N-(2-Methyl­phen­yl)benzene­sulfonamide

In the title compound, C₁₃H₁₃NO₂S, the conformation of the N—H bond is anti to the ortho-methyl group on the aniline ring, in contrast to the syn conformation observed with respect to the ortho-chloro group in N-(2-chloro­phen­yl)benzene­sulfonamide. The dihedral angle between the two benzene rings is 61.5 (1)°. Mol­ecules are linked into chains running along the a axis by N—H...O hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 299 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.040
• wR factor = 0.106
• Data-to-parameter ratio = 12.8

checkCIF/PLATON results

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Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           26.37
           From the CIF: _reflns_number_total               2347
           Count of symmetry unique reflns         1482
           Completeness (_total/calc)            158.37%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured       865
           Fraction of Friedel pairs measured     0.584
           Are heavy atom types Z>Si present        yes

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

   0 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
   0 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

As part of a study of the substituent effects on the crystal structures of N-(aryl)-sulfonamides the structure of N-(2-methylphenyl)-benzenesulfonamide (N2MPBSA) has been determined (Gowda et al., 2007a,b, 2008). The conformations of the N—H and S═O bonds of the SO₂—NH—C group are trans to each other (Fig. 1). Further, the conformation of the N—H bond is anti to the ortho-methyl group in the aniline benzene ring, in contrast to the syn conformation observed with respect to the ortho-chloro group in N-(2-chlorophenyl)-benzenesulfonamide (N2CPBSA) (Perlovich et al., 2006). The two benzene rings are rotated relative to each other by 61.5 (1)° compared to the value of 49.1 (1)° in N2CPBSA. The other bond parameters in N2MPBSA are similar to those in N2CPBSA and other N-(aryl)-sulfonamides (Gelbrich et al., 2007; Gowda et al., 2007a,b, 2008).

In the crystal structure of N2MPBSA (Fig. 1), the molecules are linked into chains running along the a axis by N—H···O hydrogen bonds (Table 1).

Related literature

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

S2. Experimental

A solution of benzene (10 ml) in chloroform (40 ml) was treated dropwise with chlorosulfonic acid (25 ml) at 273 K. 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 10 min. The reaction mixture was then cooled to room temperature and added to ice cold water (100 ml). The resultant solid 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 (Gowda et al., 2005). Single crystals of the title compound used for X-ray diffraction studies were grown by slow evaporation of an ethanolic solution at room temperature.

S3. Refinement

H atoms of the methyl group were positioned geometrically and refined using a riding model, with C-H = 0.96 Å and U_iso(H) = 1.5U_eq(C). The remaining H atoms were located in a difference map and their positional parameters were refined [N-H = 0.82 (3) Å, C-H = 0.88 (4)–1.00 (4) Å] with U_iso(H) = 1.2U_eq(C,N). Three most deviating reflections (0 1 1, 0 1 2, 0 1 3) were omitted from the refinement.

Computing details

Data collection: CrysAlis CCD (Oxford Diffraction, 2004); cell refinement: CrysAlis RED (Oxford Diffraction, 2007); data reduction: CrysAlis RED (Oxford Diffraction, 2007); 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: SHELXS97 (Sheldrick, 2008).

Figures

	Fig. 1. Molecular structure of the title compound, showing the atom labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented as small spheres of arbitrary radii.
	Fig. 2. Part of the crystal structure of the title compound, viewed down the a axis. Hydrogen bonds are shown as dashed lines.

N-(2-Methylphenyl)benzenesulfonamide

Crystal data

C13H13NO2S	F(000) = 520
Mr = 247.30	Dx = 1.342 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2747 reflections
a = 6.4840 (6) Å	θ = 2.4–28.0°
b = 8.6124 (8) Å	µ = 0.25 mm^−1
c = 21.915 (2) Å	T = 299 K
V = 1223.8 (2) Å^3	Prism, colourless
Z = 4	0.50 × 0.50 × 0.45 mm

Data collection

Oxford Diffraction Xcalibur diffractometer with Sapphire CCD detector	2347 independent reflections
Radiation source: fine-focus sealed tube	2164 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
ω and ϕ scans	θmax = 26.4°, θmin = 3.3°
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	h = −7→5
Tmin = 0.884, Tmax = 0.895	k = −10→9
4256 measured reflections	l = −18→27

