organic compounds
4-Bromo-N-(4-fluorophenyl)benzenesulfonamide
aDepartment of PG Studies and Research in Chemistry, St Aloysius College, Mangalore, India, bDepartment of Chemistry, University College of Science, Tumkur University, Tumkur 572 103, India, cDepartment of Studies in Physics, University of Mysore, Manasagangotri, Mysuru-6, India, and dInstitution of Excellence, University of Mysore, Manasagangotri, Mysuru-6, India
*Correspondence e-mail: naveen@ioe.uni-mysore.ac.in
The title molecule, C12H9BrFNO2S, is U-shaped with the central C—S—N—C fragment having a torsion angle of 68.4 (3)° and a dihedral angle between the planes of the two benzene rings of 41.17 (19)°. The features strong N—H⋯O hydrogen bonds between the molecules, forming infinite one-dimensional C(4) chains along [001]. These chains are interconnected via short F⋯F contacts [F⋯F = 2.868 (4) Å], forming a one-dimensional ribbon-like architecture.
Keywords: crystal structure; sulfonamides; N—H⋯O hydrogen bonds; F⋯F contacts.
CCDC reference: 1497562
Structure description
Sulfonamide drugs were the first among the chemotherapeutic agents to be used for the curing and prevention of bacterial infection in human beings (Shiva Prasad et al., 2011). They play a vital role as a key constituent in a number of biologically active molecules. To date, have been known to exhibit a wide variety of biological activities, such as antibacterial (Subhakara Reddy et al., 2012), insecticidal (Himel et al., 1971), antifungal (Hanafy et al., 2007), antihepatitis (Zhao et al., 2010), anti-inflammatory (Küçükgüzel et al., 2013), antitumour (Ghorab et al., 2011), anticancer (Al-Said et al., 2011), anti-HIV (Sahu et al., 2007) and antitubercular activities (Vora & Mehta, 2012). In recent years, extensive research studies have been carried out on the synthesis and evaluation of the pharmacological activities of molecules containing a sulfonamide moiety, and important pharmacophores have been reported (Mohan et al., 2013). With this in mind and in our continued efforts for understanding the structures of N-(4-substituted phenyl)-4-bromobenzenesulfonamides (Rodrigues et al., 2015, 2016), we report herein the of 4-bromo-N-(4-fluorophenyl)benzenesulfonamide, (I).
The molecule of (I) (Fig. 1) is U-shaped, with the central C4—S1—N1—C7 fragment having a torsion angle of 68.4 (3)°. The dihedral angle between the planes of the two benzene rings is 41.17 (19)°. In comparison, the dihedral angles between the planes of the two benzene rings in the reported structures of 4-bromo-N-(4-bromophenyl)benzenesulfonamide, (II) (Rodrigues et al., 2015), and 4-bromo-N-(4-nitrophenyl)benzenesulfonamide, (III) (Rodrigues et al., 2016), are slightly less than that in (I), with values of 38.5 (2)° in (II) and 32.6 (6)° in (III).
The i hydrogen bonds (Table 1 and Fig. 2) between the molecules, forming infinite one-dimensional C(4) chains along [001]. These chains are interconnected via F⋯F(−x, −y, z + ) contacts [F⋯F = 2.868 (4) Å], forming a one-dimensional ribbon-like architecture (Fig. 2). In contrast, in (II) and (III), three-dimensional supramolecular architectures are present as a result of N—H⋯O(S) chains, structure-directing C—H⋯O interactions and other weak interactions of the types Br⋯Br [in (II)] and Br⋯Onitro [in (III)].
of (I) features strong N1—H1⋯O2Synthesis and crystallization
Compound (I) was prepared according to the literature method of Rodrigues et al. (2015). The purity of the compound was checked by determining its melting point (m.p. 400 K). Prismatic single crystals of (I) used for X-ray diffraction study were obtained by slow evaporation of an ethanolic solution of (I) at room temperature.
