N-(2,5-Dimethyl­phen­yl)-4-methyl­benzene­sulfonamide

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

doi:10.1107/S1600536809051174

N-(2,5-Dimethylphenyl)-4-methylbenzenesulfonamide

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

In the crystal structure of the title compound, C₁₅H₁₇NO₂S, the conformation of the N—C bond in the C—SO₂—NH—C segment has gauche torsions with respect to the S=O bonds. The molecule is bent at the S atom with a C—SO₂—NH—C torsion angle of −61.0 (2)°. The dihedral angle between the two aromatic rings is 49.4 (1)°. The crystal structure features inversion-related dimers linked by pairs of N—H

O hydrogen bonds.

Read article Similar articles

Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536809051174/ng2695sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536809051174/ng2695Isup2.hkl Contains datablock I

CCDC reference: 766715

checkCIF report

Key indicators

Single-crystal X-ray study
T = 299 K
Mean (C-C) = 0.004 Å
R factor = 0.047
wR factor = 0.140
Data-to-parameter ratio = 14.8

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT923_ALERT_1_A S    values in the CIF and FCF Differ by .......       0.07

Alert level B
PLAT922_ALERT_1_B wR2 * 100.0 in the CIF and FCF Differ by .......       0.76

Alert level C
CELLV02_ALERT_1_C  The supplied cell volume s.u. differs from that
            calculated from the cell parameter s.u.'s by > 2
            Calculated cell volume su =      13.77
            Cell volume su given      =      11.00
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.597         19
PLAT152_ALERT_1_C The Supplied and Calc. Volume s.u. Differ by ...          3 Units
PLAT921_ALERT_1_C R1  * 100.0 in the CIF and FCF Differ by .......       0.30

Alert level G
PLAT154_ALERT_1_G The su's on the Cell Angles are Equal  (x 10000)       1000 Deg.

   1 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   6 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

As part of a study of the substituent effects on the crystal structures of N-(aryl)-arylsulfonamides (Gowda et al., 2009a,b), in the present work, the structure of 4-methyl-N-(2,5-dimethylphenyl)benzenesulfonamide (I) has been determined. The conformation of the N—C bond in the C—SO₂—NH—C segment of the structure has gauche torsions with respect to the S═O bonds (Fig. 1). The molecule is bent at the S atom with the C—SO₂—NH—C torsion angle of -61.0 (2)°, compared to the values of -61.8 (2)° in 4-methyl-N-(3,4-dimethylphenyl)benzenesulfonamide (II), -51.6 (3)° in 4-Methyl-N-(phenyl)benzenesulfonamide (III) (Gowda et al., 2009b) and 62.7 (2)° in N-(2,5-dimethylphenyl)benzenesulfonamide (IV) (Gowda et al., 2009a). The two benzene rings in (I) are tilted relative to each other by 49.4 (1)°, compared to the values of 47.8 (1)° in (II), 68.4 (1)° in (III) and 40.4 (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 pairs of N—H···O hydrogen bonds (Table 1) pack the molecules into infinite chains parallel to the c-axis (Fig. 2).

Related literature top

For our study of the effects of substituents on the structures of N-(aryl)-arylsulfonamides, see: Gowda et al. (2009a,b). For related structures, 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 4-methylbenzenesulfonylchloride was treated with 2,5-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 4-methyl-N-(2,5-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. 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.

N-(2,5-Dimethylphenyl)-4-methylbenzenesulfonamide top

Crystal data top

C₁₅H₁₇NO₂S	Z = 2
M_r = 275.36	F(000) = 292
Triclinic, P1	D_x = 1.245 Mg m⁻³
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54180 Å
a = 8.6397 (7) Å	Cell parameters from 25 reflections
b = 9.7067 (8) Å	θ = 7.2–23.8°
c = 10.518 (1) Å	µ = 1.94 mm⁻¹
α = 66.97 (1)°	T = 299 K
β = 81.37 (1)°	Prism, colourless
γ = 64.82 (1)°	0.50 × 0.30 × 0.08 mm
V = 734.47 (11) Å³

