4-{[(4-Methyl­phen­yl)sulfon­yl]amino}­benzoic acid

Mustafa, G.; Khan, I.U.; Zia-ur-Rehman, M.; Sharif, S.; Arshad, M.N.

doi:10.1107/S1600536811011524

organic compounds

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ISSN: 2056-9890

Volume 67| Part 4| April 2011| Page o1018

doi:10.1107/S1600536811011524

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4-{[(4-Methylphenyl)sulfonyl]amino}benzoic acid

Ghulam Mustafa,^a Islam Ullah Khan,^a ^* Muhammad Zia-ur-Rehman,^b Shahzad Sharif ^a and Muhammad Nadeem Arshad ^a

^aDepartment of Chemistry, Government College University, Lahore 54000, Pakistan, and ^bApplied Chemistry Research Centre, PCSIR Laboratories Complex, Lahore 54600, Pakistan
^*Correspondence e-mail: iukhan.gcu@gmail.com

(Received 25 March 2011; accepted 28 March 2011; online 31 March 2011)

In the title compound, C₁₄H₁₃NO₄S, the dihedral angle between the aromatic rings is 35.47 (10)°. In the crystal, adjacent molecules are connected by pairs of O—H⋯O hydrogen bonds, forming head-to-head centrosymmetric dimers typical for carboxylic acids. Adjacent dimers are further linked through C—H⋯O interactions on one side and N—H⋯O interactions on the other, generating [010] chains.

Related literature

For background to the biological activity of sulfonamides, see: Hanson et al. (1999 ). For related structures, see: Gowda et al. (2007 ); Arshad et al. (2008 ); Shafiq et al. (2009 ).

Experimental

Crystal data

C₁₄H₁₃NO₄S
M_r = 291.31
Triclinic, $[P \overline 1]$
a = 5.1588 (2) Å
b = 6.9277 (2) Å
c = 20.0350 (6) Å
α = 83.574 (1)°
β = 86.357 (1)°
γ = 72.824 (1)°
V = 679.44 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.25 mm⁻¹
T = 296 K
0.35 × 0.31 × 0.22 mm

Data collection

Bruker APEXII CCD diffractometer
12209 measured reflections
3313 independent reflections
2660 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.147
S = 1.01
3310 reflections
186 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O1ⁱ	0.81 (3)	2.25 (3)	3.042 (2)	164.2 (2)
O3—H3O⋯O4ⁱⁱ	0.82	1.83	2.633 (2)	166
C5—H5⋯O3ⁱⁱⁱ	0.93	2.55	3.397 (2)	151
C6—H6⋯O4^iv	0.93	2.43	3.294 (3)	155
Symmetry codes: (i) x-1, y, z; (ii) -x+2, -y+1, -z+1; (iii) -x+3, -y, -z+1; (iv) x+1, y-1, z.

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global, New_Global_Publ_Block. DOI: 10.1107/S1600536811011524/hb5824sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811011524/hb5824Isup2.hkl

checkCIF report

Comment top

Sulfonamides are well known for their various types of biological activities (e.g. Hanson et al., 1999). In the present paper, the structure of the title compound, (I), is reported. Bond lengths and bond angles of the title molecule are similar to those of the related molecules (Gowda et al., 2007; Arshad et al., 2008; Shafiq et al., 2009) and are within normal ranges. In the crystal, each molecule is linked to its adjacent one through head-to-head pairs of O—H···O inter molecular interactions giving rise to dimeric motifs typical for carboxylic acids. Neighbouring dimers are further linked to each other through C—H···O interactions on one side and through N—H···O on the other side along b axis (Fig. 2).

Related literature top

For background to the biological activity of sulfonamides, see: Hanson et al. (1999). For related structures, see: Gowda et al. (2007); Arshad et al. (2008); Shafiq et al. (2009).

Experimental top

To a mixture of p-amino benzoic acid (1.0 g, 7.3 mmoles) and distilled water (10 ml) in a round bottomflask (25 ml) 1M aqueous sodium carbonate solution was added to maintain the pH between 8–9. Tosyl chloride (1.66 g, 8.70 mmol) was added to this solution and was kept stirred at room temperature untill the suspension changed to a clear solution. pH of the reaction mixture was adjusted to 1–2, using 1 N HCl and the precipitates obtained were filtered, washed with distilled water, dried and recrystallized from methanol to yield colourless needles of (I).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The moleuclar structure of (I) with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. Unit cell packing diagram for (I) with hydrogen bonds shown as dashed lines.

