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The N—H bond in the title compound, C14H14ClNO2S, the dihedral angle between the two benzene rings is 75.5 (1)°. The crystal structure features inversion-related dimers linked by pairs of N—H...O hydrogen bonds.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536809051083/ci2978sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536809051083/ci2978Isup2.hkl
Contains datablock I

CCDC reference: 766714

Key indicators

  • Single-crystal X-ray study
  • T = 299 K
  • Mean [sigma](C-C) = 0.005 Å
  • R factor = 0.052
  • wR factor = 0.156
  • Data-to-parameter ratio = 16.5

checkCIF/PLATON results

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Alert level C PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C11 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C4 PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang .. 5 PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) ..... 1 PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L= 0.600 2 PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L= 0.600 3
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 6 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 3 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

Comment top

As part of a study of the substituent effects on the structures of N-(aryl)arylsulfonamides (Gowda et al., 2009a,b,c), in the present work the structure of 4-chloro-2-methyl-N- (3-methylphenyl)benzenesulfonamide (I) has been determined (Fig. 1). The conformation of the N—H bond is anti to the meta-methyl group in the aniline benzene ring. The molecule is bent at the N atom with the C1—S1—N1—C7 torsion angle of 77.2 (3)°, compared to the values of 73.0 (3)° in 4-chloro-2-methyl-N-(2-methylphenyl)benzenesulfonamide (II) (Gowda et al., 2009c), 74.8°(4) in 2-methyl-4-chloro-N-(2-chlorophenyl)benzenesulfonamide (III) (Gowda et al., 2009b) and -61.9 (4)° (molecule 1) and 69.7 (4)° (molecule 2) in the two independent molecules of 4-chloro-2-methyl-N- (phenyl)benzenesulfonamide (III) (Gowda et al., 2009a). The two benzene rings are tilted relative to each other by 75.5 (1)°, compared to the values of 45.8 (1)° in (II), 45.5 (2)° in (III), and 86.6 (2)° (molecule 1) and 83.0 (2)° (molecule 2) in the two independent molecules of (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 crystal packing of molecules in (I) via N—H···O(S) hydrogen bonds (Table 1) is shown in Fig.2.

Related literature top

For the preparation, see: Savitha & Gowda (2006). For our study of the effect of substituents on the crystal structures of N-(aryl)arylsulfonamides, see: Gowda et al. (2009a,b,c). For related structures, see: Gelbrich et al. (2007); Perlovich et al. (2006).

Experimental top

A solution of m-chlorotoluene (10 ml) in chloroform (40 ml) was treated dropwise with chlorosulfonic acid (25 ml) 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-chloro-2-methylbenzenesulfonylchloride was treated with m-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-chloro-2-methyl-N- (3-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 (Savitha & Gowda, 2006). The single crystals used in X-ray diffraction studies were grown in ethanolic solution by slow evaporation at room temperature.

Refinement top

The H atom of the NH group was located in a difference map and its positional parameters were refined with the N-H distance restrained to 0.82 (4) Å. The other H 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 Ueq of the parent atom).