Data collection top

Enraf–Nonius CAD-4 diffractometer	2324 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.040
Graphite monochromator	θ_max = 66.9°, θ_min = 4.6°
ω/2θ scans	h = −10→4
Absorption correction: ψ scan (North et al., 1968)	k = −11→11
T_min = 0.444, T_max = 0.861	l = −12→12
3926 measured reflections	3 standard reflections every 120 min
2603 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)] = 0.047	H-atom parameters constrained
wR(F²) = 0.140	w = 1/[σ²(F_o²) + (0.0683P)² + 0.2017P] where P = (F_o² + 2F_c²)/3
S = 1.18	(Δ/σ)_max = 0.001
2603 reflections	Δρ_max = 0.39 e Å⁻³
176 parameters	Δρ_min = −0.46 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: 0.0133 (16)

Crystal data top

C₁₅H₁₇NO₂S	γ = 64.82 (1)°
M_r = 275.36	V = 734.47 (11) Å³
Triclinic, P1	Z = 2
a = 8.6397 (7) Å	Cu Kα radiation
b = 9.7067 (8) Å	µ = 1.94 mm⁻¹
c = 10.518 (1) Å	T = 299 K
α = 66.97 (1)°	0.50 × 0.30 × 0.08 mm
β = 81.37 (1)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	2324 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.040
T_min = 0.444, T_max = 0.861	3 standard reflections every 120 min
3926 measured reflections	intensity decay: 1.0%
2603 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.140	H-atom parameters constrained
S = 1.18	Δρ_max = 0.39 e Å⁻³
2603 reflections	Δρ_min = −0.46 e Å⁻³
176 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
S1	1.05078 (6)	−0.00156 (6)	0.20853 (5)	0.0456 (2)
O1	1.1338 (2)	0.0247 (2)	0.07776 (16)	0.0591 (5)
O2	1.1518 (2)	−0.0780 (2)	0.33191 (16)	0.0560 (4)
N1	0.9516 (2)	−0.1130 (2)	0.21337 (18)	0.0487 (5)
H1N	0.9621	−0.1456	0.1462	0.058*
C1	0.8925 (3)	0.1869 (3)	0.2088 (2)	0.0451 (5)
C2	0.8295 (4)	0.3162 (3)	0.0855 (3)	0.0646 (7)
H2	0.8739	0.3063	0.0018	0.078*
C3	0.6998 (4)	0.4602 (3)	0.0887 (3)	0.0761 (8)
H3	0.6568	0.5471	0.0058	0.091*
C4	0.6323 (4)	0.4792 (3)	0.2106 (3)	0.0651 (7)
C5	0.6989 (3)	0.3478 (3)	0.3329 (3)	0.0574 (6)
H5	0.6554	0.3583	0.4166	0.069*
C6	0.8281 (3)	0.2021 (3)	0.3331 (2)	0.0494 (5)
H6	0.8713	0.1151	0.4159	0.059*
C7	0.8463 (3)	−0.1581 (3)	0.3284 (2)	0.0464 (5)
C8	0.6706 (3)	−0.0938 (3)	0.3112 (3)	0.0565 (6)
C9	0.5788 (4)	−0.1463 (4)	0.4267 (3)	0.0734 (8)