4-{[(4-Methylphenyl)sulfonyl]amino}benzoic acid top

Crystal data top

C₁₄H₁₃NO₄S	Z = 2
M_r = 291.31	F(000) = 304
Triclinic, P1	D_x = 1.424 Mg m⁻³
Hall symbol: -P 1	Melting point: 503 K
a = 5.1588 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 6.9277 (2) Å	Cell parameters from 5143 reflections
c = 20.0350 (6) Å	θ = 3.1–27.8°
α = 83.574 (1)°	µ = 0.25 mm⁻¹
β = 86.357 (1)°	T = 296 K
γ = 72.824 (1)°	Needles, colourless
V = 679.44 (4) Å³	0.35 × 0.31 × 0.22 mm

Data collection top

Bruker APEXII CCD diffractometer	2660 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.029
Graphite monochromator	θ_max = 28.3°, θ_min = 1.0°
ϕ and ω scans	h = −6→6
12209 measured reflections	k = −9→9
3313 independent reflections	l = −26→26

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.147	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ²(F_o²) + (0.0982P)² + 0.0842P] where P = (F_o² + 2F_c²)/3
3310 reflections	(Δ/σ)_max = 0.001
186 parameters	Δρ_max = 0.30 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₁₄H₁₃NO₄S	γ = 72.824 (1)°
M_r = 291.31	V = 679.44 (4) Å³
Triclinic, P1	Z = 2
a = 5.1588 (2) Å	Mo Kα radiation
b = 6.9277 (2) Å	µ = 0.25 mm⁻¹
c = 20.0350 (6) Å	T = 296 K
α = 83.574 (1)°	0.35 × 0.31 × 0.22 mm
β = 86.357 (1)°

Data collection top

Bruker APEXII CCD diffractometer	2660 reflections with I > 2σ(I)
12209 measured reflections	R_int = 0.029
3313 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.147	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	Δρ_max = 0.30 e Å⁻³
3310 reflections	Δρ_min = −0.22 e Å⁻³
186 parameters

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	1.0578 (3)	−0.2205 (2)	0.33980 (8)	0.0363 (3)
C2	0.8392 (3)	−0.0474 (3)	0.33116 (9)	0.0450 (4)
H2	0.7040	−0.0414	0.3017	0.054*
C3	0.8230 (3)	0.1167 (3)	0.36655 (9)	0.0447 (4)
H3	0.6746	0.2320	0.3617	0.054*
C4	1.0281 (3)	0.1089 (2)	0.40922 (8)	0.0357 (3)
C5	1.2453 (3)	−0.0655 (3)	0.41777 (8)	0.0406 (4)
H5	1.3824	−0.0711	0.4465	0.049*
C6	1.2585 (3)	−0.2306 (3)	0.38368 (9)	0.0415 (4)
H6	1.4022	−0.3485	0.3902	0.050*
C7	1.0157 (3)	0.2840 (2)	0.44689 (8)	0.0381 (4)
C8	1.1343 (4)	−0.2279 (3)	0.17695 (9)	0.0435 (4)
C9	0.9505 (5)	−0.2551 (3)	0.13444 (11)	0.0634 (6)
H9	0.9213	−0.3814	0.1345	0.076*
C10	0.8108 (6)	−0.0924 (4)	0.09195 (13)	0.0786 (7)
H10	0.6877	−0.1112	0.0631	0.094*
