N -(4-Chloro-2-nitrophenyl)methanesulfonamide

organic compounds Acta Crystallographica Section E Z=4 Mo K radiation  = 0.58 mm1 Structure Reports Online ISSN 1600-5368 T = 296 (2) K 0.22  0.14  0.07 mm Data collection N-(4-Chloro-2-nitrophenyl)methanesulfonamide Bruker APEXII CCD area-detector diffractometer Absorption correction: none 10700 measured reflections 2590 independent reflections 1199 reflections with I > 2(I) Rint = 0.081 Refinement Muhammad Zia-ur-Rehman,a* Jamil Anwar Choudary,b Nosheen Akbar,c Islam Ullah Khand and Muhammad Nadeem Arshadd R[F 2 > 2(F 2)] = 0.050 wR(F 2) = 0.147 S = 0.97 2556 reflections 140 parameters H atoms treated by a mixture of independent and constrained refinement
max = 0.25 e Å3
min = 0.39 e Å3 a Applied Chemistry Research Centre, PCSIR Laboratories Complex, Lahore 54600, Pakistan, bInstitute of Chemistry, University of the Punjab, Lahore 54590, Pakistan, c Centre for High Energy Physics, University of the Punjab, Lahore 54590, Pakistan, and dDepartment of Chemistry, Government College University, Lahore 54000, Pakistan Correspondence e-mail: [email protected] Received 18 September 2008; accepted 25 September 2008 Key indicators: single-crystal X-ray study; T = 296 K; mean (C–C) = 0.005 Å; R factor = 0.050; wR factor = 0.147; data-to-parameter ratio = 18.3. Table 1 Hydrogen-bond geometry (Å,  ). D—H


A D—H H


A D


A D—H


A N1—H1


O3 C3—H3


O3i C5—H5


O2ii C6—H6


O2 C7—H8


O3iii 0.80 (4) 0.93 0.93 0.93 0.96 2.03 (4) 2.59 2.47 2.27 2.53 2.631 3.417 3.325 2.951 3.394 131 (3) 148 152 130 150 Symmetry codes: (i) x þ 2; y; z þ 2. The title compound, C7H7ClN2O4S, is of interest as a precursor to biologically active substituted quinolines. Its structure resembles those of the previously reported N-phenylmethane sulfonamide and its 4-nitro, 4-fluoro and 4-bromo derivatives, with slightly different geometric parameters. An intramolecular N—H


