N-(2-Chloro­phen­yl)-4-methyl­benzene­sulfonamide

The mol­ecule of the title compound, C₁₃H₁₂ClNO₂S, is bent at the S atom with a C—SO₂—NH—C torsion angle of −54.8 (2)°. The dihedral angle between the two aromatic rings is 71.6 (1)°. An intra­molecular N—H...Cl hydrogen bond is observed. The crystal structure features inversion-related dimers formed by pairs of N—H...O hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 299 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.039
• wR factor = 0.117
• Data-to-parameter ratio = 14.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.599         19
PLAT153_ALERT_1_C The su's on the Cell Axes   are Equal (x 100000)        100 Ang.

Alert level G
PLAT128_ALERT_4_G Non-standard setting of Space-group P21/c   ....      P21/n

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

   1 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
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

S1. Comment

As part of a study of the effect of substituents on crystal structures of N-(aryl)-arylsulfonamides (Gowda et al., 2009; Nirmala et al., 2009), the crystal structure of N-(2-chlorophenyl)4-methylbenzenesulfonamide (I) has been determined. The conformation of the N—H bond is syn to the 2-chloro group in the aniline benzene ring. The molecule is bent at the S atom with a C1—S1—N1—C7 torsion angle of -54.8 (2)°, compared to the value of -51.6 (3)° in N-(phenyl)4-methylbenzenesulfonamide (II) (Gowda et al., 2009) and 60.0 (2)° in N-(2-methylphenyl)4-methylbenzenesulfonamide (III) (Nirmala et al., 2009).

The two benzene rings in (I) are tilted relative to each other by 71.6 (1)°, compared to 68.4 (1)° in (II) and 49.7 (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 structure exhibits both the intramolecular N—H···Cl and the intermolecular N—H···O(S) hydrogen bonds.

In the crystal structure, pairs of intermolecular N—H···O hydrogen bonds (Table 1) link the molecules into inversion-related dimers. Part of the crystal structure is shown in Fig. 2.

Related literature

For the preparation of the title compound, see: Gowda et al. (2005). For our studies of the effects of substituents on the structures of N-(aryl)-arylsulfonamides, see: Gowda et al. (2009); Nirmala et al. (2009). For related structures, see: Gelbrich et al. (2007); Perlovich et al. (2006).

S2. Experimental

A solution of toluene (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 2-chloroaniline 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 4-methyl-N-(2-chlorophenyl)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 IR and NMR spectra. Single crystals used in X-ray diffraction studies were grown by a slow evaporation of an ethanolic solution at room temperature.

S3. Refinement

The H atom of the NH group was located in a difference map and its positional parameters were refined [N-H = 0.83 (3) Å]. The other atoms were positioned with idealized geometry using a riding model [C-H = 0.93–0.96 Å]. All H atoms were refined with isotropic displacement parameters (set to 1.2 times of the U_eq of the parent atom).

Computing details

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

	Fig. 1. Molecular structure of the title compound, showing the atom labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Crystal packing of the title compound. Hydrogen bonds are shown as dashed lines.

N-(2-Chlorophenyl)-4-methylbenzenesulfonamide

Crystal data

C13H12ClNO2S	F(000) = 584
Mr = 281.75	Dx = 1.419 Mg m^−3
Monoclinic, P21/n	Cu Kα radiation, λ = 1.54180 Å
Hall symbol: -P 2yn	Cell parameters from 25 reflections
a = 8.661 (1) Å	θ = 6.3–21.3°
b = 9.949 (1) Å	µ = 4.00 mm^−1
c = 15.509 (1) Å	T = 299 K
β = 99.384 (8)°	Needle, colourless
V = 1318.5 (2) Å^3	0.50 × 0.13 × 0.08 mm
Z = 4

Data collection

Enraf–Nonius CAD-4 diffractometer	1792 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.029
Graphite monochromator	θmax = 67.5°, θmin = 5.3°
ω/2θ scans	h = −10→2
Absorption correction: ψ scan (North et al., 1968)	k = −11→0
Tmin = 0.240, Tmax = 0.741	l = −18→18
3151 measured reflections	3 standard reflections every 120 min
2351 independent reflections	intensity decay: 1.6%

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) = 0.117	w = 1/[σ^2(Fo^2) + (0.0678P)^2 + 0.203P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.003
2351 reflections	Δρmax = 0.26 e Å^−3
168 parameters	Δρmin = −0.32 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0074 (7)

