4-Bromo-N-(4-fluoro­phen­yl)benzene­sulfonamide

Rodrigues, V.Z.; Suchetan, P.A.; Saritha, L.; Lokanath, N.K.; Naveen, S.

doi:10.1107/S2414314616012566

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 8| August 2016| x161256

doi:10.1107/S2414314616012566

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4-Bromo-N-(4-fluorophenyl)benzenesulfonamide

Vinola Z. Rodrigues,^a P. A. Suchetan,^b L. Saritha,^a N. K. Lokanath ^c and S. Naveen ^d ^*

^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

Edited by A. J. Lough, University of Toronto, Canada (Received 21 July 2016; accepted 4 August 2016; online 9 August 2016)

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 crystal structure 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, sulfonamides 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 crystal structure 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).

Figure 1
The molecular structure of the title compound, showing displacement ellipsoids drawn at the 50% probability level.

The crystal structure of (I) features strong N1—H1⋯O2ⁱ 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 + $[{1\over 2}]$ ) 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⋯O_nitro [in (III)].

Table 1
Hydrogen-bond geometry (Å, °)

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.

Figure 2
Crystal packing of the title compound, showing N—H⋯O hydrogen bonds as dotted lines. The F⋯F contacts between hydrogen-bonded chains are also shown as dotted lines.

Synthesis 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 refinement details are summarized in Table 2. Two reflections with bad agreement between F_o and F_c, viz. 110 and 120, were omitted from the final refinement.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₂H₉BrFNO₂S
M_r	330.17
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	296
a, b, c (Å)	19.7608 (6), 12.4156 (4), 5.0776 (2)
V (Å³)	1245.75 (7)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	6.14
Crystal size (mm)	0.27 × 0.24 × 0.19

Data collection
Diffractometer	Bruker APEXII
Absorption correction	Multi-scan (SADABS; Bruker, 2009 )
T_min, T_max	0.238, 0.311
No. of measured, independent and observed [I > 2σ(I)] reflections	5649, 1688, 1621
R_int	0.053
(sin θ/λ)_max (Å⁻¹)	0.583

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.083, 1.03
No. of reflections	1688
No. of parameters	167
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.40, −0.36
Absolute structure	Flack (1983 ), 547 Friedel pairs
Absolute structure parameter	0.01 (3)
Computer programs: APEX2, SAINT-Plus and XPREP (Bruker, 2009), SHELXS97 and SHELXL97 (Sheldrick, 2008 ) and Mercury (Macrae et al., 2008 ).

Structural data

CCDC reference: 1497562

Crystal structure: contains datablock I. DOI: 10.1107/S2414314616012566/lh4010sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2414314616012566/lh4010Isup2.hkl

Supporting information file. DOI: 10.1107/S2414314616012566/lh4010Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: 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).

4-Bromo-N-(4-fluorophenyl)benzenesulfonamide top

Crystal data top

C₁₂H₉BrFNO₂S	Prism
M_r = 330.17	D_x = 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

Data collection top

Bruker APEXII diffractometer	1621 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.053
Graphite monochromator	θ_max = 64.1°, θ_min = 5.7°
φ and ω scans	h = −22→22
Absorption correction: multi-scan (SADABS; Bruker, 2009)	k = −14→12
T_min = 0.238, T_max = 0.311	l = −5→5
5649 measured reflections	1 standard reflections every 1 reflections
1688 independent reflections	intensity decay: 0.1%

Refinement top

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(F_o²) + (0.0511P)²] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
1688 reflections	Δρ_max = 0.40 e Å⁻³
167 parameters	Δρ_min = −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)

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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)*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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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