2,4-Dimethyl-N-phenyl­benzene­sulfonamide

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

doi:10.1107/S160053680900573X

. 2009 Feb 21;65(Pt 3):o576. doi: 10.1107/S160053680900573X

2,4-Dimethyl-N-phenylbenzenesulfonamide

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

PMCID: PMC2968648 PMID: 21582231

Abstract

The asymmetric unit of the crystal structure of the title compound, C₁₄H₁₅NO₂S, contains two molecules. The conformations of the N—C bonds in the C—SO₂—NH—C segments of the structure have trans and gauche torsion angles with the S=O bonds. Furthermore, the torsion angles of the C—SO₂—NH—C groups in the two molecules are 46.1 (3) (glide image of molecule 1) and 47.7 (3)° (molecule 2). The ortho-methyl groups in the sulfonyl benzene ring are oriented away from the S=O bonds. The two benzene rings are tilted relative to each other by 67.5 (1) and 72.9 (1)° in the two molecules. N—H⋯O and C—H⋯O hydrogen bonds pack the molecules into one-dimensional chains in different directions, resulting in a two-dimensional network.

Related literature

For related structures, see: Gelbrich et al. (2007 ▶); Gowda et al. (2008a ▶,b ▶,c ▶); Perlovich et al. (2006 ▶). graphic file with name e-65-0o576-scheme1.jpg

Experimental

Crystal data

C₁₄H₁₅NO₂S
M _r = 261.33
Orthorhombic,
a = 19.113 (3) Å
b = 8.9290 (8) Å
c = 15.781 (1) Å
V = 2693.2 (5) Å³
Z = 8
Cu Kα radiation
μ = 2.09 mm⁻¹
T = 299 K
0.50 × 0.43 × 0.25 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ▶) T _min = 0.401, T _max = 0.593
4916 measured reflections
2505 independent reflections
2421 reflections with I > 2σ(I)
R _int = 0.050
3 standard reflections frequency: 120 min intensity decay: 1.0%

Refinement

R[F ² > 2σ(F ²)] = 0.034
wR(F ²) = 0.090
S = 1.09
2505 reflections
330 parameters
7 restraints
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.23 e Å⁻³
Absolute structure: Flack (1983 ▶), no Friedel pairs
Flack parameter: 0.008 (17)

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, 2009 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680900573X/kj2115sup1.cif

e-65-0o576-sup1.cif^{(24.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053680900573X/kj2115Isup2.hkl

e-65-0o576-Isup2.hkl^{(123.1KB, 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⋯O3ⁱ	0.86	2.41	3.164 (3)	147
N2—H2N⋯O1ⁱⁱ	0.86	2.22	3.056 (3)	164
C11—H11⋯O2ⁱⁱⁱ	0.93	2.50	3.227 (4)	135
C23—H23⋯O4ⁱⁱⁱ	0.93	2.50	3.316 (4)	147

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

Acknowledgments

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

supplementary crystallographic information

Comment

As part of a study of the substituent effects on the crystal structures of N-(aryl)-arylsulfonamides (Gowda et al., 2008a, b, c), in the present work, the structure of N-(phenyl)-2,4-dimethylbenzenesulfonamide has been determined . The asymmetric unit contains 2 molecules (Fig. 1). The conformations of the N—C bonds in the C—SO₂—NH—C segments of the structure have "trans" torsions and "gauche" torsions with the S═O bonds. Further, the torsion angles of the C—SO₂—NH—C groups in the two molecules are 46.1 (3)° (glide image of molecule 1) and 47.7 (3)° (molecule 2). The ortho-methyl groups in the sulfonyl benzene rings orient themselves away from the S═O bonds, but in the direction of N—H bonds. The two benzene rings in the title compound are tilted relative to each other by 67.5 (1)° in the molecule 1 and 72.9 (1)° in molecule 2. The other bond parameters in the title compound are similar to those observed in N-(2,6-dimethylphenyl)-benzenesulfonamide (Gowda et al., 2008a), N-(2-methylphenyl)-benzenesulfonamide (Gowda et al., 2008b)) and other aryl sulfonamides (Perlovich et al., 2006; Gelbrich et al., 2007; Gowda et al., 2008c). The N-H···O hydrogen bonds pack the molecules into a 1D chain in the direction of c- axis, while C-H···O hydrogen bonds pack them into a 1D chain in the direction of b-axis, resulting in a 2D network (Table 1, Fig. 2).

Experimental

A solution of 1,3-xylene (10 ml) in chloroform (40 ml) was treated dropwise with chlorosulfonic acid (25 ml) at 273K. 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 2,4-dimethylbenzenesulfonylchloride 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 solid N-(phenyl)-2,4-dimethylbenzenesulfonamide 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.