4-(4-Fluoro­benzene­sulfonamido)­phenyl 4-fluoro­benzene­sulfonate

Al-Najjar, B.O.; Tengku Muhammad, T.S.; Wahab, H.A.; Rosli, M.M.; Fun, H.-K.

doi:10.1107/S1600536812009877

organic compounds

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ISSN: 2056-9890

Volume 68| Part 4| April 2012| Page o1094

doi:10.1107/S1600536812009877

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4-(4-Fluorobenzenesulfonamido)phenyl 4-fluorobenzenesulfonate

Belal O. Al-Najjar,^a Tengku Sifzizul Tengku Muhammad,^b,^c Habibah A. Wahab,^a ‡ Mohd Mustaqim Rosli ^d and Hoong-Kun Fun ^d ^*§

^aPharmaceutical Design and Simulation (PhDS) Laboratory, School of Pharmaceutical Sciences, Universiti Sains Malaysia, 11800 Minden, Pulau Pinang, Malaysia, ^bMalaysian Institute of Pharmaceuticals and Nutraceuticals, Ministry of Science, Technology and Innovation, SAINS@USM, No. 10, 11900 Persiaran Bukit Jambul, Pulau Pinang, Malaysia, ^cDepartment of Biological Sciences, Universiti Malaysia Terengganu, 21030 Kuala Terengganu, Terengganu, Malaysia, and ^dX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
^*Correspondence e-mail: hkfun@usm.my

(Received 28 February 2012; accepted 6 March 2012; online 17 March 2012)

In the title compound, C₁₈H₁₃F₂NO₅S₂, the complete molecule is generated by a crystallographic inversion centre, and the O atom and the N—H group attached to the central ring are statistically disordered. The dihedral angle between the central and terminal benzene rings is 64.03 (6)°. In the crystal, N—H⋯O, C—H⋯F and C—H⋯O interactions link the molecules into a three-dimensional network.

Related literature

For a related structure showing similar statistical disorder of its O atom and NH group, see: Al Najjar et al. (2012 ). For background to the biological activity of benzenesulfonates, see: Supuran et al. (2003 ). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ).

Experimental

Crystal data

C₁₈H₁₃F₂NO₅S₂
M_r = 425.41
Monoclinic, P 2₁ /c
a = 8.9683 (1) Å
b = 11.0323 (1) Å
c = 9.3314 (1) Å
β = 102.363 (1)°
V = 901.85 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.35 mm⁻¹
T = 100 K
0.37 × 0.33 × 0.21 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.883, T_max = 0.930
12757 measured reflections
3235 independent reflections
2940 reflections with I > 2σ(I)
R_int = 0.018

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.100
S = 1.09
3235 reflections
127 parameters
H-atom parameters constrained
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O2ⁱ	0.96	2.12	3.0630 (14)	169
C5—H5A⋯F1ⁱⁱ	0.95	2.37	3.2766 (16)	159
C6—H6A⋯O3ⁱⁱⁱ	0.95	2.54	3.4130 (17)	152
C7—H7A⋯O2^iv	0.95	2.60	3.3936 (17)	142
Symmetry codes: (i) -x, -y+1, -z+1; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812009877/hb6664sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812009877/hb6664Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812009877/hb6664Isup3.cml

checkCIF report

Comment top

As part of our ongoing structural investigations of benzenesulfonates (Al Najjar et al., 2012) with potential biological activities (Supuran et al., 2003), we now describe the synthesis and structure of the title compound, (I).

The asymmetric unit of the title compound consists of half the molecule with other half being generated by inversion centre. The O1 and N1 atoms occupy the same position to the central phenyl ring (Fig 1 and Fig 2), disordered with half occupancies each. A similar disordering is seen in a related structure with meta substituents on the terminal rings (Al Najjar et al., 2012), although in this case, a crystallographic twofold axis generates the complete molecule. All parameters in (I) are within normal ranges. The dihedral angle between C1/C6 and C7—C9/C7A—C9A is 64.03 (6)° whereas the the C1/C6 ring and its symmetry equivalent C1A/C6A ring are constrained by symmetry to lie in a parallel orientation. In the crystal, N1—H1N1···O2ⁱ, C5—H5A···F1ⁱⁱ, C6—H6A···O3ⁱⁱⁱ and C7—H7A···O2^iv bonds (Table 1) link the molecules into a three-dimensional network (Fig. 3)

Related literature top

For a related structure showing similar statistical disorder of its O atom and NH group, see: Al Najjar et al. (2012). For background to the biological activity of benzenesulfonates, see: Supuran et al. (2003). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986).

