4-Methyl-N-(2-methyl­phen­yl)benzene­sulfonamide

Nirmala, P.G.; Gowda, B.T.; Foro, S.; Fuess, H.

doi:10.1107/S1600536809049411

organic compounds

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ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page o3184

doi:10.1107/S1600536809049411

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4-Methyl-N-(2-methylphenyl)benzenesulfonamide

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

^aDepartment of Chemistry, Mangalore University, Mangalagangotri 574 199, Mangalore, India, and ^bInstitute of Materials Science, Darmstadt University of Technology, Petersenstrasse 23, D-64287 Darmstadt, Germany
^*Correspondence e-mail: gowdabt@yahoo.com

(Received 15 November 2009; accepted 19 November 2009; online 21 November 2009)

In the title compound, C₁₄H₁₅NO₂S, the dihedral angle between the aromatic rings is 49.7 (1)°. In the crystal, inversion dimers linked by pairs of N—H⋯O hydrogen bonds occur.

Related literature

For our study of the effect of substituents on the crystal structures of N-(aryl)-arylsulfonamides, see: Gowda et al. (2008 ; 2009 ). For bond lengths in other aryl sulfonamides, see: Gelbrich et al. (2007 ); Perlovich et al. (2006 ).

Experimental

Crystal data

C₁₄H₁₅NO₂S
M_r = 261.33
Orthorhombic, P b c a
a = 14.650 (3) Å
b = 12.019 (1) Å
c = 15.634 (3) Å
V = 2752.8 (8) Å³
Z = 8
Cu Kα radiation
μ = 2.04 mm⁻¹
T = 299 K
0.55 × 0.55 × 0.35 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.400, T_max = 0.535
3596 measured reflections
2450 independent reflections
1899 reflections with I > 2σ(I)
R_int = 0.044
3 standard reflections frequency: 120 min intensity decay: 1.0%

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.134
S = 1.06
2450 reflections
167 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O1ⁱ	0.838 (17)	2.219 (18)	3.036 (3)	165 (2)
Symmetry code: (i) -x, -y, -z+1.

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 .

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809049411/ng2688sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809049411/ng2688Isup2.hkl

checkCIF report

Comment top

As part of a study of the effect of substituents on the crystal structures of N-(aryl)-arylsulfonamides (Gowda et al., 2008; 2009), in the present work, the structure of 4-methyl-N-(2-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). The molecule is bent at the S atom with the C1—SO₂—NH—C7 torsion angle of 60.0 (2)°, compared to the values of 72.0 (2)° in N-(2-methylphenyl)- benzenesulfonamide (II)(Gowda et al.,2008) and 51.6 (3)° in 4-methyl-N-(phenyl)benzenesulfonamide (III) (Gowda et al., 2009). The N—H bond orients itself away from the ortho-methyl group in the anilino benzene ring. The two benzene rings in (I) are tilted relative to each other by 49.7 (1)°, compared to the values of 61.5 (1)° in (II) and 68.4 (1)° in (III). The other bond parameters are similar to those observed in (II), (III) and other aryl sulfonamides(Perlovich et al., 2006; Gelbrich et al., 2007). The crystal packing of molecules in (I) via N—H···O(S) hydrogen bonds (Table 1) is shown in Fig.2.

Related literature top

For our study of the effect of substituents on the crystal structures of N-(aryl)-arylsulfonamides, see: Gowda et al. (2008; 2009). For bond lengths in other aryl sulfonamides, see: Gelbrich et al. (2007); Perlovich et al. (2006)

Experimental top

The solution of toluene (10 cc) in chloroform (40 cc) was treated dropwise with chlorosulfonic acid (25 cc) 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 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 cc). The resultant solid 4-methyl-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. The single crystals used in X-ray diffraction studies were grown in ethanolic solution by a slow evaporation at room temperature.

Computing details top

Data collection: CAD-4-PC (Enraf–Nonius, 1996); cell refinement: CAD-4-PC (Enraf–Nonius, 1996); 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 (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of (I), showing the atom labelling scheme and displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Molecular packing of (I) with hydrogen bonding shown as dashed lines.

