N-(2,6-Dimethyl­phen­yl)benzene­sulfonamide

Gowda, B.T.; Foro, S.; Babitha, K.S.; Fuess, H.

doi:10.1107/S1600536808024653

organic compounds

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ISSN: 2056-9890

Volume 64| Part 9| September 2008| Page o1691

doi:10.1107/S1600536808024653

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N-(2,6-Dimethylphenyl)benzenesulfonamide

B. Thimme Gowda,^a ^* Sabine Foro,^b K. S. Babitha ^a 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 30 July 2008; accepted 31 July 2008; online 6 August 2008)

In the crystal structure of the title compound, C₁₄H₁₅NO₂S, the N—H bond is trans to one of the S=O double bonds, similar to what is observed in N-(2-methylphenyl)benzenesulfonamide and other aryl sulfonamides. The two aromatic rings enclose a dihedral angle of 44.9 (1)°. The molecules are connected by intermolecular N—H⋯O hydrogen bonds into chains running along the a axis. An intermolecular C—H⋯O hydrogen bond is also present.

Related literature

For related literature, see: Gelbrich et al. (2007 ); Gowda et al. (2005 , 2008 ); Gowda, Babitha et al. (2007 ); Gowda, Foro et al. (2007 ); Perlovich et al. (2006 ).

Experimental

Crystal data

C₁₄H₁₅NO₂S
M_r = 261.33
Monoclinic, P 2₁ /n
a = 5.2133 (7) Å
b = 17.971 (2) Å
c = 14.040 (1) Å
β = 91.681 (9)°
V = 1314.8 (2) Å³
Z = 4
Cu Kα radiation
μ = 2.13 mm⁻¹
T = 299 (2) K
0.55 × 0.35 × 0.33 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: none
2622 measured reflections
2340 independent reflections
2197 reflections with I > 2σ(I)
R_int = 0.071
3 standard reflections frequency: 120 min intensity decay: 1.0%

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.134
S = 1.08
2340 reflections
164 parameters
H-atom parameters constrained
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.41 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O1ⁱ	0.86	2.55	3.179 (2)	131
C5—H5⋯O2ⁱⁱ	0.93	2.57	3.229 (3)	129
Symmetry codes: (i) x-1, y, z; (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

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, 2003 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808024653/bt2760sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808024653/bt2760Isup2.hkl

checkCIF report

Comment top

As part of a study of the substituent effects on the crystal structures of N-(aryl)-sulfonamides, in the present work, the structure of N-(2,6-dimethylphenyl)-benzenesulfonamide (N26DMPBSA) has been determined (Gowda et al., 2005, 2008; Gowda, Babitha et al. 2007; Gowda, Foro et al. 2007). The the N—H bond is trans to one of the S—O double bonds (Fig. 1), similar to what is observed in N-(2-methylphenyl)-benzenesulfonamide (N2MPBSA)(Gowda et al., 2008) and other aryl sulfonamides (Perlovich et al., 2006; Gelbrich et al., 2007;). The two aromatic rings are rotated relative to each other by 44.9 (1)°, compared with the value of 61.5 (1)° in N2MPBSA. The other bond parameters in N26DMPBSA are similar to those observed in N2MPBSA and other N-(aryl)-sulfonamides (Gowda, Babitha et al., 2007; Gowda, Foro et al. 2007; Gowda et al. 2008; Perlovich et al., 2006; Gelbrich et al., 2007). The packing diagram of N26DMPBSA via intermolecular N—H···O and C—H···O hydrogen bonds (Table 1) is shown in Fig. 2.

Related literature top

For related literature, see: Gelbrich et al. (2007); Gowda et al. (2005, 2008); Gowda, Babitha et al. (2007); Gowda, Foro et al. (2007); Perlovich et al. (2006)

Experimental top

The solution of benzene (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 2,6-dimethylaniline 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 N-(2,6-dimethylphenyl)-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 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, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of the title compound, showing the atom labeling scheme. The displacement ellipsoids are drawn at the 50% probability level. The H atoms are represented as small spheres of arbitrary radii.
	Fig. 2. Molecular packing of the title compound with hydrogen bonding shown as dashed lines.

