018273

4-Bromothiobenzamide

Mahmood-ul-Hassan Khan ^a, Shahid Hameed ^a,^*, Tashfeen Akhtar ^a, Jason D Masuda ^b

PMCID: PMC2969588 PMID: 21583187

Abstract

The title compound, C₇H₆BrNS, crystallizes with two molecules in the asymmetric unit. The dihedral angles between the aromatic ring and the thioamide fragment are 23.6 (4) and 20.5 (3)° in the two molecules. In the crystal, there are intermolecular N—H⋯S hydrogen-bonding interactions between the amine group and the S atoms.

Related literature

For the uses of thioamides, see: Akhtar et al. (2006 ▶, 2007 ▶, 2008 ▶); Jagodzinski et al. (2003 ▶). For the biological activity of thioamides, see: Wei et al. (2006 ▶); Klimesova et al. (1999 ▶). For the synthesis of thioamides, see: Kaboudin et al. (2006 ▶); Cava et al. (1985 ▶). For related crystal structures, see: Khan et al. (2009 ▶); Jian et al. (2006 ▶); Manaka & Sato (2005 ▶).

Experimental

Crystal data

C₇H₆BrNS
M _r = 216.10
Monoclinic,
a = 19.6325 (11) Å
b = 10.6101 (6) Å
c = 7.8859 (5) Å
β = 100.078 (1)°
V = 1617.31 (16) Å³
Z = 8
Mo Kα radiation
μ = 5.26 mm⁻¹
T = 296 K
0.21 × 0.17 × 0.09 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T _min = 0.384, T _max = 0.620
12968 measured reflections
3911 independent reflections
2706 reflections with I > 2σ(I)
R _int = 0.025

Refinement

R[F ² > 2σ(F ²)] = 0.035
wR(F ²) = 0.087
S = 1.03
3911 reflections
181 parameters
H-atom parameters constrained
Δρ_max = 0.82 e Å⁻³
Δρ_min = −0.78 e Å⁻³

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); 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 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809018273/bt2956sup1.cif

e-65-o1333-sup1.cif^{(16KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809018273/bt2956Isup2.hkl

e-65-o1333-Isup2.hkl^{(191.7KB, 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—H2A⋯S2ⁱ	0.86	2.73	3.583 (2)	172
N2—H2B⋯S1ⁱⁱ	0.86	2.65	3.500 (2)	173
N1—H1A⋯S1ⁱⁱⁱ	0.86	2.78	3.605 (3)	160
N1—H1B⋯S2ⁱⁱ	0.86	2.71	3.523 (2)	158

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

Acknowledgments

The authours thank the HEC, Pakistan, for a Ph.D. fellowship awarded to MuHK under the indiginous Ph.D. Program. JDM thanks Saint Mary’s University for funding.

supplementary crystallographic information

Comment

Thioamides are biologically active compounds, possessing a wide spectrum of activities (Klimesova et al., 1999; Wei et al., 2006). They have enormous practical and synthetic applicability and their importance and impact as synthetic intermediates is continuously growing (Jagodzinski et al., 2003). Thioamides are generally synthesized using Lawesson's reagent (Cava et al., 1985) or phosphorus penta sulfide (Kaboudin et al., 2006). In this article, we wish to report the crystal structure of 4-bromobenzothioamide, which was synthesized by treating 4-bromobenzonitrile with 70% sodium hydrogen sulfide hydrate and magnesium chloride hexahydrate (Manaka & Sato, 2005) in continuation of our previous work on the synthesis and biological screenings of five membered heterocycles (Akhtar et al., 2006, 2007, 2008).

The hydrogen bonding interactions between the nitrogen and sulfur atoms (3.500 (2)Å to 3.605 (3) Å) are in the range of those seen in p-trifluoromethylbenzothioamide where the corresponding interactions are between 3.3735Å and 3.5133Å (Jian et al., 2006) and in the analogus chloride compound where the N···S distances are 3.3769 (15)Å and 3.4527 (15)Å (Khan et al., 2009).

Experimental

The slurry of 70% sodium hydrogen sulfide hydrate (21.98 mmol) and magnesium chloride hexahydrate (10.99 mmol) was prepared in DMF (40 mL). 4-Bromobenzonitrile (11.0 mmol) was added to the slurry and the mixture stirred at room temperature for 2 h. The resulting mixture was poured into water (100 mL) and the precipitated solid collected by filtration. The product obtained was resuspended in 1 N HCl (50 ml), stirred for another 30 min, filtered and washed with excess water. The recrystallization of the product from chloroform afforded the crystals of 4-bromobenzothioamide suitable for X-ray analysis.