4-Methyl-N-(2-methylphenyl)benzenesulfonamide top

Crystal data top

C₁₄H₁₅NO₂S	F(000) = 1104
M_r = 261.33	D_x = 1.261 Mg m⁻³
Orthorhombic, Pbca	Cu Kα radiation, λ = 1.54180 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 25 reflections
a = 14.650 (3) Å	θ = 5.7–18.7°
b = 12.019 (1) Å	µ = 2.04 mm⁻¹
c = 15.634 (3) Å	T = 299 K
V = 2752.8 (8) Å³	Prism, colourless
Z = 8	0.55 × 0.55 × 0.35 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	1899 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.044
Graphite monochromator	θ_max = 66.8°, θ_min = 5.5°
ω–2θ scans	h = −17→1
Absorption correction: ψ scan (North et al., 1968)	k = −14→1
T_min = 0.400, T_max = 0.535	l = −6→18
3596 measured reflections	3 standard reflections every 120 min
2450 independent reflections	intensity decay: 1.0%

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.044	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.134	w = 1/[σ²(F_o²) + (0.066P)² + 0.6125P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
2450 reflections	Δρ_max = 0.18 e Å⁻³
167 parameters	Δρ_min = −0.23 e Å⁻³
1 restraint	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0052 (4)

Crystal data top

C₁₄H₁₅NO₂S	V = 2752.8 (8) Å³
M_r = 261.33	Z = 8
Orthorhombic, Pbca	Cu Kα radiation
a = 14.650 (3) Å	µ = 2.04 mm⁻¹
b = 12.019 (1) Å	T = 299 K
c = 15.634 (3) Å	0.55 × 0.55 × 0.35 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	1899 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.044
T_min = 0.400, T_max = 0.535	3 standard reflections every 120 min
3596 measured reflections	intensity decay: 1.0%
2450 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	1 restraint
wR(F²) = 0.134	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.18 e Å⁻³
2450 reflections	Δρ_min = −0.23 e Å⁻³
167 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	−0.03969 (15)	0.17693 (18)	0.64937 (14)	0.0620 (6)
C2	−0.12664 (19)	0.1429 (2)	0.6286 (2)	0.0857 (8)
H2	−0.1359	0.0754	0.6008	0.103*
C3	−0.19886 (19)	0.2088 (3)	0.6489 (2)	0.0898 (8)
H3	−0.2574	0.1845	0.6356	0.108*
C4	−0.18818 (18)	0.3102 (2)	0.68837 (15)	0.0733 (6)
C5	−0.10123 (19)	0.3429 (2)	0.70810 (17)	0.0817 (7)
H5	−0.0923	0.4112	0.7348	0.098*
C6	−0.02714 (18)	0.2779 (2)	0.68964 (16)	0.0744 (7)
H6	0.0313	0.3017	0.7041	0.089*
C7	0.12097 (16)	0.2537 (2)	0.52015 (16)	0.0689 (6)
