organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

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

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[Hanson, P. R., Probst, D. A., Robinson, R. E. & Yau, M. (1999). Tetrahedron Lett. 40, 4761-4763.]). For related structures, see: Gowda et al. (2007[Gowda, B. T., Foro, S. & Fuess, H. (2007). Acta Cryst. E63, o2339.]); Arshad et al. (2008[Arshad, M. N., Khan, I. U. & Zia-ur-Rehman, M. (2008). Acta Cryst. E64, o2283-o2284.]); Shafiq et al. (2009[Shafiq, M., Zia-ur-Rehman, M., Khan, I. U., Arshad, M. N. & Ahmad, I. (2009). Acta Cryst. E65, o2453.]).

[Scheme 1]

Experimental

Crystal data
  • C14H13NO4S

  • Mr = 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)

  • Rint = 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

  • Δρmax = 0.30 e Å−3

  • Δρmin = −0.22 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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⋯O4iv 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[Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2007[Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information


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).

Refinement top

The aromatic C—H H-atoms were positioned with idealized geometry with C—H = 0.93 Å and were refined using a riding model with Uiso(H) = 1.2 Ueq(C). The O—H H-atom was also positioned with idealized geometry with O—H = 0.82 Å and was refined using a riding model with Uiso(H) = 1.5 Ueq(O). The N—H H atom were located in difference map and its position refiined freely to N—H= 0.82 (2) Å, Uiso(H) = 1.2Uiso(N). Three reflection 011, 001 and 002 were omitted in the final refinement as these were obscured by beam stop.