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.039	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.106	w = 1/[σ^2(Fo^2) + (0.06P)^2 + 0.3217P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max = 0.014
2347 reflections	Δρmax = 0.22 e Å^−3
184 parameters	Δρmin = −0.35 e Å^−3
0 restraints	Absolute structure: Flack (1983), 883 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.02 (10)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
S1	0.47917 (9)	0.38178 (7)	0.43612 (2)	0.04060 (17)
O1	0.5270 (3)	0.3651 (2)	0.49979 (8)	0.0608 (5)
O2	0.6400 (3)	0.4082 (2)	0.39280 (9)	0.0589 (5)
N1	0.3623 (3)	0.2218 (2)	0.41762 (8)	0.0391 (4)
H1N	0.271 (5)	0.195 (3)	0.4409 (13)	0.047*
C1	0.2996 (3)	0.5346 (2)	0.43031 (10)	0.0362 (5)
C2	0.3264 (5)	0.6510 (3)	0.38754 (11)	0.0493 (6)
H2	0.436 (5)	0.649 (3)	0.3609 (13)	0.059*
C3	0.1819 (6)	0.7692 (3)	0.38473 (14)	0.0617 (8)
H3	0.199 (5)	0.847 (4)	0.3560 (15)	0.074*
C4	0.0157 (5)	0.7710 (3)	0.42368 (14)	0.0600 (7)
H4	−0.075 (5)	0.847 (4)	0.4198 (14)	0.072*
C5	−0.0106 (4)	0.6534 (3)	0.46522 (13)	0.0569 (7)
H5	−0.132 (5)	0.657 (4)	0.4885 (14)	0.068*
C6	0.1308 (4)	0.5347 (3)	0.46890 (11)	0.0462 (6)
H6	0.111 (5)	0.447 (3)	0.4956 (12)	0.055*
C7	0.3086 (4)	0.1940 (3)	0.35437 (10)	0.0378 (5)
C8	0.4396 (4)	0.1005 (3)	0.31992 (10)	0.0455 (5)
C9	0.3803 (6)	0.0680 (4)	0.25957 (12)	0.0601 (7)
H9	0.469 (5)	0.004 (4)	0.2348 (15)	0.072*
C10	0.2019 (6)	0.1273 (4)	0.23580 (13)	0.0689 (9)
H10	0.181 (5)	0.100 (4)	0.1956 (16)	0.083*
C11	0.0750 (6)	0.2190 (4)	0.27027 (14)	0.0668 (9)
H11	−0.059 (6)	0.265 (4)	0.2564 (17)	0.080*
C12	0.1286 (4)	0.2529 (3)	0.33042 (12)	0.0522 (6)
H12	0.043 (5)	0.318 (4)	0.3561 (14)	0.063*
C13	0.6314 (5)	0.0302 (4)	0.34651 (15)	0.0661 (8)
H13A	0.5953	−0.0343	0.3806	0.079*
H13B	0.7222	0.1114	0.3599	0.079*
H13C	0.6994	−0.0314	0.3160	0.079*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0369 (3)	0.0429 (3)	0.0419 (3)	0.0025 (2)	−0.0041 (2)	−0.0025 (2)
O1	0.0723 (13)	0.0611 (11)	0.0490 (9)	0.0122 (11)	−0.0249 (9)	−0.0039 (8)
O2	0.0390 (9)	0.0623 (12)	0.0755 (12)	−0.0041 (9)	0.0128 (9)	−0.0048 (9)
N1	0.0410 (10)	0.0420 (10)	0.0342 (9)	−0.0013 (9)	0.0041 (8)	−0.0002 (7)
C1	0.0388 (11)	0.0359 (11)	0.0338 (10)	0.0002 (9)	−0.0040 (9)	−0.0036 (9)
C2	0.0624 (16)	0.0477 (14)	0.0377 (11)	−0.0049 (12)	0.0043 (11)	0.0037 (10)
C3	0.090 (2)	0.0435 (15)	0.0517 (15)	0.0008 (15)	−0.0140 (15)	0.0098 (12)
C4	0.0627 (17)	0.0513 (14)	0.0661 (16)	0.0170 (14)	−0.0170 (15)	−0.0092 (12)
C5	0.0451 (15)	0.0594 (16)	0.0663 (16)	0.0085 (13)	0.0036 (13)	−0.0143 (12)
C6	0.0468 (14)	0.0462 (14)	0.0454 (12)	−0.0019 (12)	0.0068 (11)	−0.0003 (10)
C7	0.0427 (12)	0.0373 (11)	0.0333 (10)	−0.0047 (9)	0.0036 (9)	0.0033 (9)
C8	0.0520 (13)	0.0447 (12)	0.0398 (11)	0.0000 (11)	0.0103 (9)	0.0012 (10)
C9	0.081 (2)	0.0590 (16)	0.0408 (12)	−0.0032 (15)	0.0152 (14)	−0.0044 (12)
C10	0.095 (2)	0.075 (2)	0.0368 (12)	−0.0140 (19)	−0.0078 (15)	−0.0007 (14)
C11	0.068 (2)	0.077 (2)	0.0549 (16)	0.0008 (16)	−0.0181 (15)	0.0022 (15)
C12	0.0490 (15)	0.0592 (15)	0.0484 (13)	0.0050 (14)	−0.0045 (12)	−0.0036 (11)
C13	0.0553 (17)	0.0716 (19)	0.0713 (18)	0.0198 (16)	0.0099 (15)	−0.0114 (15)