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
Cl1	0.61691 (9)	−0.13179 (7)	0.05985 (5)	0.0700 (3)
S1	1.00511 (7)	0.16393 (6)	0.10719 (4)	0.0503 (2)
O1	1.0698 (2)	0.2235 (2)	0.18850 (12)	0.0636 (5)
O2	1.1070 (2)	0.0996 (2)	0.05640 (13)	0.0656 (5)
N1	0.8841 (2)	0.0448 (2)	0.12574 (15)	0.0521 (5)
H1N	0.867 (3)	−0.009 (3)	0.0838 (19)	0.062*
C1	0.8918 (3)	0.2840 (2)	0.04327 (15)	0.0471 (6)
C2	0.8224 (3)	0.2501 (3)	−0.04057 (16)	0.0574 (7)
H2	0.8376	0.1651	−0.0627	0.069*
C3	0.7314 (4)	0.3424 (3)	−0.09075 (19)	0.0626 (7)
H3	0.6840	0.3189	−0.1469	0.075*
C4	0.7084 (4)	0.4705 (3)	−0.0596 (2)	0.0669 (8)
C5	0.7801 (4)	0.5015 (3)	0.0238 (2)	0.0827 (10)
H5	0.7666	0.5868	0.0459	0.099*
C6	0.8711 (4)	0.4099 (3)	0.07551 (19)	0.0691 (8)
H6	0.9182	0.4331	0.1318	0.083*
C7	0.7485 (3)	0.0701 (2)	0.16324 (15)	0.0460 (5)
C8	0.6155 (3)	−0.0057 (2)	0.13720 (15)	0.0505 (6)
C9	0.4813 (3)	0.0161 (3)	0.17153 (18)	0.0641 (7)
H9	0.3933	−0.0368	0.1538	0.077*
C10	0.4771 (4)	0.1159 (3)	0.23198 (19)	0.0688 (8)
H10	0.3854	0.1333	0.2539	0.083*
C11	0.6092 (4)	0.1897 (3)	0.25992 (19)	0.0660 (7)
H11	0.6073	0.2561	0.3019	0.079*
C12	0.7438 (4)	0.1671 (3)	0.22683 (17)	0.0597 (7)
H12	0.8329	0.2173	0.2472	0.072*
C13	0.6086 (5)	0.5708 (4)	−0.1163 (3)	0.1005 (12)
H13A	0.5015	0.5415	−0.1254	0.121*
H13B	0.6440	0.5777	−0.1717	0.121*
H13C	0.6166	0.6569	−0.0881	0.121*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0684 (5)	0.0636 (4)	0.0769 (5)	−0.0086 (3)	0.0080 (4)	−0.0160 (3)
S1	0.0432 (3)	0.0513 (4)	0.0539 (4)	−0.0004 (3)	0.0003 (2)	−0.0079 (3)
O1	0.0575 (11)	0.0704 (13)	0.0567 (11)	−0.0045 (9)	−0.0093 (8)	−0.0096 (9)
O2	0.0466 (10)	0.0718 (12)	0.0789 (13)	0.0026 (9)	0.0112 (9)	−0.0164 (11)
N1	0.0515 (11)	0.0439 (12)	0.0604 (13)	0.0025 (9)	0.0078 (10)	−0.0039 (9)
C1	0.0456 (12)	0.0466 (13)	0.0480 (13)	−0.0063 (10)	0.0048 (10)	−0.0050 (10)
C2	0.0664 (17)	0.0524 (15)	0.0499 (14)	−0.0071 (13)	−0.0012 (12)	−0.0088 (11)
C3	0.0664 (17)	0.0697 (18)	0.0486 (14)	−0.0134 (14)	0.0001 (12)	0.0021 (13)
C4	0.0685 (18)	0.0590 (17)	0.0723 (19)	−0.0021 (14)	0.0087 (15)	0.0189 (14)
C5	0.116 (3)	0.0499 (17)	0.076 (2)	0.0135 (18)	−0.0039 (18)	−0.0046 (15)
C6	0.091 (2)	0.0537 (16)	0.0577 (16)	0.0036 (15)	−0.0025 (15)	−0.0152 (13)
C7	0.0493 (13)	0.0429 (12)	0.0446 (12)	0.0071 (10)	0.0038 (10)	0.0078 (10)
C8	0.0556 (14)	0.0453 (13)	0.0479 (13)	0.0042 (11)	0.0003 (11)	0.0054 (11)
C9	0.0512 (15)	0.078 (2)	0.0612 (16)	−0.0008 (14)	0.0050 (12)	0.0063 (15)
C10	0.0616 (17)	0.086 (2)	0.0607 (17)	0.0153 (16)	0.0168 (14)	0.0080 (16)
C11	0.078 (2)	0.0641 (17)	0.0570 (16)	0.0117 (15)	0.0133 (14)	−0.0037 (14)
C12	0.0629 (16)	0.0589 (16)	0.0566 (16)	−0.0002 (13)	0.0076 (13)	−0.0083 (13)
C13	0.107 (3)	0.085 (3)	0.102 (3)	0.011 (2)	−0.005 (2)	0.034 (2)

Geometric parameters (Å, º)

