N-(2,4-Dichloro­phen­yl)-2,4-dimethyl­benzene­sulfonamide

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

doi:10.1107/S1600536810045563

. 2010 Nov 13;66(Pt 12):o3144. doi: 10.1107/S1600536810045563

N-(2,4-Dichlorophenyl)-2,4-dimethylbenzenesulfonamide

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

PMCID: PMC3011417 PMID: 21589443

Abstract

In the title compound, C₁₄H₁₃Cl₂NO₂S, the molecule is bent at the S atom with an C—SO₂—NH—C torsion angle of −69.9 (2)°. The dihedral angle between the sulfonyl and aniline benzene rings is 44.0 (1)°. The crystal structure features inversion dimers linked by pairs of N—H⋯O hydrogen bonds. An intramolecular N—H⋯Cl hydrogen bond is also observed.

Related literature

For the preparation of the compound, see: Savitha & Gowda (2006 ▶). For our study of the effect of substituents on the structures of N-(aryl)arylsulfonamides, see: Gowda et al. (2009 ▶); Nirmala et al. (2010a ▶,b ▶). For related structures, see: Gelbrich et al. (2007 ▶); Perlovich et al. (2006 ▶).

Experimental

Crystal data

C₁₄H₁₃Cl₂NO₂S
M _r = 330.21
Triclinic,
a = 8.2407 (9) Å
b = 8.3418 (9) Å
c = 10.849 (1) Å
α = 84.59 (1)°
β = 89.06 (1)°
γ = 85.07 (1)°
V = 739.69 (13) Å³
Z = 2
Cu Kα radiation
μ = 5.27 mm⁻¹
T = 293 K
0.45 × 0.40 × 0.13 mm

Data collection

Ennraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ▶) T _min = 0.200, T _max = 0.547
5173 measured reflections
2629 independent reflections
2496 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)] = 0.056
wR(F ²) = 0.159
S = 1.05
2629 reflections
187 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.80 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/S1600536810045563/bq2251sup1.cif

e-66-o3144-sup1.cif^{(18KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810045563/bq2251Isup2.hkl

e-66-o3144-Isup2.hkl^{(129.1KB, 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⋯O2ⁱ	0.85 (2)	2.24 (2)	3.056 (3)	159 (3)
N1—H1N⋯Cl1	0.85 (2)	2.68 (3)	3.020 (2)	105 (2)

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Symmetry code: (i) Inline graphic .

supplementary crystallographic information

Comment

In the present work, as part of a study of the substituent effects on the structures of N-(aryl)arylsulfonamides (Gowda et al., 2009; Nirmala et al., 2010a,b), the structure of 2,4-dimethyl-N-(2,4-dichlorophenyl)benzenesulfonamide (I) has been determined (Fig. 1). The molecule is bent at the N atom with the C1—SO₂—NH—C7 torsion angle of -69.9 (2)°, compared to the values of 46.1 (3)° (glide image of molecule 1) and 47.7 (3)° (molecule 2) in the two independent molecules of 2,4-dimethyl-N-(phenyl)benzenesulfonamide (II) (Gowda et al., 2009), -54.9 (3)° in 2,4-dimethyl-N-(3,5-dichlorophenyl)benzenesulfonamide (III) (Nirmala et al., 2010b) and 66.5 (2)° in 2,4-dimethyl-N-(2,4-dimethylphenyl)-benzenesulfonamide (IV) (Nirmala et al., 2010a)

The two benzene rings in (I) are tilted relative to each other by 44.0 (1)°, compared to the values of 67.5 (1)° (molecule 1) and 72.9 (1)° (molecule 2) in the two independent molecules of(II), 82.3 (1)° in (III) and 41.0 (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).

The structure shows simultaneous N—H···Cl intramolecular and N—H···O intermolecular H-bonding (Table 1). The crystal packing of molecules in (I) via N—H···O(S) hydrogen bonds is shown in Fig.2.

Experimental

The solution of 1,3-xylene (1,3-dimethylbenzene) (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-dimethylbenzenesulfonylchloride was treated with 2,4-dichloroaniline 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-dimethyl-N-(2,4-dichlorophenyl)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).

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