4-Methyl-N-(3-methyl­phen­yl)benzene­sulfonamide

P G Nirmala; B Thimme Gowda; Sabine Foro; Hartmut Fuess

doi:10.1107/S1600536809049332

. 2009 Nov 25;65(Pt 12):o3208. doi: 10.1107/S1600536809049332

4-Methyl-N-(3-methylphenyl)benzenesulfonamide

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

PMCID: PMC2972154 PMID: 21578916

Abstract

In the title compound, C₁₄H₁₅NO₂S, the conformation of the N—C bond in the C—SO₂—NH—C segment has gauche torsion angles with respect to the S=O bonds. Further, the conformation of the N—H bond is anti to the 3-methyl group in the aniline benzene ring. The molecule is bent at the N atom with a C—SO₂—NH—C torsion angle of 56.7 (3)°. The dihedral angle between the benzene rings is 83.9 (1)°. In the crystal, intermolecular N—H⋯O hydrogen bonds pack the molecules into a supramolecular structure.

Related literature

For the preparation of the title compound, see: Gowda et al. (2005 ▶). For a study of the effect of substituents on the crystal structures of N-(aryl)-arylsulfonamides, see: Gowda et al. (2009a ▶,b ▶); Nirmala et al.(2009 ▶). For bond lengths in other aryl sulfonamides, see: Gelbrich et al. (2007 ▶); Perlovich et al. (2006 ▶). graphic file with name e-65-o3208-scheme1.jpg

Experimental

Crystal data

C₁₄H₁₅NO₂S
M _r = 261.33
Monoclinic,
a = 14.076 (3) Å
b = 14.519 (3) Å
c = 13.482 (2) Å
β = 98.10 (2)°
V = 2727.8 (9) Å³
Z = 8
Cu Kα radiation
μ = 2.06 mm⁻¹
T = 299 K
0.50 × 0.45 × 0.35 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ▶) T _min = 0.426, T _max = 0.533
5405 measured reflections
2436 independent reflections
2285 reflections with I > 2σ(I)
R _int = 0.148
3 standard reflections frequency: 120 min intensity decay: 1.5%

Refinement

R[F ² > 2σ(F ²)] = 0.061
wR(F ²) = 0.163
S = 1.05
2436 reflections
169 parameters
13 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.42 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, 2009 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809049332/lx2127sup1.cif

e-65-o3208-sup1.cif^{(17.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809049332/lx2127Isup2.hkl

e-65-o3208-Isup2.hkl^{(119.8KB, 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	0.839 (18)	2.10 (2)	2.914 (3)	163 (3)

Open in a new tab

Symmetry code: (i) Inline graphic .

supplementary crystallographic information

Comment

As part of a study of the effect of substituents on the crystal structures of N–(aryl)–arylsulfonamides (Gowda et al., 2009a,b; Nirmala et al., 2009), in the present work, the structure of 4–methyl–N–(3–methylphenyl)benzenesulfonamide (I) has been determined.

The conformation of the N—C bond in the C1—SO₂—NH—C7 segment of the structure has gauche torsions with respect to the SO bonds (Fig. 1). Further, the conformation of the N—H bond is anti to the 3–methyl group in the aniline benzene ring. The molecule is bent at the N atom with the C1—SO₂—NH—C7 torsion angle of 56.7 (3)°, compared to the values of -51.6 (3)° in 4–methyl–N–(phenyl)–benzenesulfonamide (II)(Gowda et al., 2009b), 60.0 (2)° in 4–methyl–N–(2–methylphenyl)benzenesulfonamide (III) (Nirmala et al., 2009) and -61.8 (2)° in 4–methyl–N–(3,4–dimethylphenyl)benzenesulfonamide (IV) (Gowda et al., 2009a). The two benzene rings in (I) are tilted relative to each other by 83.9 (1)°, compared to the values of 68.4 (1)° in (II), 49.7 (1)° in (III) and 47.8 (1)° in (IV). The other bond parameters are similar to those observed in (II), (III), (IV) and other aryl sulfonamides (Perlovich et al., 2006; Gelbrich et al., 2007). The crystal packing stabilized by intermolecular N—H···O hydrogen bonds (Table 1) is shown in Fig.2.

Experimental

The solution of toluene (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 benzenesulfonylchloride was treated with m–toluidine 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 4–methyl–N–(3–methylphenyl)benzenesulfonamide 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 (Gowda et al., 2005). The single crystals used in X-ray diffraction studies were grown in ethanolic solution by a slow evaporation at room temperature.