N-(2,6-Dimethylphenyl)benzenesulfonamide top

Crystal data top

C₁₄H₁₅NO₂S	F(000) = 552
M_r = 261.33	D_x = 1.320 Mg m⁻³
Monoclinic, P2₁/n	Cu Kα radiation, λ = 1.54180 Å
Hall symbol: -P 2yn	Cell parameters from 25 reflections
a = 5.2133 (7) Å	θ = 4.0–19.2°
b = 17.971 (2) Å	µ = 2.14 mm⁻¹
c = 14.040 (1) Å	T = 299 K
β = 91.681 (9)°	Prism, colourless
V = 1314.8 (2) Å³	0.55 × 0.35 × 0.33 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.071
Radiation source: fine-focus sealed tube	θ_max = 66.9°, θ_min = 4.0°
Graphite monochromator	h = −6→1
ω/2θ scans	k = −21→0
2622 measured reflections	l = −16→16
2340 independent reflections	3 standard reflections every 120 min
2197 reflections with I > 2σ(I)	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)] = 0.047	H-atom parameters constrained
wR(F²) = 0.134	w = 1/[σ²(F_o²) + (0.0807P)² + 0.6081P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max = 0.001
2340 reflections	Δρ_max = 0.35 e Å⁻³
164 parameters	Δρ_min = −0.42 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0060 (9)

Crystal data top

C₁₄H₁₅NO₂S	V = 1314.8 (2) Å³
M_r = 261.33	Z = 4
Monoclinic, P2₁/n	Cu Kα radiation
a = 5.2133 (7) Å	µ = 2.14 mm⁻¹
b = 17.971 (2) Å	T = 299 K
c = 14.040 (1) Å	0.55 × 0.35 × 0.33 mm
β = 91.681 (9)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.071
2622 measured reflections	3 standard reflections every 120 min
2340 independent reflections	intensity decay: 1.0%
2197 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.134	H-atom parameters constrained
S = 1.08	Δρ_max = 0.35 e Å⁻³
2340 reflections	Δρ_min = −0.42 e Å⁻³
164 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	−0.0070 (4)	0.19125 (11)	0.78195 (15)	0.0359 (5)
C2	−0.2175 (4)	0.23812 (13)	0.7860 (2)	0.0518 (6)
H2	−0.3303	0.2434	0.7339	0.062*
C3	−0.2557 (5)	0.27695 (15)	0.8699 (3)	0.0677 (8)
H3	−0.3972	0.3081	0.8744	0.081*
C4	−0.0875 (6)	0.26990 (16)	0.9461 (2)	0.0666 (8)
H4	−0.1141	0.2969	1.0014	0.080*
C5	0.1186 (6)	0.22354 (15)	0.94146 (19)	0.0590 (7)
H5	0.2309	0.2186	0.9938	0.071*
C6	0.1608 (4)	0.18376 (13)	0.85885 (17)	0.0453 (5)
H6	0.3017	0.1522	0.8554	0.054*
C7	−0.0178 (4)	0.00007 (11)	0.74093 (15)	0.0373 (5)
C8	−0.1139 (4)	−0.01229 (12)	0.83144 (16)	0.0437 (5)