Refinement
Crystal data, data collection and structure . Two reflections with bad agreement between Fo and Fc, viz. 110 and 120, were omitted from the final refinement.
details are summarized in Table 2Structural data
CCDC reference: 1497562
10.1107/S2414314616012566/lh4010sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2414314616012566/lh4010Isup2.hkl
Supporting information file. DOI: 10.1107/S2414314616012566/lh4010Isup3.cml
Data collection: APEX2 (Bruker, 2009); cell
APEX2 and SAINT-Plus (Bruker, 2009); data reduction: SAINT-Plus and XPREP (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).C12H9BrFNO2S | Prism |
Mr = 330.17 | Dx = 1.760 Mg m−3 |
Orthorhombic, Pna21 | Cu Kα radiation, λ = 1.54178 Å |
Hall symbol: P 2c -2n | Cell parameters from 137 reflections |
a = 19.7608 (6) Å | θ = 5.7–64.1° |
b = 12.4156 (4) Å | µ = 6.14 mm−1 |
c = 5.0776 (2) Å | T = 296 K |
V = 1245.75 (7) Å3 | Prism, colourless |
Z = 4 | 0.27 × 0.24 × 0.19 mm |
F(000) = 656 |
Bruker APEXII diffractometer | 1621 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.053 |
Graphite monochromator | θmax = 64.1°, θmin = 5.7° |
φ and ω scans | h = −22→22 |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | k = −14→12 |
Tmin = 0.238, Tmax = 0.311 | l = −5→5 |
5649 measured reflections | 1 standard reflections every 1 reflections |
1688 independent reflections | intensity decay: 0.1% |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.033 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.083 | w = 1/[σ2(Fo2) + (0.0511P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max < 0.001 |
1688 reflections | Δρmax = 0.40 e Å−3 |
167 parameters | Δρmin = −0.36 e Å−3 |
2 restraints | Absolute structure: Flack (1983), 547 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.01 (3) |
Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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 | 0.39127 (18) | 0.1909 (3) | 0.1353 (8) | 0.0265 (8) | |
C2 | 0.34960 (19) | 0.1649 (3) | 0.3425 (9) | 0.0296 (9) | |
H2 | 0.3549 | 0.0997 | 0.4302 | 0.036* | |
C3 | 0.2997 (2) | 0.2365 (3) | 0.4200 (8) | 0.0289 (9) | |
H3 | 0.2707 | 0.2196 | 0.5580 | 0.035* | |
C4 | 0.29376 (18) | 0.3337 (3) | 0.2885 (7) | 0.0217 (8) | |
C5 | 0.3370 (2) | 0.3607 (4) | 0.0829 (8) | 0.0300 (10) | |
H5 | 0.3328 | 0.4267 | −0.0022 | 0.036* | |
C6 | 0.38626 (18) | 0.2882 (3) | 0.0067 (10) | 0.0326 (9) | |
H6 | 0.4157 | 0.3049 | −0.1301 | 0.039* | |
C7 | 0.13069 (18) | 0.2839 (3) | 0.2275 (7) | 0.0227 (8) | |
C8 | 0.08360 (19) | 0.2754 (3) | 0.4302 (7) | 0.0266 (9) | |
H8 | 0.0739 | 0.3348 | 0.5351 | 0.032* | |
