organic compounds
2,5-Dichloro-N-(2,3-dimethylphenyl)benzenesulfonamide
aMaterials Chemistry Laboratory, Department of Chemistry, GC University, Lahore 54000, Pakistan, bDepartment of Chemistry, University of Aberdeen, Meston Walk, Aberdeen AB24 3UE, Scotland, cQuestioned Documents Unit, Punjab Forensic Science Agency, Home Department, Lahore, Pakistan, and dDepartment of Physics, University of Sargodha, Punjab, Pakistan.
*Correspondence e-mail: koolmuneeb@yahoo.com
In the title compound, C14H13Cl2NO2S, the dihedral angle between the aromatic rings is 62.21 (7)° and the C—S—N—C group adopts a gauche conformation [torsion angle = 60.22 (17)°]. In the crystal, N—H⋯O hydrogen bonds link the molecules into C(4) chains propagating in [010]. A short intermolecular Cl⋯O contact of 3.1115 (17) Å is seen.
Experimental
Crystal data
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Data collection
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Refinement
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Data collection: APEX2 (Bruker, 2007); cell SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
Supporting information
10.1107/S1600536812035787/bt6820sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812035787/bt6820Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812035787/bt6820Isup3.cml
0.1 g of 2,3 dimethyl aniline was dissolved in 15 ml dichloromethane and 0.2 g of 2,5-dichloro benzene sulfonylchloride was added: the mixture was stirred at room temperature overnight with the pH maintained at 8–9 with triethyamine. On completion of reaction (after TLC) the mixture was poured into a separating flask and 1 M HCl solution added. The lower DCM layer was separated and the solvent was allowed to evaporate at room temperature. Brown blocks of (I) were recrystallized from acetonitrile solution at room temperature in 96% yield.
The N-bond H atom was located in a difference map and its position was freely refined. The C-bound H atoms were placed in calculated positions (C—H = 0.93–0.97 Å) and refined as riding. The constraint Uiso(H) = 1.2Ueq(C,N) or 1.5Ueq(methyl C) was applied. The methyl groups were allowed to rotate, but not to tip, to best fit the electron density.
Data collection: APEX2 (Bruker, 2007); cell
SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).Fig. 1. The molecular structure of (I), showing displacement ellipsoids at the 50% probability level. Fig. 2. Fragment of a C(4) chain in the crystal of (I), with N—H···O hydrogen bonds shown as double-dashed lines. All C-bound H atoms omitted for clarity. Symmetry code: (i) 1/2 - x, y + 1/2, z. |
C14H13Cl2NO2S | Dx = 1.494 Mg m−3 |
Mr = 330.21 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pbca | Cell parameters from 1890 reflections |
a = 13.0069 (11) Å | θ = 4.2–21.6° |