C9	−0.0176 (6)	−0.07186 (15)	0.8839 (2)	0.0609 (7)
H9	−0.0788	−0.0809	0.9444	0.073*
C10	0.1675 (7)	−0.11784 (16)	0.8480 (3)	0.0730 (9)
H10	0.2336	−0.1568	0.8848	0.088*
C11	0.2541 (6)	−0.10620 (14)	0.7582 (2)	0.0680 (8)
H11	0.3769	−0.1382	0.7343	0.082*
C12	0.1628 (5)	−0.04751 (13)	0.70148 (18)	0.0498 (6)
C13	−0.3213 (5)	0.03545 (14)	0.87194 (18)	0.0521 (6)
H13A	−0.4740	0.0316	0.8323	0.063*
H13B	−0.2651	0.0863	0.8741	0.063*
H13C	−0.3570	0.0189	0.9352	0.063*
C14	0.2511 (6)	−0.03980 (16)	0.6006 (2)	0.0683 (8)
H14A	0.2690	0.0120	0.5853	0.082*
H14B	0.1270	−0.0622	0.5576	0.082*
H14C	0.4135	−0.0643	0.5947	0.082*
N1	−0.1132 (3)	0.06164 (9)	0.68444 (12)	0.0371 (4)
H1N	−0.2573	0.0571	0.6536	0.044*
O1	0.3127 (3)	0.12146 (10)	0.67758 (12)	0.0478 (4)
O2	−0.0692 (4)	0.17882 (10)	0.59926 (12)	0.0576 (5)
S1	0.04474 (9)	0.13941 (3)	0.67748 (3)	0.0358 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0330 (10)	0.0277 (9)	0.0476 (11)	−0.0044 (7)	0.0082 (8)	0.0010 (8)
C2	0.0383 (11)	0.0382 (12)	0.0794 (17)	0.0005 (9)	0.0079 (11)	−0.0024 (11)
C3	0.0519 (14)	0.0440 (14)	0.109 (2)	0.0011 (11)	0.0324 (16)	−0.0178 (14)
C4	0.0731 (18)	0.0538 (15)	0.0749 (19)	−0.0173 (14)	0.0336 (15)	−0.0237 (14)
C5	0.0697 (16)	0.0576 (15)	0.0500 (14)	−0.0172 (13)	0.0086 (12)	−0.0106 (12)
C6	0.0437 (11)	0.0425 (12)	0.0500 (12)	−0.0010 (9)	0.0044 (9)	−0.0046 (9)
C7	0.0377 (10)	0.0300 (10)	0.0437 (11)	−0.0023 (8)	−0.0068 (8)	−0.0014 (8)
C8	0.0421 (11)	0.0398 (11)	0.0490 (12)	−0.0076 (9)	−0.0027 (9)	0.0031 (9)
C9	0.0698 (17)	0.0511 (14)	0.0614 (16)	−0.0060 (12)	−0.0037 (12)	0.0180 (12)
C10	0.088 (2)	0.0455 (14)	0.085 (2)	0.0092 (14)	−0.0165 (17)	0.0183 (14)
C11	0.0701 (18)	0.0419 (14)	0.091 (2)	0.0179 (13)	−0.0075 (15)	−0.0061 (14)
C12	0.0523 (13)	0.0388 (12)	0.0579 (14)	0.0040 (10)	−0.0045 (10)	−0.0108 (10)
C13	0.0489 (13)	0.0557 (14)	0.0523 (13)	−0.0057 (11)	0.0106 (10)	0.0054 (11)
C14	0.0828 (19)	0.0587 (16)	0.0638 (17)	0.0143 (14)	0.0110 (14)	−0.0211 (13)
N1	0.0333 (8)	0.0372 (9)	0.0402 (9)	−0.0016 (7)	−0.0069 (7)	0.0004 (7)
O1	0.0331 (8)	0.0539 (9)	0.0569 (10)	−0.0006 (7)	0.0104 (7)	−0.0048 (7)
O2	0.0690 (11)	0.0563 (10)	0.0473 (9)	0.0011 (8)	−0.0016 (8)	0.0193 (8)
S1	0.0351 (3)	0.0364 (3)	0.0361 (3)	−0.00027 (18)	0.0040 (2)	0.00487 (18)

