4-(3-Methyl­benzene­sulfonamido)­phenyl 3-methyl­benzene­sulfonate

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

doi:10.1107/S1600536811054808

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 68| Part 2| February 2012| Page o258

doi:10.1107/S1600536811054808

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4-(3-Methylbenzenesulfonamido)phenyl 3-methylbenzenesulfonate

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 30 November 2011; accepted 20 December 2011; online 7 January 2012)

The complete molecule of the title compound, C₂₀H₁₉NO₅S₂, is generated by a crystallographic twofold axis and the O atom and N—H group attached to the central benzene ring are statistically disordered. The dihedral angle between the central and terminal benzene rings is 56.91 (5)° and that between the terminal benzene rings is 29.80 (5)°. In the crystal, N—H⋯O hydrogen bonding links the molecules into sheets lying parallel to the ab plane.

Related literature

For the biological properties of sulfonyl derivatives, see: Supuran et al. (2003 ). For a related structure, see: Sinha et al. (2011 ). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ).

Experimental

Crystal data

C₂₀H₁₉NO₅S₂
M_r = 417.48
Monoclinic, C 2/c
a = 14.4352 (1) Å
b = 9.1250 (1) Å
c = 15.4402 (2) Å
β = 109.700 (1)°
V = 1914.76 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.31 mm⁻¹
T = 100 K
0.41 × 0.34 × 0.25 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.883, T_max = 0.926
21937 measured reflections
3533 independent reflections
3249 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.090
S = 1.08
3533 reflections
128 parameters
H-atom parameters constrained
Δρ_max = 0.46 e Å⁻³
Δρ_min = −0.40 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O3ⁱ	1.02	1.97	2.9854 (11)	178
Symmetry code: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

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/S1600536811054808/hb6544sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811054808/hb6544Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811054808/hb6544Isup3.cml

checkCIF report

Comment top

Sulfonyl compounds have attracted our interest and many others, due to their varied biological activities (Sinha et al., 2011). Sulfonyl derivatives are found to be active against inflammation, various viral infections as well as cancer (Supuran et al., 2003).

The asymmetric unit of the title compound consists of half the molecule with the other half of the molecule being generated by a twofold axis. The crystal structure is disordered with the O1 and the N1 atoms attached at the same position with half occupancies each to the central phenyl ring (Fig 1 and Fig 2). All parameters in (I) are within normal ranges. The dihedral angle between C1/C6 and C8—C12/C8a—C12a is 56.91 (5)° whereas the dihedral angle between C1—C6 and C1a—C6a is 29.80 (5)°. In the crystal structure, (Fig. 3), N1—H1···O3ⁱ hydrogen bonds (Table 1) link the molecules into infinite layers parallel to ab-plane.

Related literature top

For the biological properties of sulfonyl derivatives, see: Supuran et al. (2003). For a related structure, see: Sinha et al. (2011). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986).

Experimental top

0.02 mole of m-toluenesulfonyl chloride was added to 0.01 mole of p-aminophenol dissolved in pyridine. The reaction mixture was then 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 ethanol gave colourless blocks of the title compound.

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. A disorder component of the structure with 50% probability displacement ellipsoids. Hydrogen atoms are shown as spheres of arbitrary radius.
	Fig. 2. The other 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-(3-Methylbenzenesulfonamido)phenyl 3-methylbenzenesulfonate top

Crystal data top

C₂₀H₁₉NO₅S₂	F(000) = 872
M_r = 417.48	D_x = 1.448 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 9887 reflections
a = 14.4352 (1) Å	θ = 2.7–32.8°
b = 9.1250 (1) Å	µ = 0.31 mm⁻¹
c = 15.4402 (2) Å	T = 100 K
β = 109.700 (1)°	Block, colourless
V = 1914.76 (4) Å³	0.41 × 0.34 × 0.25 mm
Z = 4

Data collection top

Bruker SMART APEXII CCD diffractometer	3533 independent reflections
Radiation source: fine-focus sealed tube	3249 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
ϕ and ω scans	θ_max = 33.0°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −22→19
T_min = 0.883, T_max = 0.926	k = −13→13
21937 measured reflections	l = −23→23

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.090	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0485P)² + 1.0937P] where P = (F_o² + 2F_c²)/3
3533 reflections	(Δ/σ)_max = 0.001
128 parameters	Δρ_max = 0.46 e Å⁻³
0 restraints	Δρ_min = −0.40 e Å⁻³

Crystal data top

C₂₀H₁₉NO₅S₂	V = 1914.76 (4) Å³
M_r = 417.48	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 14.4352 (1) Å	µ = 0.31 mm⁻¹
b = 9.1250 (1) Å	T = 100 K
c = 15.4402 (2) Å	0.41 × 0.34 × 0.25 mm
β = 109.700 (1)°