b = 10.0775 (9) Å | µ = 0.58 mm−1 |
c = 22.408 (2) Å | T = 296 K |
V = 2937.2 (4) Å3 | Block, colourless |
Z = 8 | 0.30 × 0.20 × 0.18 mm |
F(000) = 1360 |
Bruker APEXII CCD diffractometer | 2377 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.045 |
Graphite monochromator | θmax = 27.2°, θmin = 1.8° |
ω scans | h = −16→15 |
23820 measured reflections | k = −12→12 |
3260 independent reflections | l = −28→28 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.090 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.98 | w = 1/[σ2(Fo2) + (0.0396P)2 + 1.0864P] where P = (Fo2 + 2Fc2)/3 |
3260 reflections | (Δ/σ)max = 0.001 |
186 parameters | Δρmax = 0.26 e Å−3 |
0 restraints | Δρmin = −0.31 e Å−3 |
C14H13Cl2NO2S | V = 2937.2 (4) Å3 |
Mr = 330.21 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 13.0069 (11) Å | µ = 0.58 mm−1 |
b = 10.0775 (9) Å | T = 296 K |
c = 22.408 (2) Å | 0.30 × 0.20 × 0.18 mm |
Bruker APEXII CCD diffractometer | 2377 reflections with I > 2σ(I) |
23820 measured reflections | Rint = 0.045 |
3260 independent reflections |
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.090 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.98 | Δρmax = 0.26 e Å−3 |
3260 reflections | Δρmin = −0.31 e Å−3 |
186 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.36432 (15) | 0.2392 (2) | 0.27761 (9) | 0.0380 (5) | |
C2 | 0.34175 (15) | 0.1626 (2) | 0.22779 (9) | 0.0403 (5) | |
C3 | 0.41472 (17) | 0.1589 (2) | 0.18170 (10) | 0.0471 (6) | |
C4 | 0.50361 (19) | 0.2333 (3) | 0.18622 (11) | 0.0607 (7) | |
H1A | 0.5523 | 0.2287 | 0.1559 | 0.073* | |
C5 | 0.52163 (19) | 0.3142 (3) | 0.23476 (12) | 0.0648 (7) | |
H13 | 0.5802 | 0.3670 | 0.2362 | 0.078* | |
C6 | 0.45235 (17) | 0.3159 (2) | 0.28092 (11) | 0.0510 (6) | |
H14 | 0.4645 | 0.3685 | 0.3143 | 0.061* | |
C7 | 0.24248 (18) | 0.0871 (3) | 0.22183 (11) | 0.0593 (7) | |
H11A | 0.2014 | 0.1006 | 0.2569 | 0.089* | |
H11B | 0.2570 | −0.0058 | 0.2174 | 0.089* | |
H11C | 0.2057 | 0.1183 | 0.1874 | 0.089* | |
C8 | 0.3960 (2) | 0.0772 (3) | 0.12657 (11) | 0.0689 (8) | |
H12A | 0.4552 | 0.0817 | 0.1011 | 0.103* | |
H12B | 0.3371 | 0.1111 | 0.1057 | 0.103* | |
H12C | 0.3838 | −0.0134 | 0.1377 | 0.103* | |
C9 | 0.42663 (14) | 0.14693 (19) | 0.41375 (8) | 0.0334 (4) | |
C10 | 0.45813 (15) | 0.2588 (2) | 0.44538 (9) | 0.0376 (5) | |
C11 | 0.55332 (16) | 0.2609 (2) | 0.47257 (10) | 0.0469 (5) | |
H7 | 0.5742 | 0.3358 | 0.4936 | 0.056* | |
C12 | 0.61758 (16) | 0.1526 (2) | 0.46883 (10) | 0.0490 (6) | |
H8 | 0.6814 | 0.1538 | 0.4875 | 0.059* | |
C13 | 0.58658 (16) | 0.0429 (2) | 0.43732 (9) | 0.0416 (5) | |
C14 | 0.49226 (15) | 0.0390 (2) | 0.40944 (9) | 0.0389 (5) | |
H10 | 0.4727 | −0.0356 | 0.3878 | 0.047* | |
Cl1 | 0.38122 (4) | 0.39770 (5) | 0.45093 (3) | 0.04880 (16) | |