C8	0.07178 (18)	0.3294 (2)	0.47154 (17)	0.0722 (7)
C9	0.1070 (2)	0.4370 (2)	0.4659 (2)	0.0922 (9)
H9	0.0766	0.4895	0.4328	0.111*
C10	0.1853 (3)	0.4672 (3)	0.5079 (3)	0.1076 (11)
H10	0.2063	0.5400	0.5040	0.129*
C11	0.2329 (2)	0.3912 (3)	0.5557 (2)	0.1046 (11)
H11	0.2862	0.4118	0.5839	0.125*
C12	0.20070 (18)	0.2843 (2)	0.5612 (2)	0.0871 (8)
H12	0.2329	0.2318	0.5928	0.105*
C13	−0.2691 (2)	0.3820 (3)	0.7071 (2)	0.1058 (10)
H13A	−0.3106	0.3425	0.7437	0.127*
H13B	−0.2993	0.4008	0.6546	0.127*
H13C	−0.2493	0.4489	0.7352	0.127*
C14	−0.0145 (2)	0.2995 (2)	0.4273 (2)	0.0950 (9)
H14A	−0.0583	0.2740	0.4686	0.114*
H14B	−0.0028	0.2415	0.3865	0.114*
H14C	−0.0381	0.3637	0.3983	0.114*
N1	0.09033 (14)	0.14056 (16)	0.52843 (14)	0.0700 (5)
H1N	0.0544 (16)	0.118 (2)	0.4904 (15)	0.084*
O1	0.02213 (13)	−0.01564 (13)	0.60343 (13)	0.0853 (6)
O2	0.12395 (13)	0.11202 (15)	0.68176 (13)	0.0885 (6)
S1	0.05391 (4)	0.09508 (5)	0.62032 (4)	0.0692 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0703 (13)	0.0502 (11)	0.0654 (12)	−0.0088 (10)	−0.0110 (11)	0.0036 (9)
C2	0.0693 (15)	0.0638 (14)	0.124 (2)	−0.0106 (13)	−0.0150 (15)	−0.0180 (15)
C3	0.0678 (15)	0.0908 (19)	0.111 (2)	−0.0118 (15)	−0.0145 (15)	−0.0120 (16)
C4	0.0772 (15)	0.0814 (16)	0.0614 (13)	0.0030 (13)	0.0008 (12)	0.0042 (12)
C5	0.0939 (19)	0.0689 (15)	0.0821 (16)	−0.0029 (14)	−0.0014 (15)	−0.0193 (13)
C6	0.0727 (14)	0.0705 (15)	0.0801 (15)	−0.0096 (12)	−0.0102 (13)	−0.0162 (12)
C7	0.0686 (13)	0.0572 (12)	0.0809 (15)	−0.0060 (11)	0.0124 (12)	−0.0126 (11)
C8	0.0782 (15)	0.0539 (12)	0.0844 (16)	−0.0001 (11)	0.0177 (13)	−0.0083 (11)
C9	0.111 (2)	0.0598 (14)	0.106 (2)	−0.0032 (15)	0.0331 (19)	−0.0051 (14)
C10	0.121 (3)	0.0745 (19)	0.127 (3)	−0.034 (2)	0.046 (2)	−0.025 (2)
C11	0.094 (2)	0.105 (2)	0.115 (2)	−0.038 (2)	0.019 (2)	−0.030 (2)
C12	0.0727 (15)	0.0891 (19)	0.0996 (19)	−0.0145 (14)	0.0054 (15)	−0.0142 (15)
C13	0.098 (2)	0.120 (3)	0.099 (2)	0.0238 (19)	0.0124 (18)	−0.0002 (19)
C14	0.110 (2)	0.0680 (16)	0.107 (2)	0.0131 (16)	−0.0100 (19)	0.0042 (15)
N1	0.0709 (12)	0.0544 (10)	0.0849 (14)	0.0011 (9)	−0.0057 (10)	−0.0087 (9)
O1	0.1035 (13)	0.0437 (8)	0.1087 (13)	−0.0029 (9)	−0.0176 (11)	0.0040 (8)
O2	0.0823 (11)	0.0824 (12)	0.1009 (13)	0.0038 (9)	−0.0332 (11)	0.0064 (10)
S1	0.0729 (4)	0.0495 (3)	0.0852 (4)	0.0014 (3)	−0.0171 (3)	0.0035 (3)