Geometric parameters (Å, º)

S1—O2	1.4284 (19)	C6—H6	0.96 (3)
S1—O1	1.4365 (17)	C7—C12	1.376 (4)
S1—N1	1.624 (2)	C7—C8	1.393 (3)
S1—C1	1.762 (2)	C8—C9	1.405 (4)
N1—C7	1.449 (3)	C8—C13	1.501 (4)
N1—H1N	0.82 (3)	C9—C10	1.368 (5)
C1—C6	1.383 (3)	C9—H9	0.97 (3)
C1—C2	1.384 (3)	C10—C11	1.368 (5)
C2—C3	1.385 (4)	C10—H10	0.92 (3)
C2—H2	0.92 (3)	C11—C12	1.394 (4)
C3—C4	1.375 (5)	C11—H11	1.00 (4)
C3—H3	0.93 (3)	C12—H12	0.97 (3)
C4—C5	1.373 (4)	C13—H13A	0.96
C4—H4	0.88 (4)	C13—H13B	0.96
C5—C6	1.376 (4)	C13—H13C	0.96
C5—H5	0.94 (3)
O2—S1—O1	120.26 (13)	C1—C6—H6	118.4 (18)
O2—S1—N1	108.05 (11)	C12—C7—C8	121.6 (2)
O1—S1—N1	104.97 (11)	C12—C7—N1	120.5 (2)
O2—S1—C1	108.38 (11)	C8—C7—N1	117.8 (2)
O1—S1—C1	106.73 (11)	C7—C8—C9	117.3 (2)
N1—S1—C1	107.90 (10)	C7—C8—C13	121.9 (2)
C7—N1—S1	119.41 (15)	C9—C8—C13	120.8 (3)
C7—N1—H1N	112 (2)	C10—C9—C8	121.0 (3)
S1—N1—H1N	115 (2)	C10—C9—H9	120.4 (19)
C6—C1—C2	120.9 (2)	C8—C9—H9	118.6 (19)
C6—C1—S1	118.63 (17)	C11—C10—C9	121.0 (3)
C2—C1—S1	120.5 (2)	C11—C10—H10	126 (2)
C1—C2—C3	118.5 (3)	C9—C10—H10	113 (2)
C1—C2—H2	120.8 (19)	C10—C11—C12	119.5 (3)
C3—C2—H2	120.7 (19)	C10—C11—H11	126 (2)
C4—C3—C2	120.7 (3)	C12—C11—H11	115 (2)
C4—C3—H3	120 (2)	C7—C12—C11	119.7 (3)
C2—C3—H3	119 (2)	C7—C12—H12	118.6 (18)
C5—C4—C3	120.0 (3)	C11—C12—H12	121.8 (18)
C5—C4—H4	122 (2)	C8—C13—H13A	109.5
C3—C4—H4	118 (2)	C8—C13—H13B	109.5
C4—C5—C6	120.3 (3)	H13A—C13—H13B	109.5
C4—C5—H5	116 (2)	C8—C13—H13C	109.5
C6—C5—H5	123 (2)	H13A—C13—H13C	109.5
C5—C6—C1	119.5 (2)	H13B—C13—H13C	109.5
C5—C6—H6	122.0 (18)
O2—S1—N1—C7	−45.0 (2)	C2—C1—C6—C5	−0.9 (4)
O1—S1—N1—C7	−174.43 (18)	S1—C1—C6—C5	179.7 (2)
C1—S1—N1—C7	72.0 (2)	S1—N1—C7—C12	−84.6 (3)
O2—S1—C1—C6	−179.00 (18)	S1—N1—C7—C8	98.4 (2)
O1—S1—C1—C6	−48.1 (2)	C12—C7—C8—C9	−0.2 (4)
N1—S1—C1—C6	64.23 (19)	N1—C7—C8—C9	176.8 (2)
O2—S1—C1—C2	1.6 (2)	C12—C7—C8—C13	−177.3 (3)
O1—S1—C1—C2	132.5 (2)	N1—C7—C8—C13	−0.3 (3)
N1—S1—C1—C2	−115.2 (2)	C7—C8—C9—C10	0.6 (4)
C6—C1—C2—C3	0.9 (4)	C13—C8—C9—C10	177.7 (3)
S1—C1—C2—C3	−179.7 (2)	C8—C9—C10—C11	−0.6 (5)
C1—C2—C3—C4	0.2 (4)	C9—C10—C11—C12	0.3 (5)
C2—C3—C4—C5	−1.2 (4)	C8—C7—C12—C11	−0.1 (4)
C3—C4—C5—C6	1.2 (4)	N1—C7—C12—C11	−177.1 (3)
C4—C5—C6—C1	−0.1 (4)	C10—C11—C12—C7	0.1 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1^i	0.82 (3)	2.11 (3)	2.926 (3)	178 (3)

Symmetry code: (i) x−1/2, −y+1/2, −z+1.