Cl1—C8	1.737 (3)	C5—H5	0.93
S1—O1	1.4233 (18)	C6—H6	0.93
S1—O2	1.4266 (19)	C7—C8	1.381 (3)
S1—N1	1.639 (2)	C7—C12	1.385 (3)
S1—C1	1.748 (3)	C8—C9	1.373 (4)
N1—C7	1.415 (3)	C9—C10	1.370 (4)
N1—H1N	0.83 (3)	C9—H9	0.93
C1—C6	1.371 (4)	C10—C11	1.369 (4)
C1—C2	1.382 (3)	C10—H10	0.93
C2—C3	1.368 (4)	C11—C12	1.367 (4)
C2—H2	0.93	C11—H11	0.93
C3—C4	1.388 (4)	C12—H12	0.93
C3—H3	0.93	C13—H13A	0.96
C4—C5	1.376 (4)	C13—H13B	0.96
C4—C13	1.506 (4)	C13—H13C	0.96
C5—C6	1.374 (4)
O1—S1—O2	119.12 (12)	C5—C6—H6	120.3
O1—S1—N1	108.46 (12)	C8—C7—C12	118.0 (2)
O2—S1—N1	104.08 (12)	C8—C7—N1	119.4 (2)
O1—S1—C1	108.75 (12)	C12—C7—N1	122.6 (2)
O2—S1—C1	109.52 (12)	C9—C8—C7	121.3 (2)
N1—S1—C1	106.12 (11)	C9—C8—Cl1	118.9 (2)
C7—N1—S1	122.74 (17)	C7—C8—Cl1	119.8 (2)
C7—N1—H1N	112 (2)	C10—C9—C8	119.9 (3)
S1—N1—H1N	111 (2)	C10—C9—H9	120.1
C6—C1—C2	120.2 (3)	C8—C9—H9	120.1
C6—C1—S1	120.8 (2)	C11—C10—C9	119.5 (3)
C2—C1—S1	119.0 (2)	C11—C10—H10	120.3
C3—C2—C1	119.5 (3)	C9—C10—H10	120.3
C3—C2—H2	120.2	C12—C11—C10	120.8 (3)
C1—C2—H2	120.2	C12—C11—H11	119.6
C2—C3—C4	121.4 (3)	C10—C11—H11	119.6
C2—C3—H3	119.3	C11—C12—C7	120.5 (3)
C4—C3—H3	119.3	C11—C12—H12	119.7
C5—C4—C3	117.7 (3)	C7—C12—H12	119.7
C5—C4—C13	121.9 (3)	C4—C13—H13A	109.5
C3—C4—C13	120.4 (3)	C4—C13—H13B	109.5
C6—C5—C4	121.9 (3)	H13A—C13—H13B	109.5
C6—C5—H5	119.1	C4—C13—H13C	109.5
C4—C5—H5	119.1	H13A—C13—H13C	109.5
C1—C6—C5	119.3 (3)	H13B—C13—H13C	109.5
C1—C6—H6	120.3
O1—S1—N1—C7	61.9 (2)	C2—C1—C6—C5	0.4 (4)
O2—S1—N1—C7	−170.36 (19)	S1—C1—C6—C5	−179.4 (3)
C1—S1—N1—C7	−54.8 (2)	C4—C5—C6—C1	0.2 (5)
O1—S1—C1—C6	−3.0 (3)	S1—N1—C7—C8	145.7 (2)
O2—S1—C1—C6	−134.7 (2)	S1—N1—C7—C12	−35.5 (3)
N1—S1—C1—C6	113.5 (2)	C12—C7—C8—C9	1.5 (4)
O1—S1—C1—C2	177.2 (2)	N1—C7—C8—C9	−179.6 (2)
O2—S1—C1—C2	45.5 (2)	C12—C7—C8—Cl1	−178.24 (19)
N1—S1—C1—C2	−66.3 (2)	N1—C7—C8—Cl1	0.6 (3)
C6—C1—C2—C3	−0.8 (4)	C7—C8—C9—C10	0.9 (4)
S1—C1—C2—C3	179.0 (2)	Cl1—C8—C9—C10	−179.4 (2)
C1—C2—C3—C4	0.7 (4)	C8—C9—C10—C11	−2.4 (4)
C2—C3—C4—C5	−0.2 (5)	C9—C10—C11—C12	1.5 (5)
C2—C3—C4—C13	179.6 (3)	C10—C11—C12—C7	1.0 (4)
C3—C4—C5—C6	−0.3 (5)	C8—C7—C12—C11	−2.5 (4)
C13—C4—C5—C6	180.0 (3)	N1—C7—C12—C11	178.7 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O2^i	0.83 (3)	2.40 (3)	3.181 (3)	156 (3)
N1—H1N···Cl1	0.83 (3)	2.46 (3)	2.952 (2)	119 (2)

Symmetry code: (i) −x+2, −y, −z.