4-Chloro-2-methyl-N-phenyl­benzene­sulfonamide

B Thimme Gowda; Sabine Foro; P G Nirmala; K S Babitha; Hartmut Fuess

doi:10.1107/S1600536809003845

. 2009 Feb 6;65(Pt 3):o476. doi: 10.1107/S1600536809003845

4-Chloro-2-methyl-N-phenylbenzenesulfonamide

B Thimme Gowda ^a,^*, Sabine Foro ^b, P G Nirmala ^a, K S Babitha ^a, Hartmut Fuess ^b

PMCID: PMC2968641 PMID: 21582145

Abstract

There are two molecules in the asymmetric unit of the title compound, C₁₃H₁₂ClNO₂S, with similar conformations. The orientations of the ortho-methyl groups in the sulfonyl benzene rings are in the direction of the N—H bonds of the sulfonamide groups. In the crystal, the molecules are each linked into centrosymmetric dimers through N—H⋯O hydrogen bonds and packed into a layered structure diagonally in the bc plane.

Related literature

For related structures, see: Gelbrich et al. (2007 ▶); Gowda et al. (2008a ▶,b ▶, 2009 ▶); Perlovich et al. (2006 ▶)

Experimental

Crystal data

C₁₃H₁₂ClNO₂S
M _r = 281.75
Triclinic,
a = 8.609 (1) Å
b = 11.143 (1) Å
c = 14.726 (2) Å
α = 98.618 (7)°
β = 90.951 (8)°
γ = 105.79 (1)°
V = 1341.6 (3) Å³
Z = 4
Cu Kα radiation
μ = 3.93 mm⁻¹
T = 299 (2) K
0.33 × 0.23 × 0.08 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ▶) T _min = 0.350, T _max = 0.729
7620 measured reflections
4784 independent reflections
2980 reflections with I > 2σ(I)
R _int = 0.045
3 standard reflections frequency: 120 min intensity decay: 1.0%

Refinement

R[F ² > 2σ(F ²)] = 0.057
wR(F ²) = 0.176
S = 1.03
4784 reflections
333 parameters
12 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Data collection: CAD-4-PC (Enraf–Nonius, 1996 ▶); cell refinement: CAD-4-PC; data reduction: REDU4 (Stoe & Cie, 1987 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2003 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809003845/fj2192sup1.cif

e-65-0o476-sup1.cif^{(23.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809003845/fj2192Isup2.hkl

e-65-0o476-Isup2.hkl^{(234.3KB, 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—H1N⋯O2ⁱ	0.91 (5)	2.02 (5)	2.922 (4)	175 (4)
N2—H2N⋯O3ⁱⁱ	0.88 (4)	2.03 (5)	2.906 (4)	173 (4)

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

Acknowledgments

BTG thanks the Alexander von Humboldt Foundation, Bonn, Germany, for extensions of his research fellowship.

supplementary crystallographic information

Comment

In the present work, as part of a study of substituent effects on the structures of N-(aryl)-arylsulfonamides, the structure of N-(phenyl)-2-methyl-4-chlorobenzenesulfonamide (NP2M4CBSA) has been determined (Gowda et al. 2008a,b, 2009). The asymmetric unit of NP2M4CBSA contains 2 molecules. The orientations of the ortho- methyl groups in the sulfonyl benzene rings are in the direction of the N—H bonds of the sulfonamido groups (Fig. 1). The opposite signs of the C—S—N—C torsion angles in the two independent molecules, -61.9 (4)° (molecule 1) and 69.7 (4)° (molecule 2), indicates that they have opposite chirality, although the choice of the chirality of the second molecule relative to the first may be arbitary. The two benzene rings in NP2M4CBSA are tilted relative to each other by 86.6 (2)° in the molecule 1 and 83.0 (2)° in molecule 2, compared with the values of 67.5 (1)° (molecule 1) and 72.9 (1)° (molecule 2) for N-(phenyl)-2,4-dimethylbenzenesulfonamide (NP24DMBSA) (Gowda et al., 2009). The other bond parameters in NP2M4CBSA are similar to those observed for N-(2-methylphenyl)-benzenesulfonamide (Gowda et al., 2008a), NP24DMBSA and other aryl sulfonamides (Perlovich et al., 2006; Gelbrich et al., 2007; Gowda et al., 2008b). The crystal packing of molecules in NP2M4CBSA via intermolecular N—H···O hydrogen bonds (Table 1) is shown in Fig.2.

Experimental

The solution of m-chlorotoluene (10 cc) in chloroform (40 cc) was treated dropwise with chlorosulfonic acid (25 cc) 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 2-methyl-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 cc). The resultant solid N-(phenyl)-2-methyl-4-chlorobenzenesulfonamide was filtered under suction and washed thoroughly with cold water. It was then recrystallized to constant melting point from dilute ethanol. The purity of the compound was checked and characterized by recording its infrared and NMR spectra. The single crystals used in X-ray diffraction studies were grown in ethanolic solution by slow evaporation at room temperature.