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2009); cell refinement: CrysAlis RED (Oxford Diffraction, 2009); data reduction: CrysAlis RED (Oxford Diffraction, 2009); 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
[Figure 1] Fig. 1. Molecular structure of the title compound, showing the atom labeling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented as small spheres of arbitrary radii.
[Figure 2] Fig. 2. Molecular packing of the title compound with hydrogen bonding shown as dashed lines.
4-Chloro-2-methyl-N-(3-methylphenyl)benzenesulfonamide top
Crystal data top
C14H14ClNO2SF(000) = 616
Mr = 295.77Dx = 1.373 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2116 reflections
a = 7.8830 (7) Åθ = 2.6–27.9°
b = 11.602 (1) ŵ = 0.41 mm1
c = 15.645 (2) ÅT = 299 K
β = 90.593 (8)°Prism, colourless
V = 1430.8 (3) Å30.48 × 0.28 × 0.12 mm
Z = 4
Data collection top
Oxford Diffraction Xcalibur
diffractometer with a Sapphire CCD detector
2925 independent reflections
Radiation source: fine-focus sealed tube1980 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.014
Rotation method data acquisition using ω and ϕ scansθmax = 26.4°, θmin = 2.6°
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2009)
h = 96
Tmin = 0.828, Tmax = 0.953k = 1114
5563 measured reflectionsl = 1918
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.052Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.156H atoms treated by a mixture of independent and constrained refinement
S = 1.03 w = 1/[σ2(Fo2) + (0.0757P)2 + 0.6262P]
where P = (Fo2 + 2Fc2)/3
2925 reflections(Δ/σ)max = 0.020
177 parametersΔρmax = 0.36 e Å3
0 restraintsΔρmin = 0.44 e Å3
Crystal data top
C14H14ClNO2SV = 1430.8 (3) Å3
Mr = 295.77Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.8830 (7) ŵ = 0.41 mm1
b = 11.602 (1) ÅT = 299 K
c = 15.645 (2) Å0.48 × 0.28 × 0.12 mm
β = 90.593 (8)°
Data collection top
Oxford Diffraction Xcalibur
diffractometer with a Sapphire CCD detector
2925 independent reflections
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2009)
1980 reflections with I > 2σ(I)
Tmin = 0.828, Tmax = 0.953Rint = 0.014
5563 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0520 restraints
wR(F2) = 0.156H atoms treated by a mixture of independent and constrained refinement
S = 1.03Δρmax = 0.36 e Å3
2925 reflectionsΔρmin = 0.44 e Å3
177 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
xyzUiso*/Ueq
C10.6521 (3)0.1989 (2)0.83780 (16)0.0484 (6)
C20.8133 (4)0.1933 (2)0.87588 (18)0.0552 (7)
C30.9404 (4)0.2588 (3)0.8394 (2)0.0679 (8)
H31.04940.25630.86270.081*
C40.9084 (4)0.3278 (3)0.7692 (2)0.0675 (8)
C50.7500 (5)0.3331 (3)0.7328 (2)0.0725 (9)
H50.72920.38020.68580.087*
C60.6223 (4)0.2679 (3)0.76688 (18)0.0616 (8)
H60.51450.27000.74210.074*
