4-Chloro-N-phenyl­benzene­sulfonamide

K Shakuntala; Sabine Foro; B Thimme Gowda

doi:10.1107/S1600536811015108

. 2011 Apr 29;67(Pt 5):o1252. doi: 10.1107/S1600536811015108

4-Chloro-N-phenylbenzenesulfonamide

K Shakuntala ^a, Sabine Foro ^b, B Thimme Gowda ^a,^*

PMCID: PMC3089100 PMID: 21754543

Abstract

In the crystal of the title compound, C₁₂H₁₀ClNO₂S, the asymmetric unit contains two independent molecules. The N—C bonds in the C—SO₂—NH—C segments have gauche torsions with respect to the S=O bonds. The molecules are twisted at the S atoms with C—SO₂—NH—C torsion angles of −53.8 (3) and −63.4 (3)° in the two molecules. The benzene rings are tilted relative to each other by 69.1 (1) and 82.6 (1)°. The dihedral angle between the sulfonyl benzene rings of the two independent molecules is 23.7 (2)°. The crystal structure features inversion-related dimers linked by N—H⋯O hydrogen bonds.

Related literature

For hydrogen-bonding preferences of sulfonamides, see: Adsmond & Grant (2001 ▶). For our study of the effect of substituents on the structures of N-(aryl)-amides, see: Gowda et al. (2004 ▶); on the structures of N-(aryl)arylsulfonamides, see: Shakuntala et al. (2011a ▶,b ▶); and on the oxidative strengths of N-chloro,N-arylsulfonamides, see: Gowda & Kumar (2003 ▶).

Experimental

Crystal data

C₁₂H₁₀ClNO₂S
M _r = 267.72
Triclinic,
a = 10.206 (1) Å
b = 10.900 (1) Å
c = 13.461 (2) Å
α = 68.19 (1)°
β = 87.64 (2)°
γ = 67.08 (1)°
V = 1271.1 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.45 mm⁻¹
T = 293 K
0.40 × 0.36 × 0.30 mm

Data collection

Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009 ▶) T _min = 0.840, T _max = 0.876
8487 measured reflections
4831 independent reflections
2470 reflections with I > 2σ(I)
R _int = 0.018

Refinement

R[F ² > 2σ(F ²)] = 0.047
wR(F ²) = 0.133
S = 0.93
4831 reflections
313 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2009 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811015108/nc2229sup1.cif

e-67-o1252-sup1.cif^{(22.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811015108/nc2229Isup2.hkl

e-67-o1252-Isup2.hkl^{(236.6KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811015108/nc2229Isup3.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
N1—H1N⋯O1ⁱ	0.84 (2)	2.17 (2)	3.010 (3)	175 (3)
N2—H2N⋯O3ⁱⁱ	0.89 (2)	1.99 (2)	2.867 (4)	167 (3)

Open in a new tab

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

Acknowledgments

KS thanks the University Grants Commission, Government of India, New Delhi, for the award of a research fellowship under its faculty improvement program.

supplementary crystallographic information

Comment

The sulfonamide moieties are the constituents of many biologically important compounds. The hydrogen bonding preferences of sulfonamides has been investigated (Adsmond & Grant, 2001). As a part of studying the substituent effects on the structures and other aspects of this class of compounds (Gowda, & Kumar, 2003; Gowda et al., 2004; Shakuntala et al., 2011a,b), in the present work, the crystal structure of 4-chloro-N-(phenyl)-benzenesulfonamide (I) has been determined (Fig.1). The asymmetric unit of the structure contains two independent molecules. The N—C bonds in the C—SO₂—NH—C segments have gauche torsions with respect to the S═O bonds. The molecules are twisted at the S atom with the C—SO₂—NH—C torsion angles of -53.8 (3)° (molecule 1) and -63.4 (3)° (molecule 2), compared to the values of 57.6 (3)° in 4-chloro-N-(2-chlorophenyl)-benzenesulfonamide (II) (Shakuntala et al., 2011a) and -58.4 (3)° in 4-chloro-N-(3-chlorophenyl)-benzenesulfonamide (III) (Shakuntala et al., 2011b).

The sulfonyl and the anilino benzene rings in the two independent molecules of (I) are tilted relative to each other by 69.1 (1)° in molecule 1, and 82.6 (1)° in molecule 2, compared to the values of 84.7 (1)° in (II) and 77.1 (1)° in (III).

In the crystal structure of the title compound the molecules are linked by N—H···O(S) hydrogen bonding into dimers that are located on centers of inversion (Table 1 and Fig.2).

Experimental

The solution of chlorobenzene (10 ml) in chloroform (40 ml) was treated dropwise with chlorosulfonic acid (25 ml) at 0 ° C. After the initial evolution of hydrogen chloride subsided, the reaction mixture was brought to room temperature and poured into crushed ice in a beaker. The chloroform layer was separated, washed with cold water and allowed to evaporate slowly. The residual 4-chlorobenzenesulfonylchloride was treated with aniline in the stoichiometric ratio and boiled for ten minutes. The reaction mixture was then cooled to room temperature and added to ice cold water (100 ml). The resultant 4-chloro-N-(phenyl)-benzenesulfonamide was filtered under suction and washed thoroughly with cold water. It was then recrystallized to constant melting point from dilute ethanol. The compound was characterized by recording its infrared and NMR spectra.

Prism like colorless single crystals used in X-ray diffraction studies were grown in ethanolic solution by slow evaporation at room temperature.