2,4-Dichloro-N-(2-methyl­phen­yl)benzene­sulfonamide

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

doi:10.1107/S1600536810035166

. 2010 Sep 11;66(Pt 10):o2542. doi: 10.1107/S1600536810035166

2,4-Dichloro-N-(2-methylphenyl)benzenesulfonamide

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

PMCID: PMC2983146 PMID: 21587532

Abstract

In the title compound, C₁₃H₁₁Cl₂NO₂S, the methyl-substituted aromatic ring is disordered over two positions [occupancy ratio 0.705 (5):0.295 (5)]. The dihedral angles between the two aromatic rings are 74.9 (1) and 71.0 (3)° in the two disorder components. The crystal structure features centrosymmetric dimers linked by pairs of N—H⋯O hydrogen bonds.

Related literature

For the preparation of the title compound, see: Savitha & Gowda (2006 ▶). For our studies of the effect of substituents on the structures of N-(aryl)arylsulfonamides, see: Gowda et al. (2008 ▶, 2010a ▶,b ▶); For related structures, see: Gelbrich et al. (2007 ▶); Perlovich et al. (2006 ▶).

Experimental

Crystal data

C₁₃H₁₁Cl₂NO₂S
M _r = 316.19
Monoclinic,
a = 8.106 (1) Å
b = 14.854 (2) Å
c = 11.772 (1) Å
β = 97.34 (1)°
V = 1405.8 (3) Å³
Z = 4
Cu Kα radiation
μ = 5.52 mm⁻¹
T = 299 K
0.35 × 0.25 × 0.25 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: multi-scan (North et al., 1968 ▶) T _min = 0.248, T _max = 0.339
5256 measured reflections
2501 independent reflections
2205 reflections with I > 2σ(I)
R _int = 0.033
3 standard reflections every 120 min intensity decay: 1.0%

Refinement

R[F ² > 2σ(F ²)] = 0.039
wR(F ²) = 0.098
S = 1.04
2501 reflections
240 parameters
8 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.38 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/S1600536810035166/bt5340sup1.cif

e-66-o2542-sup1.cif^{(21.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810035166/bt5340Isup2.hkl

e-66-o2542-Isup2.hkl^{(122.9KB, 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	0.84 (2)	2.13 (2)	2.936 (2)	159 (2)

Open in a new tab

Symmetry code: (i) Inline graphic .

supplementary crystallographic information

Comment

As part of a study of the substituent effects on the structures of N-(aryl)arylsulfonamides (Gowda et al., 2008; Gowda et al. 2010a,b), the structure of 2,4-dichloro-N-(2-methylphenyl)-benzenesulfonamide (I) has been determined (Fig. 1). The methylsubstituted anilino ring is disordered. The conformations of the N—C bonds in the C—SO₂—NH—C segment have gauche torsions with respect to the S═O bonds in one of the disordered components.

The molecule is twisted at the S atom with the C1—SO₂—NH—C7 torsion angles of -85.1 (3)° and -47.2 (5)° in the major and minor components, respectively, compared to the values of 55.1 (3)° (molecule 1) and -48.3 (3)° (molecule 2) in 2,4-dichloro-N-(phenyl)-benzenesulfonamide (II) (Gowda et al., 2010b), -60.2 (2)° in 2,4-dichloro-N- (3-methylphenyl)benzenesulfonamide (III)(Gowda et al., 2010a) and 72.0 (2)° in N-(2-methylphenyl)-benzenesulfonamide (IV) (Gowda et al., 2008).

The sulfonyl benzene and the aniline benzene rings in (I) are tilted relative to each other by 74.9 (1)° and 71.0 (3)° in the two components, compared to the values of 80.5 (2)° in molecule 1 and 64.9 (1)° in molecule 2 of (II), 68.6 (1)° in (III) and 61.5 (1)° in (IV).

The other bond parameters in (I) are similar to those observed in (II), (III), (IV) and other aryl sulfonamides (Perlovich et al., 2006; Gelbrich et al., 2007).

In the crystal structure, the pairs of intermolecular N–H···O hydrogen bonds (Table 1) link the molecules through inversion-related dimers into infinite chains running parallel to the c-axis. Part of the crystal structure is shown in Fig. 2.

Experimental

The solution of 1,3-dichlorobenzene (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 2,4-dichlorobenzenesulfonylchloride was treated with o-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 2,4-dichloro-N-(2-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 (Savitha & Gowda, 2006).

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