Data collection top

Bruker SMART APEXII CCD diffractometer	3533 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	3249 reflections with I > 2σ(I)
T_min = 0.883, T_max = 0.926	R_int = 0.022
21937 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.090	H-atom parameters constrained
S = 1.08	Δρ_max = 0.46 e Å⁻³
3533 reflections	Δρ_min = −0.40 e Å⁻³
128 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	0.261632 (15)	0.38804 (2)	0.813408 (15)	0.01868 (7)
O1	0.30077 (5)	0.33201 (8)	0.73257 (5)	0.01910 (13)	0.50
N1	0.30077 (5)	0.33201 (8)	0.73257 (5)	0.01910 (13)	0.50
H1	0.2719	0.2309	0.7120	0.023*	0.50
O2	0.15974 (5)	0.34770 (9)	0.78153 (5)	0.02715 (16)
O3	0.28871 (6)	0.53930 (8)	0.83108 (6)	0.02607 (15)
C1	0.43833 (8)	0.12376 (12)	1.06033 (7)	0.02529 (19)
H1A	0.4772	0.0678	1.1116	0.030*
C2	0.46090 (8)	0.27063 (12)	1.05424 (7)	0.0268 (2)
H2A	0.5145	0.3140	1.1012	0.032*
C3	0.40519 (7)	0.35443 (11)	0.97948 (7)	0.02235 (17)
H3A	0.4195	0.4552	0.9750	0.027*
C4	0.32808 (6)	0.28698 (9)	0.91157 (6)	0.01695 (15)
C5	0.30453 (7)	0.14007 (10)	0.91733 (6)	0.01931 (16)
H5A	0.2511	0.0969	0.8701	0.023*
C6	0.35980 (8)	0.05647 (10)	0.99286 (7)	0.02188 (17)
C7	0.33362 (11)	−0.10114 (11)	1.00160 (9)	0.0333 (2)
H7A	0.3116	−0.1471	0.9407	0.050*
H7B	0.2807	−0.1058	1.0279	0.050*
H7C	0.3915	−0.1531	1.0419	0.050*
C8	0.40253 (6)	0.33636 (9)	0.74375 (6)	0.01551 (14)
C9	0.45112 (6)	0.20366 (9)	0.74745 (6)	0.01958 (16)
H9A	0.4176	0.1138	0.7465	0.023*
C12	0.45042 (6)	0.46948 (9)	0.74605 (6)	0.01721 (15)
H12A	0.4160	0.5593	0.7423	0.021*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.01452 (11)	0.02118 (11)	0.02237 (11)	0.00479 (7)	0.00888 (8)	0.00390 (7)
O1	0.0117 (3)	0.0267 (3)	0.0194 (3)	0.0003 (2)	0.0059 (2)	0.0029 (2)
N1	0.0117 (3)	0.0267 (3)	0.0194 (3)	0.0003 (2)	0.0059 (2)	0.0029 (2)
O2	0.0132 (3)	0.0395 (4)	0.0301 (4)	0.0052 (3)	0.0090 (3)	0.0047 (3)
O3	0.0290 (4)	0.0177 (3)	0.0358 (4)	0.0067 (3)	0.0166 (3)	0.0039 (3)
C1	0.0242 (4)	0.0312 (5)	0.0205 (4)	0.0031 (4)	0.0076 (3)	0.0049 (3)
C2	0.0220 (4)	0.0330 (5)	0.0220 (4)	−0.0049 (4)	0.0030 (3)	−0.0008 (4)
C3	0.0209 (4)	0.0220 (4)	0.0235 (4)	−0.0041 (3)	0.0066 (3)	−0.0019 (3)
C4	0.0160 (3)	0.0172 (3)	0.0188 (3)	0.0010 (3)	0.0074 (3)	−0.0003 (3)
C5	0.0208 (4)	0.0180 (4)	0.0201 (4)	−0.0017 (3)	0.0081 (3)	−0.0016 (3)
C6	0.0271 (4)	0.0196 (4)	0.0221 (4)	0.0013 (3)	0.0125 (3)	0.0021 (3)
C7	0.0497 (7)	0.0203 (4)	0.0344 (5)	−0.0012 (4)	0.0201 (5)	0.0050 (4)
C8	0.0119 (3)	0.0183 (3)	0.0161 (3)	−0.0001 (3)	0.0044 (3)	0.0026 (3)
C9	0.0171 (4)	0.0143 (3)	0.0236 (4)	−0.0018 (3)	0.0019 (3)	0.0025 (3)
C12	0.0149 (3)	0.0150 (3)	0.0221 (4)	0.0011 (3)	0.0068 (3)	0.0000 (3)