C9 | 0.05147 (18) | 0.1789 (3) | 0.4750 (9) | 0.0296 (10) | |
H9 | 0.0208 | 0.1717 | 0.6129 | 0.035* | |
C10 | 0.0654 (2) | 0.0936 (3) | 0.3131 (9) | 0.0272 (10) | |
C11 | 0.1114 (2) | 0.0990 (3) | 0.1087 (9) | 0.0290 (10) | |
H11 | 0.1195 | 0.0398 | 0.0009 | 0.035* | |
C12 | 0.14518 (19) | 0.1957 (3) | 0.0700 (8) | 0.0276 (9) | |
H12 | 0.1776 | 0.2014 | −0.0620 | 0.033* | |
N1 | 0.16334 (17) | 0.3861 (3) | 0.1795 (6) | 0.0221 (7) | |
O1 | 0.24522 (13) | 0.5284 (2) | 0.2820 (5) | 0.0270 (6) | |
O2 | 0.20711 (16) | 0.4034 (2) | 0.6338 (6) | 0.0283 (7) | |
F1 | 0.03373 (12) | −0.0025 (2) | 0.3541 (6) | 0.0388 (6) | |
S1 | 0.22670 (5) | 0.42265 (7) | 0.3659 (2) | 0.0217 (2) | |
Br1 | 0.457510 (19) | 0.09041 (3) | 0.01845 (10) | 0.03674 (18) | |
H1 | 0.170 (2) | 0.393 (3) | 0.005 (3) | 0.030 (12)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0271 (18) | 0.022 (2) | 0.031 (2) | −0.0001 (16) | −0.0040 (15) | −0.0053 (19) |
C2 | 0.035 (2) | 0.022 (2) | 0.032 (2) | −0.0024 (17) | −0.0043 (17) | 0.0052 (19) |
C3 | 0.037 (2) | 0.025 (2) | 0.025 (2) | −0.0022 (17) | 0.0048 (15) | 0.0017 (17) |
C4 | 0.0228 (17) | 0.023 (2) | 0.0193 (19) | −0.0017 (16) | −0.0004 (13) | 0.0006 (15) |
C5 | 0.036 (2) | 0.023 (2) | 0.031 (2) | 0.0010 (17) | 0.0039 (16) | 0.0071 (17) |
C6 | 0.0282 (18) | 0.037 (2) | 0.033 (2) | −0.0012 (16) | 0.0095 (18) | −0.001 (2) |
C7 | 0.0263 (19) | 0.024 (2) | 0.0178 (19) | −0.0003 (16) | −0.0008 (14) | 0.0044 (16) |
C8 | 0.0289 (19) | 0.027 (2) | 0.024 (2) | 0.0023 (17) | 0.0050 (14) | −0.0029 (16) |
C9 | 0.0265 (17) | 0.033 (2) | 0.029 (3) | 0.0018 (16) | 0.0073 (17) | 0.002 (2) |
C10 | 0.028 (2) | 0.023 (2) | 0.030 (3) | −0.0038 (15) | −0.0023 (18) | 0.0020 (16) |
C11 | 0.036 (2) | 0.026 (2) | 0.024 (2) | −0.0017 (16) | 0.0017 (17) | −0.0043 (17) |
C12 | 0.0324 (19) | 0.029 (2) | 0.021 (2) | −0.0022 (15) | 0.0053 (15) | −0.0033 (17) |
N1 | 0.0306 (17) | 0.0239 (16) | 0.0119 (18) | −0.0016 (14) | 0.0008 (13) | 0.0029 (14) |
O1 | 0.0390 (15) | 0.0165 (14) | 0.0254 (14) | −0.0004 (12) | 0.0021 (11) | 0.0033 (11) |
O2 | 0.0375 (17) | 0.0278 (17) | 0.0195 (16) | −0.0011 (11) | 0.0030 (13) | 0.0002 (11) |
F1 | 0.0447 (13) | 0.0287 (14) | 0.0430 (16) | −0.0109 (10) | −0.0002 (12) | 0.0024 (13) |
S1 | 0.0288 (5) | 0.0207 (5) | 0.0156 (4) | −0.0003 (3) | 0.0014 (4) | 0.0003 (4) |
Br1 | 0.0296 (3) | 0.0300 (3) | 0.0506 (3) | 0.00444 (15) | 0.0016 (2) | −0.0070 (3) |
C1—C2 | 1.374 (6) | C7—N1 | 1.445 (5) |
C1—C6 | 1.377 (6) | C8—C9 | 1.375 (6) |
C1—Br1 | 1.903 (4) | C8—H8 | 0.9300 |
C2—C3 | 1.385 (6) | C9—C10 | 1.369 (6) |
C2—H2 | 0.9300 | C9—H9 | 0.9300 |
C3—C4 | 1.384 (6) | C10—F1 | 1.363 (5) |