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
[Figure 1] Fig. 1. The moleuclar structure of (I) with displacement ellipsoids drawn at the 50% probability level.
[Figure 2] 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
C14H13NO4SZ = 2
Mr = 291.31F(000) = 304
Triclinic, P1Dx = 1.424 Mg m3
Hall symbol: -P 1Melting point: 503 K
a = 5.1588 (2) ÅMo Kα radiation, λ = 0.71073 Å
b = 6.9277 (2) ÅCell parameters from 5143 reflections
c = 20.0350 (6) Åθ = 3.1–27.8°
α = 83.574 (1)°µ = 0.25 mm1
β = 86.357 (1)°T = 296 K
γ = 72.824 (1)°Needles, colourless
V = 679.44 (4) Å30.35 × 0.31 × 0.22 mm
Data collection top
Bruker APEXII CCD
diffractometer
2660 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.029
Graphite monochromatorθmax = 28.3°, θmin = 1.0°
ϕ and ω scansh = 66
12209 measured reflectionsk = 99
3313 independent reflectionsl = 2626
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.044Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.147H atoms treated by a mixture of independent and constrained refinement
S = 1.01 w = 1/[σ2(Fo2) + (0.0982P)2 + 0.0842P]
where P = (Fo2 + 2Fc2)/3
3310 reflections(Δ/σ)max = 0.001
186 parametersΔρmax = 0.30 e Å3
0 restraintsΔρmin = 0.22 e Å3
Crystal data top
C14H13NO4Sγ = 72.824 (1)°
Mr = 291.31V = 679.44 (4) Å3
Triclinic, P1Z = 2
a = 5.1588 (2) ÅMo Kα radiation
b = 6.9277 (2) ŵ = 0.25 mm1
c = 20.0350 (6) ÅT = 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 reflectionsRint = 0.029
3313 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0440 restraints
wR(F2) = 0.147H atoms treated by a mixture of independent and constrained refinement
S = 1.01Δρmax = 0.30 e Å3
3310 reflectionsΔρmin = 0.22 e Å3
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
xyzUiso*/Ueq
C11.0578 (3)0.2205 (2)0.33980 (8)0.0363 (3)
C20.8392 (3)0.0474 (3)0.33116 (9)0.0450 (4)
H20.70400.04140.30170.054*
C30.8230 (3)0.1167 (3)0.36655 (9)0.0447 (4)
H30.67460.23200.36170.054*
C41.0281 (3)0.1089 (2)0.40922 (8)0.0357 (3)
C51.2453 (3)0.0655 (3)0.41777 (8)0.0406 (4)
H51.38240.07110.44650.049*
C61.2585 (3)0.2306 (3)0.38368 (9)0.0415 (4)
H61.40220.34850.39020.050*
C71.0157 (3)0.2840 (2)0.44689 (8)0.0381 (4)
C81.1343 (4)0.2279 (3)0.17695 (9)0.0435 (4)
C90.9505 (5)0.2551 (3)0.13444 (11)0.0634 (6)
H90.92130.38140.13450.076*
C100.8108 (6)0.0924 (4)0.09195 (13)0.0786 (7)
H100.68770.11120.06310.094*
C110.8470 (5)0.0958 (4)0.09073 (12)0.0670 (6)
C121.0313 (6)0.1180 (4)0.13297 (14)0.0757 (7)
H121.06030.24440.13260.091*
C131.1759 (5)0.0405 (3)0.17613 (12)0.0652 (6)
H131.30020.02110.20440.078*
C140.6831 (8)0.2757 (5)0.04587 (16)0.1065 (11)
H14A0.64200.22970.00550.160*
H14B0.78640.37030.03470.160*
H14C0.51720.34110.06910.160*
N11.0818 (3)0.3933 (2)0.30382 (7)0.0424 (3)
O11.5356 (2)0.3963 (2)0.25576 (7)0.0559 (4)
O21.2874 (3)0.6138 (2)0.21531 (8)0.0617 (4)
O31.2221 (3)0.2721 (2)0.47994 (7)0.0549 (4)
H3O1.19590.37550.49890.082*
O40.8069 (3)0.43283 (18)0.44517 (7)0.0507 (3)
S11.28689 (8)0.42565 (6)0.23758 (2)0.04325 (17)
H1N0.937 (4)0.412 (3)0.2967 (10)0.052*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0353 (8)0.0366 (8)0.0385 (8)0.0115 (6)0.0060 (6)0.0040 (6)
C20.0334 (8)0.0505 (10)0.0511 (10)0.0074 (7)0.0150 (7)0.0102 (8)
C30.0359 (8)0.0417 (9)0.0527 (10)0.0019 (7)0.0148 (7)0.0066 (7)
C40.0349 (8)0.0357 (8)0.0363 (8)0.0092 (6)0.0071 (6)0.0023 (6)
C50.0350 (8)0.0420 (9)0.0434 (9)0.0058 (7)0.0146 (6)0.0063 (7)
C60.0374 (8)0.0368 (8)0.0459 (9)0.0015 (7)0.0125 (7)0.0052 (7)
C70.0373 (8)0.0374 (8)0.0392 (8)0.0092 (6)0.0081 (6)0.0022 (6)
C80.0424 (9)0.0475 (10)0.0422 (9)0.0129 (7)0.0053 (7)0.0104 (7)
C90.0781 (14)0.0604 (13)0.0591 (12)0.0270 (11)0.0262 (11)0.0055 (10)
C100.0892 (17)0.0836 (17)0.0660 (14)0.0247 (14)0.0404 (13)0.0000 (12)
C110.0753 (15)0.0612 (13)0.0551 (12)0.0048 (11)0.0143 (11)0.0003 (10)
C120.1027 (19)0.0499 (13)0.0779 (16)0.0253 (12)0.0269 (14)0.0012 (11)
C130.0770 (15)0.0537 (12)0.0718 (14)0.0258 (11)0.0268 (11)0.0027 (10)
C140.124 (3)0.089 (2)0.088 (2)0.0063 (18)0.037 (2)0.0206 (16)
N10.0406 (8)0.0443 (8)0.0478 (8)0.0178 (6)0.0080 (6)0.0087 (6)
O10.0349 (7)0.0683 (9)0.0644 (8)0.0120 (6)0.0093 (6)0.0104 (7)
O20.0688 (9)0.0442 (8)0.0713 (9)0.0070 (7)0.0126 (7)0.0218 (7)
O30.0473 (7)0.0476 (8)0.0707 (9)0.0054 (6)0.0238 (6)0.0202 (6)
O40.0473 (7)0.0399 (7)0.0603 (8)0.0001 (5)0.0193 (6)0.0110 (6)
S10.0381 (3)0.0422 (3)0.0497 (3)0.00771 (18)0.00885 (18)0.01246 (18)
Geometric parameters (Å, º) top
C1—C61.382 (2)C9—C101.378 (3)
C1—C21.386 (2)C9—H90.9300
C1—N11.436 (2)C10—C111.368 (3)
C2—C31.385 (2)C10—H100.9300
C2—H20.9300C11—C121.364 (3)
C3—C41.387 (2)C11—C141.517 (3)
C3—H30.9300C12—C131.377 (3)
C4—C51.387 (2)C12—H120.9300
C4—C71.482 (2)C13—H130.9300
C5—C61.379 (2)C14—H14A0.9600
C5—H50.9300C14—H14B0.9600
C6—H60.9300C14—H14C0.9600
C7—O41.251 (2)N1—S11.6366 (16)
C7—O31.2670 (19)N1—H1N0.82 (2)
C8—C131.375 (3)O1—S11.4321 (13)
C8—C91.380 (2)O2—S11.4232 (13)
C8—S11.7564 (19)O3—H3O0.8200
C6—C1—C2120.40 (15)C11—C10—H10118.9
C6—C1—N1118.37 (14)C9—C10—H10118.9
C2—C1—N1121.23 (14)C12—C11—C10117.6 (2)
C3—C2—C1119.66 (15)C12—C11—C14120.8 (2)
C3—C2—H2120.2C10—C11—C14121.7 (2)
C1—C2—H2120.2C11—C12—C13122.2 (2)
C2—C3—C4120.00 (15)C11—C12—H12118.9
C2—C3—H3120.0C13—C12—H12118.9
C4—C3—H3120.0C8—C13—C12119.23 (19)
C5—C4—C3119.86 (14)C8—C13—H13120.4
C5—C4—C7119.40 (14)C12—C13—H13120.4
C3—C4—C7120.73 (14)C11—C14—H14A109.5
C6—C5—C4120.15 (14)C11—C14—H14B109.5
C6—C5—H5119.9H14A—C14—H14B109.5
C4—C5—H5119.9C11—C14—H14C109.5
C5—C6—C1119.89 (15)H14A—C14—H14C109.5
C5—C6—H6120.1H14B—C14—H14C109.5
C1—C6—H6120.1C1—N1—S1118.23 (11)
O4—C7—O3123.49 (15)C1—N1—H1N114.4 (15)
O4—C7—C4119.73 (14)S1—N1—H1N111.3 (15)
O3—C7—C4116.78 (14)C7—O3—H3O109.5
C13—C8—C9119.84 (19)O2—S1—O1119.96 (9)
C13—C8—S1120.34 (14)O2—S1—N1106.32 (8)
C9—C8—S1119.49 (15)O1—S1—N1106.96 (8)
C10—C9—C8119.0 (2)O2—S1—C8108.93 (8)
C10—C9—H9120.5O1—S1—C8108.33 (9)
C8—C9—H9120.5N1—S1—C8105.41 (8)
C11—C10—C9122.2 (2)
C6—C1—C2—C30.3 (3)C9—C10—C11—C14177.3 (3)
N1—C1—C2—C3179.80 (15)C10—C11—C12—C130.7 (4)
C1—C2—C3—C41.5 (3)C14—C11—C12—C13177.5 (3)
C2—C3—C4—C51.8 (3)C9—C8—C13—C120.4 (3)
C2—C3—C4—C7179.29 (16)S1—C8—C13—C12173.0 (2)
C3—C4—C5—C60.4 (3)C11—C12—C13—C80.1 (4)
C7—C4—C5—C6179.27 (15)C6—C1—N1—S179.40 (18)
C4—C5—C6—C11.4 (3)C2—C1—N1—S1100.69 (17)
C2—C1—C6—C51.7 (3)C1—N1—S1—O2175.57 (12)
N1—C1—C6—C5178.34 (15)C1—N1—S1—O146.27 (15)
C5—C4—C7—O4172.22 (16)C1—N1—S1—C868.88 (13)
C3—C4—C7—O46.7 (3)C13—C8—S1—O2161.30 (17)
C5—C4—C7—O37.4 (2)C9—C8—S1—O225.26 (19)
C3—C4—C7—O3173.74 (16)C13—C8—S1—O129.26 (19)
C13—C8—C9—C100.2 (3)C9—C8—S1—O1157.30 (17)
S1—C8—C9—C10173.2 (2)C13—C8—S1—N184.95 (18)
C8—C9—C10—C110.4 (4)C9—C8—S1—N188.49 (18)
C9—C10—C11—C120.8 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···O1i0.81 (3)2.25 (3)3.042 (2)164.2 (2)
O3—H3O···O4ii0.821.832.633 (2)166
C5—H5···O3iii0.932.553.397 (2)151
C6—H6···O4iv0.932.433.294 (3)155
Symmetry codes: (i) x1, y, z; (ii) x+2, y+1, z+1; (iii) x+3, y, z+1; (iv) x+1, y1, z.