O hydrogen bond gives rise to a six-membered ring. Intermolecular C—H


O contacts stabilize the crystal packing. Related literature For related literature, see: Ahn et al. (1997); Allen et al. (1987); Ozbek et al. (2007); Siddiqui et al. (2007); Gennarti et al. (1994); Gowda et al. (2007a,b,c); Hanson et al. (1999); Moree et al. (1991); Oppolzer et al. (1991); Rough et al. (1998); Zia-urRehman et al. (2005, 2006, 2007, 2008). x þ 32; y  12; z þ 32; (ii) (4) (4) (5) (5) (5) x þ 1; y þ 1; z þ 2; (iii) Data collection: APEX2 (Bruker, 2007); cell refinement: 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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2003). The authors are grateful to the PCSIR Laboratories Complex, Lahore, Pakistan, for provision of the necessary chemicals, and to the Higher Education Commission of Pakistan for the grant to purchase the diffractometer. Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BT2794). References Experimental Crystal data C7H7ClN2O4S Mr = 250.67 Monoclinic, P21 =n a = 11.728 (3) Å o2034 Zia-ur-Rehman et al. b = 4.9798 (13) Å c = 17.988 (5) Å = 107.334 (8) V = 1002.8 (5) Å3 Ahn, K. H., Ham, C., Kim, S.-K. & Cho, C.-W. (1997). J. Org. Chem. 62, 7047– 7048. Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. Gennarti, C., Salom, B., Potenza, D. & Williams, A. (1994). Angew. Chem. Int. Ed. Engl. 33, 2067–2069. Gowda, B. T., Foro, S. & Fuess, H. (2007a). Acta Cryst. E63, o2339. Gowda, B. T., Foro, S. & Fuess, H. (2007b). Acta Cryst. E63, o2570. Gowda, B. T., Foro, S. & Fuess, H. (2007c). Acta Cryst. E63, o2597. Hanson, P. R., Probst, D. A., Robinson, R. E. & Yau, M. (1999). Tetrahedron Lett. 40, 4761–4763. Moree, W. J., Van der Marel, G. A. & Liskamp, R. M. (1991). Tetrahedron Lett. 32, 409–411. Oppolzer, W., Kingma, A. J. & Pillai, S.-K. (1991). Tetrahedron Lett. 32, 4893– 4895. Ozbek, N., Katircioğlu, H., Karacan, N. & Baykal, T. (2007). Bioorg. Med. Chem. 15, 5105–5109. doi:10.1107/S1600536808031048 Acta Cryst. (2008). E64, o2034–o2035 organic compounds Rough, W. R., Gwaltney, S. L., Cheng, J., Scheidt, K. A., Mc Kerrow, J. H. & Hansell, E. (1998). J. Am. Chem. Soc. 120, 10994–10995. Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Siddiqui, N., Pandeya, S. N., Khan, S. A., Stables, J., Rana, A., Alam, M., Arshad, M. F. & Bhat, M. A. (2007). Bioorg. Med. Chem. Lett. 17, 255–259. Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Zia-ur-Rehman, M., Choudary, J. A. & Ahmad, S. (2005). Bull. Korean Chem. Soc. 26, 1771–1775. Acta Cryst. (2008). E64, o2034–o2035 Zia-ur-Rehman, M. Z., Choudary, J. A., Ahmad, S. & Siddiqui, H. L. (2006). Chem. Pharm. Bull. 54, 1175–1178. Zia-ur-Rehman, M., Choudary, J. A., Elsegood, M. R. J., Siddiqui, H. L. & Khan, K. M. (2008). Eur. J. Med. Chem. In the press. doi: 10.1016/ j.ejmech.2008.08.002. Zia-ur-Rehman, M., Choudary, J. A., Elsegood, M. R. J., Siddiqui, H. L. & Weaver, G. W. (2007). Acta Cryst. E63, o4215–o4216. Zia-ur-Rehman et al.  C7H7ClN2O4S o2035 supplementary materials supplementary materials Acta Cryst. (2008). E64, o2034-o2035 [ doi:10.1107/S1600536808031048 ] N-(4-Chloro-2-nitrophenyl)methanesulfonamide M. Zia-ur-Rehman, J. A. Choudary, N. Akbar, I. U. Khan and M. Nadeem Arshad Comment Sulfonamides are familiar for their enormous potential as biologically active molecules (Hanson et al., 1999; Moree et al., 1991; Rough et al., 1998). They are being used as anti-microbial (Ozbek et al., 2007), anti-convulsant (Siddiqui et al., 2007), and for the treatment of inflammatory rheumatic and non-rheumatic processes including onsets and traumatologic lesions (Gennarti et al., 1994). Besides, these are known as compounds being used as agricultural agents and chiral auxiliaries (Ahn et al., 1997; Oppolzer et al., 1991). Among