Cl2 | 0.66673 (5) | −0.09408 (7) | 0.43314 (3) | 0.0630 (2) | |
S1 | 0.30265 (4) | 0.13320 (5) | 0.38004 (2) | 0.03558 (14) | |
N1 | 0.29345 (12) | 0.24200 (17) | 0.32771 (8) | 0.0376 (4) | |
H1 | 0.2777 (16) | 0.322 (2) | 0.3392 (10) | 0.045* | |
O1 | 0.30173 (10) | 0.00454 (14) | 0.35289 (7) | 0.0443 (4) | |
O2 | 0.22658 (11) | 0.16635 (16) | 0.42321 (7) | 0.0487 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0366 (10) | 0.0394 (12) | 0.0381 (11) | 0.0035 (9) | −0.0028 (8) | 0.0021 (10) |
C2 | 0.0406 (11) | 0.0416 (12) | 0.0386 (12) | 0.0063 (10) | −0.0032 (9) | −0.0006 (10) |
C3 | 0.0519 (13) | 0.0519 (14) | 0.0375 (12) | 0.0134 (11) | 0.0019 (10) | 0.0036 (11) |
C4 | 0.0500 (13) | 0.0814 (19) | 0.0506 (15) | 0.0037 (13) | 0.0089 (11) | 0.0181 (14) |
C5 | 0.0498 (14) | 0.0821 (19) | 0.0627 (17) | −0.0222 (14) | −0.0005 (12) | 0.0166 (15) |
C6 | 0.0541 (13) | 0.0544 (14) | 0.0446 (13) | −0.0158 (12) | −0.0040 (11) | 0.0014 (12) |
C7 | 0.0507 (13) | 0.0732 (17) | 0.0540 (14) | −0.0088 (13) | −0.0089 (11) | −0.0155 (14) |
C8 | 0.0825 (19) | 0.078 (2) | 0.0458 (14) | 0.0175 (15) | 0.0057 (13) | −0.0104 (14) |
C9 | 0.0351 (10) | 0.0356 (11) | 0.0296 (10) | −0.0050 (9) | 0.0024 (8) | −0.0019 (9) |
C10 | 0.0390 (10) | 0.0374 (11) | 0.0365 (11) | −0.0029 (9) | −0.0006 (8) | −0.0027 (9) |
C11 | 0.0462 (12) | 0.0483 (13) | 0.0461 (13) | −0.0077 (11) | −0.0079 (10) | −0.0096 (11) |
C12 | 0.0382 (11) | 0.0592 (15) | 0.0497 (14) | −0.0038 (11) | −0.0091 (10) | −0.0002 (12) |
C13 | 0.0401 (11) | 0.0439 (12) | 0.0407 (12) | 0.0038 (10) | 0.0028 (9) | 0.0077 (10) |
C14 | 0.0412 (11) | 0.0373 (11) | 0.0384 (11) | −0.0036 (9) | 0.0018 (9) | −0.0021 (9) |
Cl1 | 0.0479 (3) | 0.0399 (3) | 0.0586 (4) | 0.0005 (2) | −0.0035 (2) | −0.0150 (3) |
Cl2 | 0.0558 (4) | 0.0571 (4) | 0.0760 (4) | 0.0165 (3) | −0.0020 (3) | 0.0082 (3) |
S1 | 0.0320 (2) | 0.0373 (3) | 0.0374 (3) | −0.0063 (2) | 0.0019 (2) | −0.0072 (2) |
N1 | 0.0382 (9) | 0.0360 (9) | 0.0386 (9) | 0.0041 (8) | 0.0001 (7) | −0.0077 (8) |
O1 | 0.0438 (8) | 0.0374 (8) | 0.0515 (9) | −0.0084 (7) | −0.0015 (7) | −0.0112 (7) |
O2 | 0.0393 (8) | 0.0595 (10) | 0.0473 (9) | −0.0077 (7) | 0.0115 (7) | −0.0117 (8) |
C1—C6 | 1.384 (3) | C8—H12C | 0.9600 |
C1—C2 | 1.388 (3) | C9—C14 | 1.386 (3) |
C1—N1 | 1.453 (3) | C9—C10 | 1.394 (3) |
C2—C3 | 1.403 (3) | C9—S1 | 1.786 (2) |
C2—C7 | 1.505 (3) | C10—C11 | 1.380 (3) |
C3—C4 | 1.381 (3) | C10—Cl1 | 1.725 (2) |
C3—C8 | 1.505 (3) | C11—C12 | 1.377 (3) |
C4—C5 | 1.379 (4) | C11—H7 | 0.9300 |
C4—H1A | 0.9300 | C12—C13 | 1.372 (3) |
C5—C6 | 1.372 (3) | C12—H8 | 0.9300 |
C5—H13 | 0.9300 | C13—C14 | 1.377 (3) |
C6—H14 | 0.9300 | C13—Cl2 | 1.732 (2) |
C7—H11A | 0.9600 | C14—H10 | 0.9300 |
C7—H11B | 0.9600 | S1—O2 | 1.4235 (14) |