C11	0.8470 (5)	0.0958 (4)	0.09073 (12)	0.0670 (6)
C12	1.0313 (6)	0.1180 (4)	0.13297 (14)	0.0757 (7)
H12	1.0603	0.2444	0.1326	0.091*
C13	1.1759 (5)	−0.0405 (3)	0.17613 (12)	0.0652 (6)
H13	1.3002	−0.0211	0.2044	0.078*
C14	0.6831 (8)	0.2757 (5)	0.04587 (16)	0.1065 (11)
H14A	0.6420	0.2297	0.0055	0.160*
H14B	0.7864	0.3703	0.0347	0.160*
H14C	0.5172	0.3411	0.0691	0.160*
N1	1.0818 (3)	−0.3933 (2)	0.30382 (7)	0.0424 (3)
O1	1.5356 (2)	−0.3963 (2)	0.25576 (7)	0.0559 (4)
O2	1.2874 (3)	−0.6138 (2)	0.21531 (8)	0.0617 (4)
O3	1.2221 (3)	0.2721 (2)	0.47994 (7)	0.0549 (4)
H3O	1.1959	0.3755	0.4989	0.082*
O4	0.8069 (3)	0.43283 (18)	0.44517 (7)	0.0507 (3)
S1	1.28689 (8)	−0.42565 (6)	0.23758 (2)	0.04325 (17)
H1N	0.937 (4)	−0.412 (3)	0.2967 (10)	0.052*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0353 (8)	0.0366 (8)	0.0385 (8)	−0.0115 (6)	−0.0060 (6)	−0.0040 (6)
C2	0.0334 (8)	0.0505 (10)	0.0511 (10)	−0.0074 (7)	−0.0150 (7)	−0.0102 (8)
C3	0.0359 (8)	0.0417 (9)	0.0527 (10)	−0.0019 (7)	−0.0148 (7)	−0.0066 (7)
C4	0.0349 (8)	0.0357 (8)	0.0363 (8)	−0.0092 (6)	−0.0071 (6)	−0.0023 (6)
C5	0.0350 (8)	0.0420 (9)	0.0434 (9)	−0.0058 (7)	−0.0146 (6)	−0.0063 (7)
C6	0.0374 (8)	0.0368 (8)	0.0459 (9)	−0.0015 (7)	−0.0125 (7)	−0.0052 (7)
C7	0.0373 (8)	0.0374 (8)	0.0392 (8)	−0.0092 (6)	−0.0081 (6)	−0.0022 (6)
C8	0.0424 (9)	0.0475 (10)	0.0422 (9)	−0.0129 (7)	−0.0053 (7)	−0.0104 (7)
C9	0.0781 (14)	0.0604 (13)	0.0591 (12)	−0.0270 (11)	−0.0262 (11)	−0.0055 (10)
C10	0.0892 (17)	0.0836 (17)	0.0660 (14)	−0.0247 (14)	−0.0404 (13)	0.0000 (12)
C11	0.0753 (15)	0.0612 (13)	0.0551 (12)	−0.0048 (11)	−0.0143 (11)	−0.0003 (10)
C12	0.1027 (19)	0.0499 (13)	0.0779 (16)	−0.0253 (12)	−0.0269 (14)	0.0012 (11)
C13	0.0770 (15)	0.0537 (12)	0.0718 (14)	−0.0258 (11)	−0.0268 (11)	−0.0027 (10)
C14	0.124 (3)	0.089 (2)	0.088 (2)	−0.0063 (18)	−0.037 (2)	0.0206 (16)
N1	0.0406 (8)	0.0443 (8)	0.0478 (8)	−0.0178 (6)	−0.0080 (6)	−0.0087 (6)
O1	0.0349 (7)	0.0683 (9)	0.0644 (8)	−0.0120 (6)	−0.0093 (6)	−0.0104 (7)
O2	0.0688 (9)	0.0442 (8)	0.0713 (9)	−0.0070 (7)	−0.0126 (7)	−0.0218 (7)
O3	0.0473 (7)	0.0476 (8)	0.0707 (9)	−0.0054 (6)	−0.0238 (6)	−0.0202 (6)
O4	0.0473 (7)	0.0399 (7)	0.0603 (8)	0.0001 (5)	−0.0193 (6)	−0.0110 (6)
S1	0.0381 (3)	0.0422 (3)	0.0497 (3)	−0.00771 (18)	−0.00885 (18)	−0.01246 (18)