C3—H3 | 0.9300 | C10—C11 | 1.382 (7) |
C4—C5 | 1.390 (5) | C11—C12 | 1.388 (6) |
C4—S1 | 1.769 (4) | C11—H11 | 0.9300 |
C5—C6 | 1.382 (6) | C12—H12 | 0.9300 |
C5—H5 | 0.9300 | N1—S1 | 1.634 (3) |
C6—H6 | 0.9300 | N1—H1 | 0.900 (10) |
C7—C12 | 1.386 (5) | O1—S1 | 1.428 (3) |
C7—C8 | 1.392 (5) | O2—S1 | 1.434 (3) |
C2—C1—C6 | 121.7 (4) | C7—C8—H8 | 120.1 |
C2—C1—Br1 | 119.8 (3) | C10—C9—C8 | 118.8 (4) |
C6—C1—Br1 | 118.5 (3) | C10—C9—H9 | 120.6 |
C1—C2—C3 | 119.6 (4) | C8—C9—H9 | 120.6 |
C1—C2—H2 | 120.2 | F1—C10—C9 | 119.6 (4) |
C3—C2—H2 | 120.2 | F1—C10—C11 | 117.3 (4) |
C4—C3—C2 | 118.9 (4) | C9—C10—C11 | 123.1 (4) |
C4—C3—H3 | 120.6 | C10—C11—C12 | 117.7 (4) |
C2—C3—H3 | 120.6 | C10—C11—H11 | 121.1 |
C3—C4—C5 | 121.4 (4) | C12—C11—H11 | 121.1 |
C3—C4—S1 | 120.0 (3) | C7—C12—C11 | 120.2 (4) |
C5—C4—S1 | 118.4 (3) | C7—C12—H12 | 119.9 |
C6—C5—C4 | 119.1 (4) | C11—C12—H12 | 119.9 |
C6—C5—H5 | 120.5 | C7—N1—S1 | 119.2 (2) |
C4—C5—H5 | 120.5 | C7—N1—H1 | 108 (3) |
C1—C6—C5 | 119.3 (4) | S1—N1—H1 | 116 (3) |
C1—C6—H6 | 120.3 | O1—S1—O2 | 120.34 (16) |
C5—C6—H6 | 120.3 | O1—S1—N1 | 106.20 (17) |
C12—C7—C8 | 120.3 (4) | O2—S1—N1 | 107.23 (17) |
C12—C7—N1 | 120.3 (3) | O1—S1—C4 | 108.41 (17) |
C8—C7—N1 | 119.4 (4) | O2—S1—C4 | 107.98 (18) |
C9—C8—C7 | 119.8 (4) | N1—S1—C4 | 105.81 (17) |
C9—C8—H8 | 120.1 | ||
C6—C1—C2—C3 | 2.1 (6) | C9—C10—C11—C12 | 0.6 (7) |
Br1—C1—C2—C3 | −177.4 (3) | C8—C7—C12—C11 | 1.8 (6) |
C1—C2—C3—C4 | −1.0 (6) | N1—C7—C12—C11 | −177.0 (4) |
C2—C3—C4—C5 | −0.4 (6) | C10—C11—C12—C7 | −2.1 (6) |
C2—C3—C4—S1 | 175.3 (3) | C12—C7—N1—S1 | −101.4 (4) |
C3—C4—C5—C6 | 0.8 (6) | C8—C7—N1—S1 | 79.8 (4) |
S1—C4—C5—C6 | −174.9 (3) | C7—N1—S1—O1 | −176.5 (3) |
C2—C1—C6—C5 | −1.7 (6) | C7—N1—S1—O2 | −46.7 (3) |
Br1—C1—C6—C5 | 177.8 (3) | C7—N1—S1—C4 | 68.4 (3) |
C4—C5—C6—C1 | 0.2 (6) | C3—C4—S1—O1 | 158.8 (3) |
C12—C7—C8—C9 | 0.2 (6) | C5—C4—S1—O1 | −25.4 (4) |
N1—C7—C8—C9 | 179.0 (4) | C3—C4—S1—O2 | 26.9 (4) |
C7—C8—C9—C10 | −1.8 (6) | C5—C4—S1—O2 | −157.3 (3) |
C8—C9—C10—F1 | −179.7 (4) | C3—C4—S1—N1 | −87.7 (3) |
C8—C9—C10—C11 | 1.4 (7) | C5—C4—S1—N1 | 88.2 (3) |
F1—C10—C11—C12 | −178.3 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O2i | 0.90 (2) | 2.03 (2) | 2.911 (4) | 167 (4) |
Symmetry code: (i) x, y, z−1. |
Acknowledgements
The authors are thankful to the Institution of Excellence, Vijnana Bhavana, University of Mysore, Mysore, for providing the single-crystal X-ray diffraction data. VZR is thankful to the University Grants Commission, Delhi, for financial assistance under its MRP scheme.
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