C7—H11C | 0.9600 | S1—O1 | 1.4323 (14) |
C8—H12A | 0.9600 | S1—N1 | 1.6098 (18) |
C8—H12B | 0.9600 | N1—H1 | 0.87 (2) |
C6—C1—C2 | 121.9 (2) | H12B—C8—H12C | 109.5 |
C6—C1—N1 | 118.21 (19) | C14—C9—C10 | 119.30 (18) |
C2—C1—N1 | 119.86 (18) | C14—C9—S1 | 117.77 (15) |
C1—C2—C3 | 117.6 (2) | C10—C9—S1 | 122.90 (15) |
C1—C2—C7 | 122.27 (19) | C11—C10—C9 | 120.01 (19) |
C3—C2—C7 | 120.1 (2) | C11—C10—Cl1 | 118.46 (16) |
C4—C3—C2 | 119.9 (2) | C9—C10—Cl1 | 121.52 (15) |
C4—C3—C8 | 119.5 (2) | C12—C11—C10 | 120.4 (2) |
C2—C3—C8 | 120.6 (2) | C12—C11—H7 | 119.8 |
C5—C4—C3 | 121.4 (2) | C10—C11—H7 | 119.8 |
C5—C4—H1A | 119.3 | C13—C12—C11 | 119.42 (19) |
C3—C4—H1A | 119.3 | C13—C12—H8 | 120.3 |
C6—C5—C4 | 119.4 (2) | C11—C12—H8 | 120.3 |
C6—C5—H13 | 120.3 | C12—C13—C14 | 121.2 (2) |
C4—C5—H13 | 120.3 | C12—C13—Cl2 | 119.53 (17) |
C5—C6—C1 | 119.7 (2) | C14—C13—Cl2 | 119.27 (18) |
C5—C6—H14 | 120.1 | C13—C14—C9 | 119.7 (2) |
C1—C6—H14 | 120.1 | C13—C14—H10 | 120.2 |
C2—C7—H11A | 109.5 | C9—C14—H10 | 120.2 |
C2—C7—H11B | 109.5 | O2—S1—O1 | 119.69 (9) |
H11A—C7—H11B | 109.5 | O2—S1—N1 | 106.47 (9) |
C2—C7—H11C | 109.5 | O1—S1—N1 | 107.85 (9) |
H11A—C7—H11C | 109.5 | O2—S1—C9 | 108.78 (9) |
H11B—C7—H11C | 109.5 | O1—S1—C9 | 104.91 (9) |
C3—C8—H12A | 109.5 | N1—S1—C9 | 108.81 (9) |
C3—C8—H12B | 109.5 | C1—N1—S1 | 120.16 (14) |
H12A—C8—H12B | 109.5 | C1—N1—H1 | 113.4 (15) |
C3—C8—H12C | 109.5 | S1—N1—H1 | 115.5 (15) |
H12A—C8—H12C | 109.5 | ||
C6—C1—C2—C3 | 3.8 (3) | Cl1—C10—C11—C12 | −179.43 (18) |
N1—C1—C2—C3 | −177.39 (18) | C10—C11—C12—C13 | 0.6 (3) |
C6—C1—C2—C7 | −175.2 (2) | C11—C12—C13—C14 | −0.1 (3) |
N1—C1—C2—C7 | 3.6 (3) | C11—C12—C13—Cl2 | −179.36 (17) |
C1—C2—C3—C4 | −2.0 (3) | C12—C13—C14—C9 | −0.8 (3) |
C7—C2—C3—C4 | 177.0 (2) | Cl2—C13—C14—C9 | 178.45 (15) |
C1—C2—C3—C8 | 179.5 (2) | C10—C9—C14—C13 | 1.2 (3) |
C7—C2—C3—C8 | −1.5 (3) | S1—C9—C14—C13 | −176.79 (16) |
C2—C3—C4—C5 | −1.5 (4) | C14—C9—S1—O2 | 127.48 (16) |
C8—C3—C4—C5 | 177.1 (2) | C10—C9—S1—O2 | −50.46 (19) |
C3—C4—C5—C6 | 3.3 (4) | C14—C9—S1—O1 | −1.71 (18) |
C4—C5—C6—C1 | −1.5 (4) | C10—C9—S1—O1 | −179.65 (16) |
C2—C1—C6—C5 | −2.0 (3) | C14—C9—S1—N1 | −116.91 (16) |
N1—C1—C6—C5 | 179.1 (2) | C10—C9—S1—N1 | 65.14 (18) |
C14—C9—C10—C11 | −0.7 (3) | C6—C1—N1—S1 | −93.2 (2) |
S1—C9—C10—C11 | 177.17 (16) | C2—C1—N1—S1 | 87.9 (2) |
C14—C9—C10—Cl1 | 178.49 (15) | O2—S1—N1—C1 | 177.30 (15) |
S1—C9—C10—Cl1 | −3.6 (2) | O1—S1—N1—C1 | −53.06 (17) |
C9—C10—C11—C12 | −0.2 (3) | C9—S1—N1—C1 | 60.22 (17) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.87 (2) | 2.14 (2) | 2.975 (2) | 162.9 (19) |
Symmetry code: (i) −x+1/2, y+1/2, z. |
Experimental details
Crystal data | |
Chemical formula | C14H13Cl2NO2S |
Mr | 330.21 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 296 |