Geometric parameters (Å, º) top

C1—C6	1.382 (2)	C9—C10	1.378 (3)
C1—C2	1.386 (2)	C9—H9	0.9300
C1—N1	1.436 (2)	C10—C11	1.368 (3)
C2—C3	1.385 (2)	C10—H10	0.9300
C2—H2	0.9300	C11—C12	1.364 (3)
C3—C4	1.387 (2)	C11—C14	1.517 (3)
C3—H3	0.9300	C12—C13	1.377 (3)
C4—C5	1.387 (2)	C12—H12	0.9300
C4—C7	1.482 (2)	C13—H13	0.9300
C5—C6	1.379 (2)	C14—H14A	0.9600
C5—H5	0.9300	C14—H14B	0.9600
C6—H6	0.9300	C14—H14C	0.9600
C7—O4	1.251 (2)	N1—S1	1.6366 (16)
C7—O3	1.2670 (19)	N1—H1N	0.82 (2)
C8—C13	1.375 (3)	O1—S1	1.4321 (13)
C8—C9	1.380 (2)	O2—S1	1.4232 (13)
C8—S1	1.7564 (19)	O3—H3O	0.8200

C6—C1—C2	120.40 (15)	C11—C10—H10	118.9
C6—C1—N1	118.37 (14)	C9—C10—H10	118.9
C2—C1—N1	121.23 (14)	C12—C11—C10	117.6 (2)
C3—C2—C1	119.66 (15)	C12—C11—C14	120.8 (2)
C3—C2—H2	120.2	C10—C11—C14	121.7 (2)
C1—C2—H2	120.2	C11—C12—C13	122.2 (2)
C2—C3—C4	120.00 (15)	C11—C12—H12	118.9
C2—C3—H3	120.0	C13—C12—H12	118.9
C4—C3—H3	120.0	C8—C13—C12	119.23 (19)
C5—C4—C3	119.86 (14)	C8—C13—H13	120.4
C5—C4—C7	119.40 (14)	C12—C13—H13	120.4
C3—C4—C7	120.73 (14)	C11—C14—H14A	109.5
C6—C5—C4	120.15 (14)	C11—C14—H14B	109.5
C6—C5—H5	119.9	H14A—C14—H14B	109.5
C4—C5—H5	119.9	C11—C14—H14C	109.5
C5—C6—C1	119.89 (15)	H14A—C14—H14C	109.5
C5—C6—H6	120.1	H14B—C14—H14C	109.5
C1—C6—H6	120.1	C1—N1—S1	118.23 (11)
O4—C7—O3	123.49 (15)	C1—N1—H1N	114.4 (15)
O4—C7—C4	119.73 (14)	S1—N1—H1N	111.3 (15)
O3—C7—C4	116.78 (14)	C7—O3—H3O	109.5
C13—C8—C9	119.84 (19)	O2—S1—O1	119.96 (9)
C13—C8—S1	120.34 (14)	O2—S1—N1	106.32 (8)
C9—C8—S1	119.49 (15)	O1—S1—N1	106.96 (8)
C10—C9—C8	119.0 (2)	O2—S1—C8	108.93 (8)
C10—C9—H9	120.5	O1—S1—C8	108.33 (9)
C8—C9—H9	120.5	N1—S1—C8	105.41 (8)
C11—C10—C9	122.2 (2)

C6—C1—C2—C3	0.3 (3)	C9—C10—C11—C14	−177.3 (3)
N1—C1—C2—C3	−179.80 (15)	C10—C11—C12—C13	−0.7 (4)
C1—C2—C3—C4	1.5 (3)	C14—C11—C12—C13	177.5 (3)
C2—C3—C4—C5	−1.8 (3)	C9—C8—C13—C12	0.4 (3)
C2—C3—C4—C7	179.29 (16)	S1—C8—C13—C12	−173.0 (2)
C3—C4—C5—C6	0.4 (3)	C11—C12—C13—C8	0.1 (4)
C7—C4—C5—C6	179.27 (15)	C6—C1—N1—S1	−79.40 (18)
C4—C5—C6—C1	1.4 (3)	C2—C1—N1—S1	100.69 (17)
C2—C1—C6—C5	−1.7 (3)	C1—N1—S1—O2	175.57 (12)
N1—C1—C6—C5	178.34 (15)	C1—N1—S1—O1	46.27 (15)
C5—C4—C7—O4	−172.22 (16)	C1—N1—S1—C8	−68.88 (13)
C3—C4—C7—O4	6.7 (3)	C13—C8—S1—O2	−161.30 (17)
C5—C4—C7—O3	7.4 (2)	C9—C8—S1—O2	25.26 (19)
C3—C4—C7—O3	−173.74 (16)	C13—C8—S1—O1	−29.26 (19)
C13—C8—C9—C10	−0.2 (3)	C9—C8—S1—O1	157.30 (17)
S1—C8—C9—C10	173.2 (2)	C13—C8—S1—N1	84.95 (18)
C8—C9—C10—C11	−0.4 (4)	C9—C8—S1—N1	−88.49 (18)
C9—C10—C11—C12	0.8 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1ⁱ	0.81 (3)	2.25 (3)	3.042 (2)	164.2 (2)
O3—H3O···O4ⁱⁱ	0.82	1.83	2.633 (2)	166
C5—H5···O3ⁱⁱⁱ	0.93	2.55	3.397 (2)	151
C6—H6···O4^iv	0.93	2.43	3.294 (3)	155

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

Experimental details

Crystal data
Chemical formula	C₁₄H₁₃NO₄S
M_r	291.31
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	5.1588 (2), 6.9277 (2), 20.0350 (6)
α, β, γ (°)	83.574 (1), 86.357 (1), 72.824 (1)
V (Å³)	679.44 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.25
Crystal size (mm)	0.35 × 0.31 × 0.22

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	12209, 3313, 2660
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.147, 1.01
No. of reflections	3310
No. of parameters	186
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.22

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1ⁱ	0.81 (3)	2.25 (3)	3.042 (2)	164.2 (2)
O3—H3O···O4ⁱⁱ	0.82	1.83	2.633 (2)	166
C5—H5···O3ⁱⁱⁱ	0.93	2.55	3.397 (2)	151
C6—H6···O4^iv	0.93	2.43	3.294 (3)	155

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

References

Arshad, M. N., Khan, I. U. & Zia-ur-Rehman, M. (2008). Acta Cryst. E64, o2283–o2284. Web of Science CSD CrossRef IUCr Journals Google Scholar
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
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Volume 67| Part 4| April 2011| Page o1018

doi:10.1107/S1600536811011524

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