Geometric parameters (Å, º) top

S1—O2	1.4329 (8)	C4—C5	1.3931 (12)
S1—O3	1.4354 (8)	C5—C6	1.3969 (13)
S1—O1	1.6167 (7)	C5—H5A	0.9500
S1—C4	1.7572 (9)	C6—C7	1.5046 (14)
O1—C8	1.4206 (10)	C7—H7A	0.9800
O1—H1	1.0188	C7—H7B	0.9800
C1—C2	1.3899 (15)	C7—H7C	0.9800
C1—C6	1.3968 (15)	C8—C9	1.3909 (12)
C1—H1A	0.9500	C8—C12	1.3921 (12)
C2—C3	1.3922 (14)	C9—C9ⁱ	1.3866 (18)
C2—H2A	0.9500	C9—H9A	0.9500
C3—C4	1.3894 (13)	C12—C12ⁱ	1.3949 (16)
C3—H3A	0.9500	C12—H12A	0.9500

O2—S1—O3	119.64 (5)	C4—C5—C6	119.72 (9)
O2—S1—O1	103.82 (4)	C4—C5—H5A	120.1
O3—S1—O1	107.89 (4)	C6—C5—H5A	120.1
O2—S1—C4	111.11 (4)	C1—C6—C5	118.30 (9)
O3—S1—C4	107.83 (5)	C1—C6—C7	121.23 (9)
O1—S1—C4	105.59 (4)	C5—C6—C7	120.45 (10)
C8—O1—S1	120.90 (6)	C6—C7—H7A	109.5
C8—O1—H1	111.2	C6—C7—H7B	109.5
S1—O1—H1	108.3	H7A—C7—H7B	109.5
C2—C1—C6	121.55 (9)	C6—C7—H7C	109.5
C2—C1—H1A	119.2	H7A—C7—H7C	109.5
C6—C1—H1A	119.2	H7B—C7—H7C	109.5
C1—C2—C3	120.17 (9)	C9—C8—C12	121.29 (8)
C1—C2—H2A	119.9	C9—C8—O1	117.85 (7)
C3—C2—H2A	119.9	C12—C8—O1	120.78 (8)
C4—C3—C2	118.32 (9)	C9ⁱ—C9—C8	119.46 (5)
C4—C3—H3A	120.8	C9ⁱ—C9—H9A	120.3
C2—C3—H3A	120.8	C8—C9—H9A	120.3
C3—C4—C5	121.92 (8)	C8—C12—C12ⁱ	119.23 (5)
C3—C4—S1	118.94 (7)	C8—C12—H12A	120.4
C5—C4—S1	119.08 (7)	C12ⁱ—C12—H12A	120.4

O2—S1—O1—C8	−172.37 (7)	C3—C4—C5—C6	−0.44 (13)
O3—S1—O1—C8	59.70 (8)	S1—C4—C5—C6	176.91 (7)
C4—S1—O1—C8	−55.39 (7)	C2—C1—C6—C5	1.03 (15)
C6—C1—C2—C3	−0.35 (16)	C2—C1—C6—C7	−177.82 (10)
C1—C2—C3—C4	−0.71 (15)	C4—C5—C6—C1	−0.63 (14)
C2—C3—C4—C5	1.11 (14)	C4—C5—C6—C7	178.23 (9)
C2—C3—C4—S1	−176.24 (8)	S1—O1—C8—C9	113.82 (8)
O2—S1—C4—C3	−144.83 (8)	S1—O1—C8—C12	−69.45 (10)
O3—S1—C4—C3	−11.90 (9)	C12—C8—C9—C9ⁱ	−0.70 (16)
O1—S1—C4—C3	103.24 (8)	O1—C8—C9—C9ⁱ	176.01 (10)
O2—S1—C4—C5	37.75 (8)	C9—C8—C12—C12ⁱ	−1.20 (15)
O3—S1—C4—C5	170.68 (7)	O1—C8—C12—C12ⁱ	−177.81 (10)
O1—S1—C4—C5	−74.19 (8)

Symmetry code: (i) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O3ⁱⁱ	1.02	1.97	2.9854 (11)	178

Symmetry code: (ii) −x+1/2, y−1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₂₀H₁₉NO₅S₂
M_r	417.48
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	100
a, b, c (Å)	14.4352 (1), 9.1250 (1), 15.4402 (2)
β (°)	109.700 (1)
V (Å³)	1914.76 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.31
Crystal size (mm)	0.41 × 0.34 × 0.25

Data collection
Diffractometer	Bruker SMART APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.883, 0.926
No. of measured, independent and observed [I > 2σ(I)] reflections	21937, 3533, 3249
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.765

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.090, 1.08
No. of reflections	3533
No. of parameters	128
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.46, −0.40

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—H1···O3ⁱ	1.02	1.97	2.9854 (11)	178

Symmetry code: (i) −x+1/2, y−1/2, −z+3/2.

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.

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