C70.3599 (3)0.2701 (2)0.99538 (18)0.0509 (6)
C80.3539 (3)0.3658 (2)0.94325 (19)0.0584 (7)
H80.40120.36220.88910.070*
C90.2787 (4)0.4672 (3)0.9703 (2)0.0630 (8)
C100.2096 (5)0.4692 (3)1.0506 (2)0.0882 (11)
H100.15770.53621.07000.106*
C110.2159 (5)0.3740 (4)1.1028 (2)0.0929 (12)
H110.16980.37761.15720.111*
C120.2895 (4)0.2737 (3)1.07543 (19)0.0663 (8)
H120.29190.20901.11050.080*
C130.8530 (4)0.1198 (3)0.9571 (2)0.0703 (9)
H13A0.83130.04000.94510.084*
H13B0.78230.14481.00320.084*
H13C0.97010.12950.97320.084*
C140.2762 (5)0.5716 (3)0.9131 (3)0.0857 (11)
H14A0.20780.55600.86340.103*
H14B0.38980.58960.89610.103*
H14C0.22930.63590.94350.103*
N10.4428 (4)0.1662 (2)0.97214 (17)0.0692 (8)
H1N0.445 (4)0.118 (3)1.011 (2)0.083*
O10.3367 (3)0.1432 (2)0.82291 (15)0.0752 (6)
O20.5297 (3)0.00166 (16)0.88893 (14)0.0708 (6)
Cl11.07032 (16)0.41278 (11)0.72879 (9)0.1237 (5)
S10.47841 (9)0.11958 (6)0.87689 (5)0.0572 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0546 (15)0.0446 (13)0.0461 (14)0.0116 (12)0.0020 (11)0.0040 (12)
C20.0599 (16)0.0479 (15)0.0576 (16)0.0147 (13)0.0036 (13)0.0032 (13)
C30.0566 (17)0.0603 (19)0.087 (2)0.0091 (15)0.0030 (16)0.0136 (17)
C40.077 (2)0.0543 (17)0.071 (2)0.0048 (15)0.0271 (17)0.0090 (16)
C50.099 (3)0.066 (2)0.0528 (17)0.0143 (19)0.0131 (17)0.0072 (15)
C60.0692 (19)0.0651 (18)0.0504 (16)0.0146 (15)0.0034 (14)0.0023 (14)
C70.0479 (14)0.0486 (15)0.0563 (16)0.0009 (11)0.0032 (12)0.0036 (12)
C80.0590 (16)0.0532 (17)0.0631 (18)0.0017 (13)0.0068 (14)0.0016 (14)
C90.0591 (18)0.0513 (16)0.078 (2)0.0032 (13)0.0098 (15)0.0089 (15)
C100.104 (3)0.081 (3)0.080 (3)0.036 (2)0.004 (2)0.022 (2)
C110.107 (3)0.108 (3)0.064 (2)0.036 (2)0.015 (2)0.009 (2)
C120.0658 (18)0.073 (2)0.0604 (18)0.0085 (15)0.0035 (15)0.0038 (15)
C130.0676 (19)0.0651 (19)0.078 (2)0.0248 (15)0.0330 (16)0.0020 (16)
C140.094 (3)0.0524 (19)0.111 (3)0.0071 (18)0.014 (2)0.0019 (19)
N10.095 (2)0.0514 (15)0.0613 (16)0.0169 (14)0.0169 (14)0.0085 (12)
O10.0598 (12)0.0789 (15)0.0866 (16)0.0024 (11)0.0155 (11)0.0093 (12)
O20.0932 (15)0.0446 (11)0.0749 (14)0.0048 (10)0.0039 (11)0.0041 (10)
Cl10.1293 (10)0.1064 (9)0.1367 (11)0.0264 (7)0.0632 (8)0.0064 (7)
S10.0630 (5)0.0485 (4)0.0600 (5)0.0044 (3)0.0008 (3)0.0033 (3)
Geometric parameters (Å, º) top
C1—C61.387 (4)C9—C101.375 (5)
C1—C21.399 (4)C9—C141.506 (5)
C1—S11.764 (3)C10—C111.375 (5)
C2—C31.386 (4)C10—H100.93
C2—C131.560 (4)C11—C121.371 (5)
C3—C41.380 (5)C11—H110.93
C3—H30.93C12—H120.93
C4—C51.369 (5)C13—H13A0.96
C4—Cl11.737 (3)C13—H13B0.96
C5—C61.371 (4)C13—H13C0.96
C5—H50.93C14—H14A0.96
C6—H60.93C14—H14B0.96
C7—C121.375 (4)C14—H14C0.96
C7—C81.378 (4)N1—S11.613 (3)
C7—N11.420 (3)N1—H1N0.82 (4)
C8—C91.386 (4)O1—S11.420 (2)
C8—H80.93O2—S11.438 (2)
C6—C1—C2120.9 (3)C9—C10—H10119.4
C6—C1—S1116.9 (2)C12—C11—C10120.6 (3)