H9	0.4606	−0.1073	0.4188	0.088*
C10	0.6579 (4)	−0.2540 (4)	0.5520 (3)	0.0726 (8)
H10	0.5918	−0.2850	0.6270	0.087*
C11	0.8321 (4)	−0.3172 (3)	0.5696 (2)	0.0591 (6)
C12	0.9274 (3)	−0.2698 (3)	0.4553 (2)	0.0530 (6)
H12	1.0459	−0.3126	0.4633	0.064*
C13	0.4892 (5)	0.6354 (4)	0.2132 (4)	0.0963 (11)
H13A	0.4227	0.6898	0.1290	0.116*
H13B	0.5359	0.7052	0.2218	0.116*
H13C	0.4175	0.6112	0.2903	0.116*
C14	0.5794 (4)	0.0286 (4)	0.1766 (3)	0.0760 (8)
H14A	0.6140	−0.0205	0.1080	0.091*
H14B	0.6079	0.1218	0.1472	0.091*
H14C	0.4581	0.0628	0.1887	0.091*
C15	0.9181 (5)	−0.4357 (4)	0.7079 (3)	0.0797 (9)
H15A	0.8746	−0.5195	0.7457	0.096*
H15B	0.8949	−0.3784	0.7697	0.096*
H15C	1.0393	−0.4847	0.6962	0.096*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0435 (3)	0.0545 (3)	0.0279 (3)	−0.0142 (2)	0.0042 (2)	−0.0118 (2)
O1	0.0546 (9)	0.0812 (11)	0.0335 (9)	−0.0253 (9)	0.0123 (7)	−0.0194 (8)
O2	0.0487 (8)	0.0694 (10)	0.0350 (8)	−0.0145 (8)	−0.0046 (6)	−0.0129 (7)
N1	0.0570 (10)	0.0528 (10)	0.0319 (9)	−0.0178 (9)	0.0057 (8)	−0.0176 (8)
C1	0.0474 (11)	0.0474 (11)	0.0330 (11)	−0.0172 (9)	0.0009 (8)	−0.0095 (9)
C2	0.0807 (17)	0.0568 (14)	0.0341 (12)	−0.0163 (13)	−0.0006 (11)	−0.0066 (10)
C3	0.094 (2)	0.0539 (14)	0.0496 (16)	−0.0122 (14)	−0.0125 (14)	−0.0029 (12)
C4	0.0660 (15)	0.0511 (13)	0.0680 (18)	−0.0148 (12)	−0.0039 (13)	−0.0195 (12)
C5	0.0587 (14)	0.0623 (14)	0.0497 (14)	−0.0194 (12)	0.0053 (11)	−0.0258 (11)
C6	0.0531 (12)	0.0530 (12)	0.0331 (11)	−0.0165 (10)	0.0011 (9)	−0.0124 (9)
C7	0.0575 (12)	0.0447 (11)	0.0351 (11)	−0.0198 (10)	0.0058 (9)	−0.0153 (9)
C8	0.0596 (14)	0.0594 (13)	0.0472 (14)	−0.0244 (11)	0.0038 (11)	−0.0168 (11)
C9	0.0642 (16)	0.090 (2)	0.0663 (19)	−0.0395 (16)	0.0140 (14)	−0.0240 (16)
C10	0.087 (2)	0.088 (2)	0.0515 (16)	−0.0551 (17)	0.0204 (14)	−0.0198 (14)
C11	0.0856 (18)	0.0582 (14)	0.0406 (13)	−0.0417 (13)	0.0075 (12)	−0.0133 (11)
C12	0.0652 (14)	0.0490 (12)	0.0391 (12)	−0.0226 (11)	0.0016 (10)	−0.0112 (10)
C13	0.097 (2)	0.0616 (17)	0.103 (3)	−0.0021 (17)	−0.011 (2)	−0.0308 (18)
C14	0.0570 (15)	0.088 (2)	0.0616 (17)	−0.0218 (14)	−0.0052 (13)	−0.0117 (15)
C15	0.122 (3)	0.0820 (19)	0.0410 (15)	−0.063 (2)	−0.0003 (15)	−0.0031 (13)