these, alkyl sulfonanilides are of special interest due to their stereochemistry with amide hydrogen on one side of the plane of benzene ring making it a good receptor site for biological reactions. In the present paper, the structure of N-(4-chloro-2-nitrophenyl)methanesulfonamide has been determined as part of a research program involving the synthesis and biological evaluation of sulfur containing heterocyclic compounds (Zia-ur-Rehman et al., 2005, 2006, 2007, 2008). In the molecule of (I) (Fig. 1), bond lengths and bond angles are almost similar to those in the related molecules (Gowda et al., 2007a,b,c) and are within normal ranges (Allen et al., 1987). Intramolecular interaction [N1—H1···O3] is observed in the title molecule giving rise to six-membered hydrogen bonded ring. Each molecule is centrosymmetrically linked to its adjacent one through intermolecular [C7—H8···O3] hydrogen bonds on one side, and via [C5—H5···O2] hydrogen bonds on the other side, giving rise to a zigzag chain along a axis. Each molecule of a chain is further linked to the member of adjacent chain via [C3—H3···O3] hydrogen bonds along c giving rise to a three dimensional network. Experimental A mixture of 4-chloro-2-nitroaniline (3.452 g; 20.0 mmoles) and mesyl chloride (2.52 g; 22.0 mmoles) and toluene (25.0 ml) was heated to reflux for half an hour. Solvent was then distilled off under reduced pressure and the resultant solids were washed with cold methanol. Crystals suitable for analysis were obtained by slow evaporation of methanolic solution over a period of two days. Refinement H atoms bound to C were placed in calculated positions (C—H distance = 0.95 Å) using a riding model. H atoms on N and O were freely refined. Figures Fig. 1. The asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 50% probability level. sup-1 supplementary materials Fig. 2. Perspective view of the crystal packing showing hydrogen bonds (dashed lines). H atoms not involved in hydrogen bonding have been omitted for clarity. N-(4-Chloro-2-nitrophenyl)methanesulfonamide Crystal data C7H7ClN2O4S F000 = 512 Mr = 250.67 Dx = 1.660 Mg m−3 Monoclinic, P21/n Melting point: 388 K Hall symbol: -P 2yn a = 11.728 (3) Å b = 4.9798 (13) Å c = 17.988 (5) Å β = 107.334 (8)º V = 1002.8 (5) Å3 Z=4 Mo Kα radiation λ = 0.71073 Å Cell parameters from 1283 reflections θ = 2.4–20.9º µ = 0.58 mm−1 T = 296 (2) K Needle, light yellow 0.22 × 0.14 × 0.07 mm Data collection Bruker APEXII CCD area-detector diffractometer Radiation source: fine-focus sealed tube Monochromator: graphite 2590 independent reflections 1199 reflections with I > 2σ(I) Rint = 0.081 Detector resolution: 7.5 pixels mm-1 θmax = 28.7º T = 296(2) K θmin = 1.9º φ and ω scans Absorption correction: none 10700 measured reflections h = −15→15 k = −6→6 l = −23→24 Refinement Refinement on F2 Least-squares matrix: full R[F2 > 2σ(F2)] = 0.050 wR(F2) = 0.148 Secondary atom site location: difference Fourier map Hydrogen site location: inferred from neighbouring sites H atoms treated by a mixture of independent and constrained refinement w = 1/[σ2(Fo2) + (0.0627P)2] where P = (Fo2 + 2Fc2)/3 S = 0.97 (Δ/σ)max < 0.001 2556 reflections Δρmax = 0.25 e Å−3 sup-2 supplementary materials Δρmin = −0.39 e Å−3 140 parameters Primary atom site location: structure-invariant direct Extinction correction: none methods 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 Rfactors(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) Cl1 S1 O1 O2 O3 O4 H1 N1 N2 C1 C2 C3 H3 C4 C5 H5 C6 H6 C7 H8 H9 H7 x y z Uiso*/Ueq 0.36565 (9) 0.82089 (9) 0.9148 (3) 0.7141 (2) 0.8855 (2) 0.8088 (2) 0.852 (3) 0.7906 (3) 0.8034 (3) 0.6920 (3) 0.6953 (3) 0.5963 (3) 0.6013 0.4913 (3) 0.4847 (3) 0.4136 0.5830 (4) 0.5767 0.8741 (4) 0.9413 0.8121 0.8984 −0.3010 (2) 0.53780 (17) 0.7102 (5) 0.6562 (5) 0.1004 (5) −0.2740 (5) 0.324 (7) 0.3571 (6) −0.0641 (6) 0.1941 (6) −0.0052 (6) −0.1573 (7) −0.2884 −0.1147 (7) 0.0733 (7) 0.0974 0.2266 (7) 0.3554 0.3148 (8) 0.2183 0.1903 0.4127 0.78879 (7) 1.02558 (6) 1.01960 (19) 1.03188 (16) 0.85222 (14) 0.80406 (15) 0.938 (2) 0.94717 (19) 0.83722 (16) 0.91264 (19) 0.85865 (19) 0.8216 (2) 0.7859 0.8376 (2) 0.8916 (2) 0.9037 0.9282 (2) 0.9642 1.1025 (3) 1.0959 1.1036 1.1507 0.0757 (4) 0.0499 (3) 0.0756 (9) 0.0647 (8) 0.0554 (7) 0.0613 (7) 0.047 (11)* 0.0509 (8) 0.0441 (7) 0.0416 (8) 0.0397 (8) 0.0473 (9) 0.057* 0.0507 (9) 0.0559 (10) 0.067* 0.0556 (10) 0.067* 0.0756 (13) 0.113* 0.113* 0.113* Atomic displacement parameters (Å2) Cl1 S1 O1 U11 0.0495 (6) 0.0594 (6) 0.083 (2) U22 0.0871 (8) 0.0414 (5) 0.0540 (15) U33 0.0875 (9) 0.0527 (6) 0.100 (2) U12 −0.0078 (5) 0.0081 (4) −0.0184 (14) U13 0.0156 (6) 0.0224 (5) 0.0431 (19) U23 −0.0033 (6) −0.0082 (4) −0.0276 (15) sup-3 supplementary materials O2 O3 O4 N1 N2 C1 C2 C3 C4 C5 C6 C7 0.0700 (18) 0.0468 (15) 0.0608 (17) 0.050 (2) 0.0457 (18) 0.048 (2) 0.042 (2) 0.050 (2) 0.042 (2) 0.044 (2) 0.060 (3) 0.086 (3) 0.0622 (16) 0.0678 (16) 0.0650 (16) 0.0539 (18) 0.0526 (17) 0.0412 (18) 0.0445 (18) 0.053 (2) 0.058 (2) 0.061 (2) 0.053 (2) 0.075 (3) 0.0661 (19) 0.0571 (18) 0.0627 (19) 0.058 (2) 0.0364 (17) 0.040 (2) 0.0361 (19) 0.040 (2) 0.053 (2) 0.071 (3) 0.063 (3) 0.058 (3) 0.0267 (13) −0.0027 (13) 0.0092 (12) 0.0022 (16) 0.0107 (15) 0.0068 (16) 0.0112 (15) 0.0066 (17) 0.0034 (17) 0.0128 (19) 0.0093 (19) 0.021 (2) 0.0267 (14) 0.0238 (13) 0.0255 (14) 0.0296 (17) 0.0157 (13) 0.0205 (17) 0.0167 (16) 0.0149 (17) 0.0137 (18) 0.029 (2) 0.032 (2) 0.010 (2) −0.0096 (13) −0.0109 (13) −0.0258 (13) −0.0131 (14) −0.0016 (13) 0.0032 (15) 0.0071 (14) −0.0007 (16) 0.0078 (18) 0.006 (2) −0.0051 (18) 0.003 (2) Geometric parameters (Å, °) Cl1—C4 S1—O2 S1—O1 S1—N1 S1—C7 O3—N2 O4—N2 N1—C1 N1—H1 N2—C2 C1—C2 1.741 (4) 1.419 (3) 1.426 (3) 1.621 (3) 1.739 (4) 1.231 (3) 1.215 (3) 1.397 (4) 0.80 (3) 1.461 (4) 1.397 (4) C1—C6 C2—C3 C3—C4 C3—H3 C4—C5 C5—C6 C5—H5 C6—H6 C7—H8 C7—H9 C7—H7 1.397 (5) 1.380 (5) 1.363 (4) 0.9300 1.368 (5) 1.375 (5) 0.9300 0.9300 0.9600 0.9600 0.9600 O2—S1—O1 O2—S1—N1 O1—S1—N1 O2—S1—C7 O1—S1—C7 N1—S1—C7 C1—N1—S1 C1—N1—H1 S1—N1—H1 O4—N2—O3 O4—N2—C2 O3—N2—C2 C2—C1—C6 C2—C1—N1 C6—C1—N1 C3—C2—C1 C3—C2—N2 C1—C2—N2 118.43 (17) 109.28 (17) 104.05 (17) 108.5 (2) 110.0 (2) 105.77 (19) 130.3 (3) 118 (3) 108 (3) 121.9 (3) 118.6 (3) 119.5 (3) 116.0 (3) 122.1 (3) 121.9 (3) 122.1 (3) 115.7 (3) 122.2 (3) C4—C3—C2 C4—C3—H3 C2—C3—H3 C3—C4—C5 C3—C4—Cl1 C5—C4—Cl1 C4—C5—C6 C4—C5—H5 C6—C5—H5 C5—C6—C1 C5—C6—H6 C1—C6—H6 S1—C7—H8 S1—C7—H9 H8—C7—H9 S1—C7—H7 H8—C7—H7 H9—C7—H7 119.7 (3) 120.1 120.1 120.2 (3) 119.5 (3) 120.3 (3) 120.2 (3) 119.9 119.9 121.8 (3) 119.1 119.1 109.5 109.5 109.5 109.5 109.5 109.5 O2—S1—N1—C1 O1—S1—N1—C1 C7—S1—N1—C1 S1—N1—C1—C2 S1—N1—C1—C6 −37.6 (4) −165.0 (3) 79.0 (4) −161.2 (3) 21.0 (5) O4—N2—C2—C1 O3—N2—C2—C1 C1—C2—C3—C4 N2—C2—C3—C4 C2—C3—C4—C5 163.9 (3) −17.0 (4) −0.1 (5) −179.5 (3) −1.7 (5) sup-4 supplementary materials C6—C1—C2—C3 N1—C1—C2—C3 C6—C1—C2—N2 N1—C1—C2—N2 O4—N2—C2—C3 O3—N2—C2—C3 1.3 (5) −176.7 (3) −179.3 (3) 2.7 (5) −16.6 (4) 162.5 (3) C2—C3—C4—Cl1 C3—C4—C5—C6 Cl1—C4—C5—C6 C4—C5—C6—C1 C2—C1—C6—C5 N1—C1—C6—C5 178.3 (3) 2.2 (6) −177.8 (3) −1.0 (6) −0.7 (5) 177.2 (3) Hydrogen-bond geometry (Å, °) D—H···A N1—H1···O3 D—H 0.80 (4) H···A 2.03 (4) D···A 2.631 (4) D—H···A 131 (3) C3—H3···O3i 0.93 2.59 3.417 (4) 148 ii C5—H5···O2 C6—H6···O2 0.93 2.47 3.325 (5) 152 0.93 2.27 2.951 (5) 130 3.394 (5) 150 0.96 2.53 C7—H8···O3iii Symmetry codes: (i) −x+3/2, y−1/2, −z+3/2; (ii) −x+1, −y+1, −z+2; (iii) −x+2, −y, −z+2. sup-5 supplementary materials Fig. 1 sup-6 supplementary materials Fig. 2 sup-7