a, b, c (Å) | 13.0069 (11), 10.0775 (9), 22.408 (2) |
V (Å3) | 2937.2 (4) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.58 |
Crystal size (mm) | 0.30 × 0.20 × 0.18 |
Data collection | |
Diffractometer | Bruker APEXII CCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 23820, 3260, 2377 |
Rint | 0.045 |
(sin θ/λ)max (Å−1) | 0.643 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.090, 0.98 |
No. of reflections | 3260 |
No. of parameters | 186 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.26, −0.31 |
Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.87 (2) | 2.14 (2) | 2.975 (2) | 162.9 (19) |
Symmetry code: (i) −x+1/2, y+1/2, z. |
Acknowledgements
The authors are grateful to the Higher Education Commission (HEC), Pakistan, for providing funds for the single-crystal XRD facilities at GC University Lahore.
References
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Mughal, S. Y., Khan, I. U., Harrison, W. T. A., Khan, M. H. & Arshad, M. N. (2012a). Acta Cryst. E68, o2433. CSD CrossRef IUCr Journals Google Scholar
Mughal, S. Y., Khan, I. U., Harrison, W. T. A., Khan, M. H. & Arshad, M. N. (2012b). Acta Cryst. E68, o2476. CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
The title compound, (I), (Fig. 1) was examined as part of our ongoing interest in the structural chemistry of sulfonamides (Mughal et al., 2012a,b).
The dihedral angle between the C1—C6 and C9—C14 benzene rings in (I) is 62.21 (7)°. The C1—N1—S1—C9 linkage adopts a near-ideal gauche conformation [torsion angle = 60.22 (17)°] and the bond-angle sum about N1 (H atom freely refined) is 349°, possibly suggesting a hybridization state intermediate between sp2 and sp3, which was also observed in a related compound (Mughal et al., 2012a). The largest bond angle at the distorted tetrahedral S atom is O1—S1—O2 [119.69 (9)°], which again is typical for this class of compound (Mughal et al., 2012b).
In the crystal, the molecules are linked by N—H···O hydrogen bonds (Table 1) to generate C(4) chains propagating in [010]: adjacent molecules are in the chain are generated by glide-symmetry. A similar chain occurs in N-(2,3-dihydro-1,4-benzodioxin-6-yl)-4-fluorobenzenesulfonamide (Mughal et al., 2012a), although in this case, adjacent molecules are generated by translational symmetry. Conversely, in 2,5-dichloro-N-(3-methylphenyl)benzenesulfonamide (Mughal et al., 2012b), pairs of N—H···O interactions lead to inversion dimers in the crystal.
Any aromatic π-π stacking in (I), if it exists at all, must be extremely weak, as the shortest inter-centroid ring separation is 4.0550 (12) Å between inversion-symmetry related C9–C14 rings (slippage = 1.906 Å). A short intermolecular Cl···O contact of 3.1115 (17) Å occurs (van der Waals' radius sum for these species = 3.27 Å).