Experimental top

0.02 Mole of 4-fluorobenzenesulfonyl chloride was added to 0.01 mole of p-aminophenol dissolved in pyridine. Next, the reaction mixture was neutralized by adding hydrochloric acid. The precipitate formed was dissolved in 5% aqueous sodium hydroxide, and the sulfonamide recovered by adding 1:1 hydrochloric acid slowly. Re-crystallization of the product by slow evaporation of an ethyl acetate solution gave yellow blocks of (I).

Structure description top

For a related structure showing similar statistical disorder of its O atom and NH group, see: Al Najjar et al. (2012). For background to the biological activity of benzenesulfonates, see: Supuran et al. (2003). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The first disorder component of the structure with 50% probability displacement ellipsoids. Hydrogen atoms are shown as spheres of arbitrary radius.
	Fig. 2. The second disorder component of the structure with 50% probability displacement ellipsoids. Hydrogen atoms are shown as spheres of arbitrary radius.
	Fig. 3. The crystal packing of (I). Dashed lines indicate hydrogen bonds. H atoms not involved in the hydrogen bond interactions have been omitted for clarity.

4-(4-Fluorobenzenesulfonamido)phenyl 4-fluorobenzenesulfonate top

Crystal data top

C₁₈H₁₃F₂NO₅S₂	F(000) = 436
M_r = 425.41	D_x = 1.567 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 7746 reflections
a = 8.9683 (1) Å	θ = 2.3–32.6°
b = 11.0323 (1) Å	µ = 0.35 mm⁻¹
c = 9.3314 (1) Å	T = 100 K
β = 102.363 (1)°	Block, yellow
V = 901.85 (2) Å³	0.37 × 0.33 × 0.21 mm
Z = 2

Data collection top

Bruker SMART APEXII CCD diffractometer	3235 independent reflections
Radiation source: fine-focus sealed tube	2940 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.018
φ and ω scans	θ_max = 32.6°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −13→13
T_min = 0.883, T_max = 0.930	k = −16→16
12757 measured reflections	l = −12→14

Refinement top

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) = 0.100	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0442P)² + 0.4073P] where P = (F_o² + 2F_c²)/3
3235 reflections	(Δ/σ)_max < 0.001
127 parameters	Δρ_max = 0.39 e Å⁻³
0 restraints	Δρ_min = −0.39 e Å⁻³

Crystal data top

C₁₈H₁₃F₂NO₅S₂	V = 901.85 (2) Å³
M_r = 425.41	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.9683 (1) Å	µ = 0.35 mm⁻¹
b = 11.0323 (1) Å	T = 100 K
c = 9.3314 (1) Å	0.37 × 0.33 × 0.21 mm
β = 102.363 (1)°

Data collection top

Bruker SMART APEXII CCD diffractometer	3235 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	2940 reflections with I > 2σ(I)
T_min = 0.883, T_max = 0.930	R_int = 0.018
12757 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.100	H-atom parameters constrained
S = 1.09	Δρ_max = 0.39 e Å⁻³
3235 reflections	Δρ_min = −0.39 e Å⁻³
127 parameters