Experimental details

Crystal data
Chemical formulaC14H13NO4S
Mr291.31
Crystal system, space groupTriclinic, 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)
V3)679.44 (4)
Z2
Radiation typeMo Kα
µ (mm1)0.25
Crystal size (mm)0.35 × 0.31 × 0.22
Data collection
DiffractometerBruker APEXII CCD
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
12209, 3313, 2660
Rint0.029
(sin θ/λ)max1)0.667
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.044, 0.147, 1.01
No. of reflections3310
No. of parameters186
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
N1—H1N···O1i0.81 (3)2.25 (3)3.042 (2)164.2 (2)
O3—H3O···O4ii0.821.832.633 (2)166
C5—H5···O3iii0.932.553.397 (2)151
C6—H6···O4iv0.932.433.294 (3)155
Symmetry codes: (i) x1, y, z; (ii) x+2, y+1, z+1; (iii) x+3, y, z+1; (iv) x+1, y1, z.
 

References

First citationArshad, M. N., Khan, I. U. & Zia-ur-Rehman, M. (2008). Acta Cryst. E64, o2283–o2284.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationBruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationGowda, B. T., Foro, S. & Fuess, H. (2007). Acta Cryst. E63, o2339.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationHanson, P. R., Probst, D. A., Robinson, R. E. & Yau, M. (1999). Tetrahedron Lett. 40, 4761–4763.  Web of Science CrossRef CAS Google Scholar
First citationShafiq, M., Zia-ur-Rehman, M., Khan, I. U., Arshad, M. N. & Ahmad, I. (2009). Acta Cryst. E65, o2453.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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