Geometric parameters (Å, º) top

C1—C2	1.377 (3)	C9—C10	1.371 (5)
C1—C6	1.380 (3)	C9—H9	0.9300
C1—S1	1.748 (2)	C10—C11	1.370 (5)
C2—C3	1.359 (4)	C10—H10	0.9300
C2—H2	0.9300	C11—C12	1.371 (4)
C3—C4	1.375 (4)	C11—H11	0.9300
C3—H3	0.9300	C12—H12	0.9300
C4—C5	1.368 (4)	C13—H13A	0.9600
C4—C13	1.495 (4)	C13—H13B	0.9600
C5—C6	1.368 (4)	C13—H13C	0.9600
C5—H5	0.9300	C14—H14A	0.9600
C6—H6	0.9300	C14—H14B	0.9600
C7—C12	1.382 (4)	C14—H14C	0.9600
C7—C8	1.387 (4)	N1—S1	1.627 (2)
C7—N1	1.437 (3)	N1—H1N	0.838 (17)
C8—C9	1.395 (4)	O1—S1	1.4344 (17)
C8—C14	1.484 (4)	O2—S1	1.4203 (18)

C2—C1—C6	119.5 (2)	C9—C10—H10	119.6
C2—C1—S1	119.82 (18)	C10—C11—C12	118.9 (3)
C6—C1—S1	120.62 (18)	C10—C11—H11	120.5
C3—C2—C1	119.5 (2)	C12—C11—H11	120.5
C3—C2—H2	120.3	C11—C12—C7	120.7 (3)
C1—C2—H2	120.3	C11—C12—H12	119.6
C2—C3—C4	122.2 (3)	C7—C12—H12	119.6
C2—C3—H3	118.9	C4—C13—H13A	109.5
C4—C3—H3	118.9	C4—C13—H13B	109.5
C5—C4—C3	117.5 (3)	H13A—C13—H13B	109.5
C5—C4—C13	121.9 (3)	C4—C13—H13C	109.5
C3—C4—C13	120.6 (3)	H13A—C13—H13C	109.5
C6—C5—C4	121.8 (2)	H13B—C13—H13C	109.5
C6—C5—H5	119.1	C8—C14—H14A	109.5
C4—C5—H5	119.1	C8—C14—H14B	109.5
C5—C6—C1	119.5 (2)	H14A—C14—H14B	109.5
C5—C6—H6	120.2	C8—C14—H14C	109.5
C1—C6—H6	120.2	H14A—C14—H14C	109.5
C12—C7—C8	121.2 (2)	H14B—C14—H14C	109.5
C12—C7—N1	118.3 (3)	C7—N1—S1	119.98 (16)
C8—C7—N1	120.5 (2)	C7—N1—H1N	115.9 (19)
C7—C8—C9	116.8 (3)	S1—N1—H1N	108 (2)
C7—C8—C14	122.6 (2)	O2—S1—O1	119.47 (11)
C9—C8—C14	120.6 (3)	O2—S1—N1	108.19 (12)
C10—C9—C8	121.6 (3)	O1—S1—N1	104.81 (11)
C10—C9—H9	119.2	O2—S1—C1	108.08 (11)
C8—C9—H9	119.2	O1—S1—C1	108.39 (11)
C11—C10—C9	120.7 (3)	N1—S1—C1	107.32 (10)
C11—C10—H10	119.6

C6—C1—C2—C3	−0.7 (4)	C8—C9—C10—C11	1.5 (5)
S1—C1—C2—C3	−177.8 (2)	C9—C10—C11—C12	−0.3 (5)
C1—C2—C3—C4	1.3 (5)	C10—C11—C12—C7	−0.8 (5)
C2—C3—C4—C5	−0.9 (5)	C8—C7—C12—C11	0.8 (4)
C2—C3—C4—C13	178.0 (3)	N1—C7—C12—C11	−179.8 (3)
C3—C4—C5—C6	−0.1 (4)	C12—C7—N1—S1	68.5 (3)
C13—C4—C5—C6	−178.9 (3)	C8—C7—N1—S1	−112.0 (2)
C4—C5—C6—C1	0.6 (4)	C7—N1—S1—O2	−56.3 (2)
C2—C1—C6—C5	−0.2 (4)	C7—N1—S1—O1	175.17 (18)
S1—C1—C6—C5	176.9 (2)	C7—N1—S1—C1	60.1 (2)
C12—C7—C8—C9	0.3 (4)	C2—C1—S1—O2	−150.3 (2)
N1—C7—C8—C9	−179.1 (2)	C6—C1—S1—O2	32.6 (2)
C12—C7—C8—C14	−179.5 (2)	C2—C1—S1—O1	−19.5 (3)
N1—C7—C8—C14	1.1 (4)	C6—C1—S1—O1	163.5 (2)
C7—C8—C9—C10	−1.4 (4)	C2—C1—S1—N1	93.2 (2)
C14—C8—C9—C10	178.4 (3)	C6—C1—S1—N1	−83.8 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1ⁱ	0.84 (2)	2.22 (2)	3.036 (3)	165 (2)

Symmetry code: (i) −x, −y, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₅NO₂S
M_r	261.33
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	299
a, b, c (Å)	14.650 (3), 12.019 (1), 15.634 (3)
V (Å³)	2752.8 (8)
Z	8
Radiation type	Cu Kα
µ (mm⁻¹)	2.04
Crystal size (mm)	0.55 × 0.55 × 0.35

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.400, 0.535
No. of measured, independent and observed [I > 2σ(I)] reflections	3596, 2450, 1899
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.134, 1.06
No. of reflections	2450
No. of parameters	167
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.23

Computer programs: CAD-4-PC (Enraf–Nonius, 1996), REDU4 (Stoe & Cie, 1987), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1ⁱ	0.838 (17)	2.219 (18)	3.036 (3)	165 (2)

Symmetry code: (i) −x, −y, −z+1.

References

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ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page o3184

doi:10.1107/S1600536809049411

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