Geometric parameters (Å, º) top

S1—O2	1.4256 (16)	C8—C9	1.391 (4)
S1—O1	1.4341 (15)	C8—C14	1.503 (4)
S1—N1	1.625 (2)	C9—C10	1.371 (4)
S1—C1	1.758 (2)	C9—H9	0.9300
N1—C7	1.442 (3)	C10—C11	1.373 (4)
N1—H1N	0.8600	C10—H10	0.9300
C1—C6	1.379 (3)	C11—C12	1.388 (3)
C1—C2	1.382 (3)	C11—C15	1.510 (4)
C2—C3	1.379 (4)	C12—H12	0.9300
C2—H2	0.9300	C13—H13A	0.9600
C3—C4	1.374 (4)	C13—H13B	0.9600
C3—H3	0.9300	C13—H13C	0.9600
C4—C5	1.388 (4)	C14—H14A	0.9600
C4—C13	1.502 (4)	C14—H14B	0.9600
C5—C6	1.380 (3)	C14—H14C	0.9600
C5—H5	0.9300	C15—H15A	0.9600
C6—H6	0.9300	C15—H15B	0.9600
C7—C8	1.384 (3)	C15—H15C	0.9600
C7—C12	1.396 (3)

O2—S1—O1	118.99 (10)	C9—C8—C14	120.5 (2)
O2—S1—N1	108.50 (10)	C10—C9—C8	121.8 (3)
O1—S1—N1	105.30 (10)	C10—C9—H9	119.1
O2—S1—C1	107.99 (10)	C8—C9—H9	119.1
O1—S1—C1	108.74 (10)	C9—C10—C11	121.7 (2)
N1—S1—C1	106.69 (10)	C9—C10—H10	119.1
C7—N1—S1	121.11 (15)	C11—C10—H10	119.1
C7—N1—H1N	119.4	C10—C11—C12	117.7 (2)
S1—N1—H1N	119.4	C10—C11—C15	121.4 (3)
C6—C1—C2	120.6 (2)	C12—C11—C15	120.9 (3)
C6—C1—S1	119.18 (17)	C11—C12—C7	120.4 (2)
C2—C1—S1	120.17 (18)	C11—C12—H12	119.8
C3—C2—C1	118.9 (2)	C7—C12—H12	119.8
C3—C2—H2	120.6	C4—C13—H13A	109.5
C1—C2—H2	120.6	C4—C13—H13B	109.5
C4—C3—C2	122.0 (2)	H13A—C13—H13B	109.5
C4—C3—H3	119.0	C4—C13—H13C	109.5
C2—C3—H3	119.0	H13A—C13—H13C	109.5
C3—C4—C5	117.9 (2)	H13B—C13—H13C	109.5
C3—C4—C13	121.7 (3)	C8—C14—H14A	109.5
C5—C4—C13	120.4 (3)	C8—C14—H14B	109.5
C6—C5—C4	121.5 (2)	H14A—C14—H14B	109.5
C6—C5—H5	119.3	C8—C14—H14C	109.5
C4—C5—H5	119.3	H14A—C14—H14C	109.5
C1—C6—C5	119.2 (2)	H14B—C14—H14C	109.5
C1—C6—H6	120.4	C11—C15—H15A	109.5
C5—C6—H6	120.4	C11—C15—H15B	109.5
C8—C7—C12	121.7 (2)	H15A—C15—H15B	109.5
C8—C7—N1	120.3 (2)	C11—C15—H15C	109.5
C12—C7—N1	118.0 (2)	H15A—C15—H15C	109.5
C7—C8—C9	116.6 (2)	H15B—C15—H15C	109.5
C7—C8—C14	122.9 (2)

O2—S1—N1—C7	54.45 (18)	S1—C1—C6—C5	−177.31 (18)
O1—S1—N1—C7	−177.12 (16)	C4—C5—C6—C1	0.1 (4)
C1—S1—N1—C7	−61.67 (18)	S1—N1—C7—C8	111.3 (2)
O2—S1—C1—C6	−31.9 (2)	S1—N1—C7—C12	−69.9 (2)
O1—S1—C1—C6	−162.32 (18)	C12—C7—C8—C9	−0.1 (4)
N1—S1—C1—C6	84.6 (2)	N1—C7—C8—C9	178.7 (2)
O2—S1—C1—C2	150.3 (2)	C12—C7—C8—C14	178.9 (3)
O1—S1—C1—C2	19.9 (2)	N1—C7—C8—C14	−2.3 (4)
N1—S1—C1—C2	−93.2 (2)	C7—C8—C9—C10	1.1 (4)
C6—C1—C2—C3	−0.7 (4)	C14—C8—C9—C10	−177.9 (3)
S1—C1—C2—C3	177.0 (2)	C8—C9—C10—C11	−0.7 (5)
C1—C2—C3—C4	0.4 (5)	C9—C10—C11—C12	−0.7 (4)
C2—C3—C4—C5	0.1 (5)	C9—C10—C11—C15	−180.0 (3)
C2—C3—C4—C13	−179.0 (3)	C10—C11—C12—C7	1.7 (4)
C3—C4—C5—C6	−0.4 (4)	C15—C11—C12—C7	−179.0 (2)
C13—C4—C5—C6	178.8 (3)	C8—C7—C12—C11	−1.3 (4)
C2—C1—C6—C5	0.5 (4)	N1—C7—C12—C11	179.9 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1ⁱ	0.86	2.28	2.957 (2)	135

Symmetry code: (i) −x+2, −y, −z.

Experimental details

Crystal data
Chemical formula	C₁₅H₁₇NO₂S
M_r	275.36
Crystal system, space group	Triclinic, P1
Temperature (K)	299
a, b, c (Å)	8.6397 (7), 9.7067 (8), 10.518 (1)
α, β, γ (°)	66.97 (1), 81.37 (1), 64.82 (1)
V (Å³)	734.47 (11)
Z	2
Radiation type	Cu Kα
µ (mm⁻¹)	1.94
Crystal size (mm)	0.50 × 0.30 × 0.08

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.444, 0.861
No. of measured, independent and observed [I > 2σ(I)] reflections	3926, 2603, 2324
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.140, 1.18
No. of reflections	2603
No. of parameters	176
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.46

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