4-Chloro­benzothio­amide

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

doi:10.1107/S1600536809014640

. 2009 Apr 25;65(Pt 5):o1128. doi: 10.1107/S1600536809014640

4-Chlorobenzothioamide

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

PMCID: PMC2977801 PMID: 21583938

Abstract

In the title compound, C₇H₆ClNS, the dihedral angle between the aromatic ring and the thioamide fragment is 28.1 (2)°. The structure features a π-stacking interaction between the aromatic rings with a slight offset of the rings, giving a centroid–centroid separation of 3.7942 (2) Å. There are intermolecular hydrogen-bonding interactions between the amino group and the S atoms.

Related literature

For the uses of thioamides, see: Akhtar et al. (2006 ▶, 2007 ▶, 2008 ▶); Jagodzinski (2003 ▶); Lebana et al. (2008 ▶). For the biological activity of thioamides, see: Wei et al. (2006 ▶). For the synthesis of thioamides, see: Bauer & Kuhlein (1985 ▶); Cava & Levinson (1985 ▶); Manaka & Sato (2005 ▶). For a comparable structure, see: Jian et al. (2006 ▶).

Experimental

Crystal data

C₇H₆ClNS
M _r = 171.64
Monoclinic,
a = 8.1592 (4) Å
b = 9.0934 (5) Å
c = 10.8915 (6) Å
β = 100.113 (10°
V = 795.54 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.66 mm⁻¹
T = 296 K
0.40 × 0.36 × 0.18 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T _min = 0.778, T _max = 0.889
6337 measured reflections
1901 independent reflections
1667 reflections with I > 2σ(I)
R _int = 0.017

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.105
S = 1.06
1901 reflections
91 parameters
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.38 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/S1600536809014640/bt2933sup1.cif

e-65-o1128-sup1.cif^{(13.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809014640/bt2933Isup2.hkl

e-65-o1128-Isup2.hkl^{(93.6KB, 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
N1—H1A⋯S1ⁱ	0.86	2.64	3.3769 (15)	145
N1—H1B⋯S1ⁱⁱ	0.86	2.63	3.4527 (15)	160

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

Acknowledgments

MuHK is thankful to the HEC, Pakistan, for a PhD fellowship under the indigenous PhD Program. JDM thanks Saint Mary’s Univeristy for funding.

supplementary crystallographic information

Comment

Thioamides are important precursors/intermediates in the synthesis of various heterocycles (Jagodzinski et al., 2003). Besides being used as synthetic intermediates, they exhibit numerous biological activities (Wei et al., 2006). In addition, thioamides have found use as important ligands in coordination chemistry (Lebana et al., 2008). Several methods for their synthesis have been published involving the uses of Lawesson's regent (Cava et al., 1985) and phosphorus pentasulphide (Bauer et al., 1985). The title compound, 4-chlorobenzothioamide was synthesized in continuation of our previous work on the synthesis and biological screenings of five membered heterocycles (Akhtar et al., 2006, 2007, 2008). In this article the crystal structure of 4-chlorobenzothioamide is being reported. The title compound was synthesized by treating 4-chlorobenzonitrile with 70% sodium hydrogen sulfide hydrate and magnesium chloride hexahydrate in dimethylformamide (Manaka & Sato, 2005) as an intermediate for the synthesis of thiazoles.

The hydrogen bonding interactions between the nitrogen and sulfur atoms 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).

Experimental

4-Chlorobenzonitrile (14.5 mmol) was added to a slurry of sodium hydrogen sulfide hydrate (70%, 29 mmol) and magnesium chloride hexahydrate (14.5 mmol) in DMF (40 mL) and the mixture stirred at room temperature for 2 h. The resulting green slurry 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 of water. The recrystallization of the residue from chloroform afforded the crystals of the title compound suitable for X-ray analysis.