4-(4-Fluoro­benzene­sulfonamido)­phenyl 4-fluoro­benzene­sulfonate

Abstract

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,

• a = 8.9683 (1) Å

• b = 11.0323 (1) Å

• c = 9.3314 (1) Å

• β = 102.363 (1)°

• V = 901.85 (2) ų

• 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[F ² > 2σ(F ²)] = 0.036

• wR(F ²) = 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

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 ▶).

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536812009877/hb6664Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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⋯O2iv	0.95	2.60	3.3936 (17)	142

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .

supplementary crystallographic information

Comment

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)

Experimental

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).

Refinement

N bound H atoms were located from a difference Fourier maps and refined using a riding model. The remaining H atoms were positioned geometrically and refined using a riding model with C—H = 0.95 Å and U_iso(H) = 1.2U_eq(C).

Figures

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.

Crystal data

C18H13F2NO5S2	F(000) = 436
Mr = 425.41	Dx = 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

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

Refinement

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(Fo2) + (0.0442P)2 + 0.4073P] where P = (Fo2 + 2Fc2)/3
3235 reflections	(Δ/σ)max < 0.001
127 parameters	Δρmax = 0.39 e Å−3
0 restraints	Δρmin = −0.39 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	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 (Ų)

	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)

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)

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···O3iv	0.95	2.54	3.4130 (17)	152
C7—H7A···O2v	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.