Special details top

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
S1	0.19643 (3)	0.57696 (3)	0.40553 (3)	0.02189 (8)
F1	0.48038 (14)	0.10387 (9)	0.39858 (12)	0.0534 (3)
O1	0.03218 (11)	0.56620 (9)	0.29564 (11)	0.0265 (2)	0.50
N1	0.03218 (11)	0.56620 (9)	0.29564 (11)	0.0265 (2)	0.50
H1N1	−0.0391	0.5177	0.3342	0.032*	0.50
O2	0.15869 (11)	0.59542 (9)	0.54583 (10)	0.02712 (18)
O3	0.28500 (11)	0.66585 (8)	0.34966 (11)	0.0302 (2)
C1	0.41366 (16)	0.21362 (12)	0.39786 (15)	0.0318 (3)
C2	0.29275 (15)	0.22427 (12)	0.46723 (16)	0.0311 (3)
H2A	0.2565	0.1562	0.5119	0.037*
C3	0.22599 (13)	0.33732 (11)	0.46964 (14)	0.0269 (2)
H3A	0.1428	0.3483	0.5166	0.032*
C4	0.28240 (12)	0.43473 (10)	0.40228 (12)	0.01905 (19)
C5	0.40364 (13)	0.42142 (11)	0.33233 (13)	0.0248 (2)
H5A	0.4402	0.4889	0.2868	0.030*
C6	0.47055 (16)	0.30807 (13)	0.32990 (15)	0.0323 (3)
H6A	0.5533	0.2962	0.2826	0.039*
C7	0.08657 (15)	0.60289 (12)	0.05220 (15)	0.0299 (3)
H7A	0.1450	0.6725	0.0882	0.036*
C8	0.02046 (14)	0.53190 (11)	0.14551 (13)	0.0258 (2)
C9	−0.06539 (15)	0.43016 (12)	0.09444 (15)	0.0300 (3)
H9A	−0.1097	0.3831	0.1597	0.036*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.02541 (13)	0.01878 (14)	0.02456 (14)	0.00237 (9)	0.01219 (10)	0.00205 (9)
F1	0.0779 (7)	0.0299 (5)	0.0536 (6)	0.0271 (5)	0.0170 (5)	0.0026 (4)
O1	0.0272 (4)	0.0288 (5)	0.0277 (4)	0.0093 (3)	0.0154 (3)	0.0084 (4)
N1	0.0272 (4)	0.0288 (5)	0.0277 (4)	0.0093 (3)	0.0154 (3)	0.0084 (4)
O2	0.0327 (4)	0.0280 (4)	0.0236 (4)	0.0023 (3)	0.0127 (3)	−0.0018 (3)
O3	0.0369 (5)	0.0206 (4)	0.0376 (5)	−0.0023 (3)	0.0183 (4)	0.0035 (3)
C1	0.0406 (6)	0.0230 (6)	0.0289 (6)	0.0110 (5)	0.0008 (5)	−0.0027 (5)
C2	0.0334 (6)	0.0211 (5)	0.0364 (6)	−0.0012 (4)	0.0020 (5)	0.0050 (5)
C3	0.0237 (5)	0.0239 (5)	0.0336 (6)	0.0002 (4)	0.0073 (4)	0.0065 (5)
C4	0.0185 (4)	0.0189 (5)	0.0197 (4)	0.0005 (3)	0.0042 (3)	−0.0003 (4)
C5	0.0237 (5)	0.0267 (6)	0.0259 (5)	0.0030 (4)	0.0096 (4)	0.0008 (4)
C6	0.0342 (6)	0.0342 (7)	0.0306 (6)	0.0130 (5)	0.0113 (5)	−0.0003 (5)
C7	0.0329 (6)	0.0269 (6)	0.0349 (6)	0.0075 (5)	0.0179 (5)	0.0146 (5)
C8	0.0281 (5)	0.0255 (5)	0.0281 (5)	0.0116 (4)	0.0159 (4)	0.0120 (4)
C9	0.0313 (6)	0.0289 (6)	0.0351 (6)	0.0076 (4)	0.0188 (5)	0.0162 (5)

Geometric parameters (Å, º) top

S1—O3	1.4289 (9)	C3—H3A	0.9500
S1—O2	1.4351 (9)	C4—C5	1.3905 (15)
S1—O1	1.6089 (11)	C5—C6	1.3893 (17)
S1—C4	1.7515 (11)	C5—H5A	0.9500
F1—C1	1.3499 (15)	C6—H6A	0.9500
O1—C8	1.4332 (16)	C7—C9ⁱ	1.389 (2)
O1—H1N1	0.9606	C7—C8	1.3943 (16)
C1—C6	1.374 (2)	C7—H7A	0.9500
C1—C2	1.382 (2)	C8—C9	1.387 (2)
C2—C3	1.3858 (18)	C9—C7ⁱ	1.389 (2)
C2—H2A	0.9500	C9—H9A	0.9500
C3—C4	1.3936 (16)