C2—C1—S1122.2 (2)C12—C11—H11119.7
C3—C2—C1117.2 (3)C10—C11—H11119.7
C3—C2—C13119.7 (3)C11—C12—C7119.1 (3)
C1—C2—C13123.1 (3)C11—C12—H12120.4
C4—C3—C2121.2 (3)C7—C12—H12120.4
C4—C3—H3119.4C2—C13—H13A109.5
C2—C3—H3119.4C2—C13—H13B109.5
C5—C4—C3121.0 (3)H13A—C13—H13B109.5
C5—C4—Cl1119.6 (3)C2—C13—H13C109.5
C3—C4—Cl1119.3 (3)H13A—C13—H13C109.5
C4—C5—C6119.0 (3)H13B—C13—H13C109.5
C4—C5—H5120.5C9—C14—H14A109.5
C6—C5—H5120.5C9—C14—H14B109.5
C5—C6—C1120.7 (3)H14A—C14—H14B109.5
C5—C6—H6119.7C9—C14—H14C109.5
C1—C6—H6119.7H14A—C14—H14C109.5
C12—C7—C8120.2 (3)H14B—C14—H14C109.5
C12—C7—N1116.7 (3)C7—N1—S1127.3 (2)
C8—C7—N1123.0 (3)C7—N1—H1N114 (3)
C7—C8—C9121.0 (3)S1—N1—H1N116 (3)
C7—C8—H8119.5O1—S1—O2118.67 (14)
C9—C8—H8119.5O1—S1—N1109.96 (14)
C10—C9—C8117.9 (3)O2—S1—N1104.43 (13)
C10—C9—C14121.7 (3)O1—S1—C1107.55 (13)
C8—C9—C14120.3 (3)O2—S1—C1108.88 (13)
C11—C10—C9121.1 (3)N1—S1—C1106.78 (14)
C11—C10—H10119.4
C6—C1—C2—C30.3 (4)C8—C9—C10—C110.5 (5)
S1—C1—C2—C3179.6 (2)C14—C9—C10—C11178.6 (4)
C6—C1—C2—C13178.3 (3)C9—C10—C11—C120.9 (6)
S1—C1—C2—C131.7 (4)C10—C11—C12—C71.1 (6)
C1—C2—C3—C40.8 (4)C8—C7—C12—C110.9 (5)
C13—C2—C3—C4177.8 (3)N1—C7—C12—C11176.6 (3)
C2—C3—C4—C50.5 (5)C12—C7—N1—S1157.2 (2)
C2—C3—C4—Cl1177.3 (2)C8—C7—N1—S125.5 (4)
C3—C4—C5—C60.5 (5)C7—N1—S1—O139.2 (3)
Cl1—C4—C5—C6178.2 (2)C7—N1—S1—O2167.5 (3)
C4—C5—C6—C11.0 (4)C7—N1—S1—C177.2 (3)
C2—C1—C6—C50.5 (4)C6—C1—S1—O11.2 (2)
S1—C1—C6—C5179.5 (2)C2—C1—S1—O1178.8 (2)
C12—C7—C8—C90.5 (4)C6—C1—S1—O2130.9 (2)
N1—C7—C8—C9176.8 (3)C2—C1—S1—O249.0 (3)
C7—C8—C9—C100.2 (4)C6—C1—S1—N1116.8 (2)
C7—C8—C9—C14178.9 (3)C2—C1—S1—N163.2 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···O2i0.82 (4)2.10 (4)2.925 (3)176 (3)
Symmetry code: (i) x+1, y, z+2.

Experimental details

Crystal data
Chemical formulaC14H14ClNO2S
Mr295.77
Crystal system, space groupMonoclinic, P21/c
Temperature (K)299
a, b, c (Å)7.8830 (7), 11.602 (1), 15.645 (2)
β (°) 90.593 (8)
V3)1430.8 (3)
Z4
Radiation typeMo Kα
µ (mm1)0.41
Crystal size (mm)0.48 × 0.28 × 0.12
Data collection
DiffractometerOxford Diffraction Xcalibur
diffractometer with a Sapphire CCD detector
Absorption correctionMulti-scan
(CrysAlis RED; Oxford Diffraction, 2009)
Tmin, Tmax0.828, 0.953
No. of measured, independent and
observed [I > 2σ(I)] reflections
5563, 2925, 1980
Rint0.014
(sin θ/λ)max1)0.625
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.052, 0.156, 1.03
No. of reflections2925
No. of parameters177
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.36, 0.44

Computer programs: CrysAlis CCD (Oxford Diffraction, 2009), CrysAlis RED (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···O2i0.82 (4)2.10 (4)2.925 (3)176 (3)
Symmetry code: (i) x+1, y, z+2.
 

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