4-Methyl-N-(4-methyl­phenyl­sulfon­yl)-N-phenyl­benzene­sulfonamide

Bilge Eren; Selçuk Demir; Hakan Dal; Tuncer Hökelek

doi:10.1107/S1600536814002086

. 2014 Feb 5;70(Pt 3):o238–o239. doi: 10.1107/S1600536814002086

4-Methyl-N-(4-methylphenylsulfonyl)-N-phenylbenzenesulfonamide

Bilge Eren ^a, Selçuk Demir ^b, Hakan Dal ^c, Tuncer Hökelek ^d,^*

PMCID: PMC3998411 PMID: 24764960

Abstract

The whole molecule of the title compound, C₂₀H₁₉NO₄S₂, is generated by twofold rotational symmetry. The N atom is located on the twofold rotation axis and has a trigonal-planar geometry. It is bonded by two S atoms of two symmetry-related 4-methylphenylsulfonyl groups and by the C atom of the phenyl ring, which is bisected by the twofold rotation axis. The benzene and phenyl rings are oriented at a dihedral angle of 51.48 (5)° while the pendant benzene rings are inclined to one another by 87.76 (9)°. In the crystal, weak C—H⋯O hydrogen bonds link the molecules, forming a three-dimensional network.

Related literature

Several sulfonamide derivatives have been used as chemotherapeutic agents for their antibacterial, antifungal, antitumor and hypoglycemic effects for many years, see: Chohan et al. (2010 ▶); El-Sayed et al. (2011 ▶); Seri et al. (2000 ▶). Some sulfonamide derivatives are reported to have carbonic anhydrases (CA) inhibition properties, see: Suparan et al. (2000 ▶). For the use of disulfonamides for their antitumor activity and CA inhibitory properties, see: Boriack-Sjodin et al. (1998 ▶). For the use as catalysts in asymmetric syntheses of complexes obtained from disulfonamides chiral derivatives, see: Guo et al. (1997 ▶). For sulfonation of aniline by 4-tolylsulfonyl chloride utilizing standard procedures with small modifications, see: DeChristopher et al. (1974 ▶). For a related structure involving 4-methylphenylsulfonyl, see: Elgemeie et al. (2013 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₂₀H₁₉NO₄S₂
M _r = 401.51
Monoclinic,
a = 18.1080 (5) Å
b = 9.3834 (3) Å
c = 11.4821 (4) Å
β = 96.015 (3)°
V = 1940.24 (11) Å³
Z = 4
Mo Kα radiation
μ = 0.30 mm⁻¹
T = 296 K
0.25 × 0.22 × 0.14 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer
9411 measured reflections
2441 independent reflections
1981 reflections with I > 2σ(I)
R _int = 0.022

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.109
S = 1.05
2441 reflections
125 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶) and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536814002086/su2692sup1.cif

e-70-0o238-sup1.cif^{(21.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814002086/su2692Isup2.hkl

e-70-0o238-Isup2.hkl^{(117.6KB, hkl)}

Click here for additional data file.^{(6.9KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814002086/su2692Isup3.cml

CCDC reference: http://scripts.iucr.org/cgi-bin/cr.cgi?rm=csd&csdid=939052

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6⋯O2ⁱ	0.93	2.59	3.337 (2)	138
C9—H9⋯O1ⁱⁱ	0.93	2.58	3.496 (2)	168
C10—H10⋯O2ⁱⁱⁱ	0.93	2.59	3.408 (3)	147
C10—H10⋯O2^iv	0.93	2.59	3.408 (3)	147

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

Acknowledgments

The authors are indebted to Anadolu University and the Medicinal Plants and Medicine Research Center of Anadolu University, Eskişehir, Turkey, for the use of the X-ray diffractometer.

supplementary crystallographic information

1. Comment

Sulfonamides, which are known as sulfa drugs, are an important class of compounds in the field of chemistry and pharmacology. Several sulfonamide derivatives are used as chemotherapeutic agents for their antibacterial, antifungal, antitumor and hypoglycemic (Chohan et al., 2010; El-Sayed et al., 2011; Seri et al., 2000). In addition, some sulfonamide derivatives are reported to have carbonic anhydrases (CA) inhibition properties (Suparan et al., 2000). Disulfonamides are sulfonamide derivatives containing two sulfone groups connected to the nitrogen atom and they are used for their antitumor activity and CA inhibitory properties (Boriack-Sjodin et al., 1998). On the other hand, the complexes obtained from their chiral derivatives are used in asymmetric syntheses as catalysts (Guo et al., 1997). The title compound, belonging to the disulfonimide group, was synthesized and its crystal structure is reported herein.

The asymmetric unit of the title compound contains half a molecule; the whole molecule is generated by two-fold rotational symmetry. Atoms N1, C7 and C10 are located on the two-fold rotation axis (Fig. 1). The geometry around atoms S1 and N1 are distorted tetrahedral and planar trigonal, respectively. The average S—O bond length is 1.4213 (13) Å, while the S—N and S—C bond lengths are 1.6822 (9) and 1.7546 (17), respectively. These distances are close to standard values (Allen et al., 1987) and may be compared with the corresponding values in 5-amino-1-(4-methylphenylsulfonyl)-4-pyrazolin-3-one (Elgemeie et al., 2013). The benzene and phenyl rings are oriented at a dihedral angle of 51.48 (5)°. Atoms S1, C11 and N1 are displaced by -0.0757 (4), -0.0172 (26) and -0.0018 (1) Å from the adjacent ring planes.

In the crystal, Fig. 2, weak C—H···O hydrogen bonds (Table 1) link the molecules into a three-dimensional network.

2. Experimental

The title compound was prepared by a two step sulfonylation of aniline by 4-toluenesulfonyl chloride utilizing standard procedures with small modifications (DeChristopher et al., 1974). Aniline (40 mmol) and benzene (10 ml) were placed in a two-necked flask fitted with a dropping funnel and a reflux condenser. A solution of 4-toluenesulfonyl chloride (20 mmol) in benzene (50 ml) was placed in the dropping funnel and was added to the aniline solution in portions with stirring. The mixture was heated under reflux for 2 h. The obtained heterogeneous mixture was cooled and the solvent was evaporated under vacuum. The crude product was treated sequentially with deionized water (20 ml) and NaOH (20%) solution. The mixture was placed in a separation funnel and the water phase was separated and acidified gently with 4M HCl. The precipitate 4-toluene sulfonanilide was collected by filtration, and then dried (yield: 3.66 g, 74%; m.p. 372-373 K). In the second step 4-toluene sulfonanilide (10 mmol) was dissolved in benzene (30 ml) and the mixture stirred under reflux. A solution of 4-toluenesulfonyl chloride (10 mmol) in benzene (30 ml) was added drop wise into the stirring solution, and then potassium tert-butoxide (12 mmol), followed by catalytic amounts of 18-crown-6 were added in portions. After the reaction system was allowed to reflux for 3 h, then the mixture was cooled and the solvent evaporated under vacuum. The crude product was treated with NaOH (20%) solution in order to remove excess 4-toluene sulfonanilide. The insoluble solids were collected by filtration, washed with deionized water, and then dried (yield: 3.21 g, 78%; m.p. 454-456 K). The suitable colourless block-like crystals were obtained by recrystallization from acetone/water (7:3).