O3—S1—O2	119.57 (6)	C5—C4—C3	121.74 (11)
O3—S1—O1	108.83 (6)	C5—C4—S1	119.61 (9)
O2—S1—O1	103.25 (5)	C3—C4—S1	118.64 (8)
O3—S1—C4	109.11 (5)	C6—C5—C4	119.12 (12)
O2—S1—C4	109.49 (5)	C6—C5—H5A	120.4
O1—S1—C4	105.62 (5)	C4—C5—H5A	120.4
C8—O1—S1	120.53 (7)	C1—C6—C5	118.09 (12)
C8—O1—H1N1	107.7	C1—C6—H6A	121.0
S1—O1—H1N1	113.2	C5—C6—H6A	121.0
F1—C1—C6	118.34 (13)	C9ⁱ—C7—C8	118.74 (13)
F1—C1—C2	117.73 (13)	C9ⁱ—C7—H7A	120.6
C6—C1—C2	123.93 (12)	C8—C7—H7A	120.6
C1—C2—C3	117.99 (12)	C9—C8—C7	121.28 (12)
C1—C2—H2A	121.0	C9—C8—O1	117.95 (10)
C3—C2—H2A	121.0	C7—C8—O1	120.67 (13)
C2—C3—C4	119.13 (11)	C8—C9—C7ⁱ	119.98 (11)
C2—C3—H3A	120.4	C8—C9—H9A	120.0
C4—C3—H3A	120.4	C7ⁱ—C9—H9A	120.0

O3—S1—O1—C8	59.87 (10)	O1—S1—C4—C3	−71.39 (10)
O2—S1—O1—C8	−172.10 (9)	C3—C4—C5—C6	−0.18 (18)
C4—S1—O1—C8	−57.16 (10)	S1—C4—C5—C6	−179.74 (10)
F1—C1—C2—C3	178.60 (12)	F1—C1—C6—C5	−178.59 (12)
C6—C1—C2—C3	−0.7 (2)	C2—C1—C6—C5	0.7 (2)
C1—C2—C3—C4	0.23 (19)	C4—C5—C6—C1	−0.25 (19)
C2—C3—C4—C5	0.18 (18)	C9ⁱ—C7—C8—C9	−0.15 (19)
C2—C3—C4—S1	179.75 (10)	C9ⁱ—C7—C8—O1	−176.54 (11)
O3—S1—C4—C5	−8.66 (11)	S1—O1—C8—C9	122.24 (11)
O2—S1—C4—C5	−141.24 (9)	S1—O1—C8—C7	−61.25 (13)
O1—S1—C4—C5	108.18 (10)	C7—C8—C9—C7ⁱ	0.2 (2)
O3—S1—C4—C3	171.77 (9)	O1—C8—C9—C7ⁱ	176.64 (11)
O2—S1—C4—C3	39.18 (11)

Symmetry code: (i) −x, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O2ⁱⁱ	0.96	2.12	3.0630 (14)	169
C5—H5A···F1ⁱⁱⁱ	0.95	2.37	3.2766 (16)	159
C6—H6A···O3^iv	0.95	2.54	3.4130 (17)	152
C7—H7A···O2^v	0.95	2.60	3.3936 (17)	142

Symmetry codes: (ii) −x, −y+1, −z+1; (iii) −x+1, y+1/2, −z+1/2; (iv) −x+1, y−1/2, −z+1/2; (v) x, −y+3/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₈H₁₃F₂NO₅S₂
M_r	425.41
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	8.9683 (1), 11.0323 (1), 9.3314 (1)
β (°)	102.363 (1)
V (Å³)	901.85 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.35
Crystal size (mm)	0.37 × 0.33 × 0.21

Data collection
Diffractometer	Bruker SMART APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.883, 0.930
No. of measured, independent and observed [I > 2σ(I)] reflections	12757, 3235, 2940
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.759

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.100, 1.09
No. of reflections	3235
No. of parameters	127
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.39

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O2ⁱ	0.96	2.12	3.0630 (14)	169
C5—H5A···F1ⁱⁱ	0.95	2.37	3.2766 (16)	159
C6—H6A···O3ⁱⁱⁱ	0.95	2.54	3.4130 (17)	152
C7—H7A···O2^iv	0.95	2.60	3.3936 (17)	142

Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, y+1/2, −z+1/2; (iii) −x+1, y−1/2, −z+1/2; (iv) x, −y+3/2, z−1/2.

Footnotes

‡Additional correspondence author, e-mail: habibahw@usm.my.

§Thomson Reuters ResearcherID: A-3561-2009.

Acknowledgements

HAW gratefully acknowledges the Malaysian Ministry of Science, Technology and Innovation for the synthesis work funded by grant Nos. 311/IFN/69230112 and 304/PFARMASI/650545/I121. HKF thanks USM for the Research University Grant No. 1001/PFIZIK/811160.

References

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