Geometric parameters (Å, º) top

C1—C6	1.376 (3)	C9—C10	1.377 (5)
C1—C2	1.386 (3)	C9—H9	0.9300
C1—S1	1.765 (2)	C10—C11	1.368 (5)
C2—C3	1.388 (4)	C10—H10	0.9300
C2—H2	0.9300	C11—C12	1.397 (4)
C3—C4	1.369 (5)	C11—H11	0.9300
C3—H3	0.9300	C12—C14	1.508 (4)
C4—C5	1.363 (4)	C13—H13A	0.9600
C4—H4	0.9300	C13—H13B	0.9600
C5—C6	1.386 (3)	C13—H13C	0.9600
C5—H5	0.9300	C14—H14A	0.9600
C6—H6	0.9300	C14—H14B	0.9600
C7—C8	1.397 (3)	C14—H14C	0.9600
C7—C12	1.398 (3)	N1—S1	1.6263 (17)
C7—N1	1.441 (3)	N1—H1N	0.8600
C8—C9	1.386 (3)	O1—S1	1.4334 (16)
C8—C13	1.505 (3)	O2—S1	1.4221 (17)

C6—C1—C2	120.9 (2)	C9—C10—H10	120.0
C6—C1—S1	119.41 (16)	C10—C11—C12	121.7 (3)
C2—C1—S1	119.71 (18)	C10—C11—H11	119.2
C1—C2—C3	118.3 (3)	C12—C11—H11	119.2
C1—C2—H2	120.8	C11—C12—C7	117.3 (3)
C3—C2—H2	120.8	C11—C12—C14	119.8 (2)
C4—C3—C2	120.8 (2)	C7—C12—C14	122.9 (2)
C4—C3—H3	119.6	C8—C13—H13A	109.5
C2—C3—H3	119.6	C8—C13—H13B	109.5
C5—C4—C3	120.5 (3)	H13A—C13—H13B	109.5
C5—C4—H4	119.8	C8—C13—H13C	109.5
C3—C4—H4	119.8	H13A—C13—H13C	109.5
C4—C5—C6	120.0 (3)	H13B—C13—H13C	109.5
C4—C5—H5	120.0	C12—C14—H14A	109.5
C6—C5—H5	120.0	C12—C14—H14B	109.5
C1—C6—C5	119.5 (2)	H14A—C14—H14B	109.5
C1—C6—H6	120.2	C12—C14—H14C	109.5
C5—C6—H6	120.2	H14A—C14—H14C	109.5
C8—C7—C12	121.8 (2)	H14B—C14—H14C	109.5
C8—C7—N1	119.69 (19)	C7—N1—S1	121.72 (13)
C12—C7—N1	118.5 (2)	C7—N1—H1N	119.1
C9—C8—C7	118.2 (2)	S1—N1—H1N	119.1
C9—C8—C13	119.5 (2)	O2—S1—O1	119.85 (11)
C7—C8—C13	122.3 (2)	O2—S1—N1	105.89 (10)
C10—C9—C8	121.0 (3)	O1—S1—N1	107.55 (10)
C10—C9—H9	119.5	O2—S1—C1	107.95 (11)
C8—C9—H9	119.5	O1—S1—C1	106.89 (10)
C11—C10—C9	120.0 (3)	N1—S1—C1	108.28 (9)
C11—C10—H10	120.0

C6—C1—C2—C3	−0.4 (3)	C10—C11—C12—C14	−176.0 (3)
S1—C1—C2—C3	178.70 (18)	C8—C7—C12—C11	−3.2 (3)
C1—C2—C3—C4	0.9 (4)	N1—C7—C12—C11	179.3 (2)
C2—C3—C4—C5	−1.1 (4)	C8—C7—C12—C14	174.0 (2)
C3—C4—C5—C6	0.7 (4)	N1—C7—C12—C14	−3.5 (3)
C2—C1—C6—C5	0.1 (3)	C8—C7—N1—S1	99.9 (2)
S1—C1—C6—C5	−179.04 (18)	C12—C7—N1—S1	−82.5 (2)
C4—C5—C6—C1	−0.2 (4)	C7—N1—S1—O2	165.74 (17)
C12—C7—C8—C9	2.6 (3)	C7—N1—S1—O1	36.48 (19)
N1—C7—C8—C9	−179.8 (2)	C7—N1—S1—C1	−78.70 (18)
C12—C7—C8—C13	−175.8 (2)	C6—C1—S1—O2	−153.98 (17)
N1—C7—C8—C13	1.8 (3)	C2—C1—S1—O2	26.9 (2)
C7—C8—C9—C10	−0.1 (4)	C6—C1—S1—O1	−23.8 (2)
C13—C8—C9—C10	178.3 (3)	C2—C1—S1—O1	157.06 (17)
C8—C9—C10—C11	−1.7 (5)	C6—C1—S1—N1	91.81 (18)
C9—C10—C11—C12	1.2 (5)	C2—C1—S1—N1	−87.33 (18)
C10—C11—C12—C7	1.2 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1ⁱ	0.86	2.55	3.179 (2)	131
C5—H5···O2ⁱⁱ	0.93	2.57	3.229 (3)	129

Symmetry codes: (i) x−1, y, z; (ii) x+1/2, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₅NO₂S
M_r	261.33
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	299
a, b, c (Å)	5.2133 (7), 17.971 (2), 14.040 (1)
β (°)	91.681 (9)
V (Å³)	1314.8 (2)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	2.14
Crystal size (mm)	0.55 × 0.35 × 0.33

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	2622, 2340, 2197
R_int	0.071
(sin θ/λ)_max (Å⁻¹)	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.134, 1.08
No. of reflections	2340
No. of parameters	164
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.42

Computer programs: CAD-4-PC (Enraf–Nonius, 1996), REDU4 (Stoe & Cie, 1987), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1ⁱ	0.86	2.55	3.179 (2)	130.5
C5—H5···O2ⁱⁱ	0.93	2.57	3.229 (3)	128.5

Symmetry codes: (i) x−1, y, z; (ii) x+1/2, −y+1/2, z+1/2.

Acknowledgements

BTG thanks the Alexander von Humboldt Foundation, Bonn, Germany, for extensions of his research fellowship.

References

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