2-Methanesulfonamidobenzoic acid

Shafiq, M.; Zia-ur-Rehman, M.; Khan, I.U.; Arshad, M.N.; Ahmad, I.

doi:10.1107/S1600536809036113

organic compounds

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ISSN: 2056-9890

Volume 65| Part 10| October 2009| Page o2453

doi:10.1107/S1600536809036113

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2-Methanesulfonamidobenzoic acid

Muhammad Shafiq,^a ^* Muhammad Zia-ur-Rehman,^b Islam Ullah Khan,^a Muhammad Nadeem Arshad ^a and Imtiaz Ahmad ^a

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

(Received 6 September 2009; accepted 7 September 2009; online 12 September 2009)

In the title compound, C₈H₉NO₄S, an intramolecular N—H⋯O hydrogen bond gives rise to a six-membered ring. In the crystal structure, two molecules are connected by O—H⋯O hydrogen bonds, forming a centrosymmetric dimer. These dimers are further connected by C—H⋯O hydrogen bonds.

Related literature

For the synthesis and biological evaluation of sulfur-containing heterocyclic compounds, see: Zia-ur-Rehman et al. (2005 , 2006 , 2009 ); Xiao & Timberlake (2000 ); Lee & Lee (2002 ). For biological evaluation of sulfonamides, see: Hanson et al. (1999 ); Moree et al. (1991 ); Rough et al. (1998 ). For related literature on sulfonamides, see: Esteve & Bidal (2002 ); Soledade et al. (2006 ). For related structures, see: Gowda et al. (2007 ); Arshad et al. (2008 ).

Experimental

Crystal data

C₈H₉NO₄S
M_r = 215.23
Triclinic, $[P \overline 1]$
a = 5.2001 (2) Å
b = 8.6120 (4) Å
c = 11.2314 (5) Å
α = 72.675 (3)°
β = 84.155 (3)°
γ = 86.846 (3)°
V = 477.50 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.33 mm⁻¹
T = 296 K
0.19 × 0.09 × 0.02 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1997 ) T_min = 0.941, T_max = 0.993
9379 measured reflections
2330 independent reflections
1261 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.121
S = 1.01
2330 reflections
131 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O1ⁱ	0.78 (3)	1.89 (3)	2.671 (2)	172 (4)
N1—H1⋯O1	0.86	2.03	2.652 (2)	128
C4—H4⋯O3ⁱⁱ	0.93	2.37	3.235 (3)	155
Symmetry codes: (i) -x+2, -y+2, -z; (ii) x, 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: PLATON (Spek, 2009 ) and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and local programs.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809036113/bt5054sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809036113/bt5054Isup2.hkl

checkCIF report

Comment top

Sulfonamides are well known for their enormous potential as biologically active molecules (Hanson et al., 1999; Moree et al., 1991; Rough et al., 1998). Few of these are familiar as anti-hypertensive, anti-convulsant, herbicidal, anti-microbial and anti-microbial activities (Esteve & Bidal, 2002; Soledade et al., 2006; Xiao & Timberlake, 2000; Lee & Lee, 2002). In the present paper, the structure of the 2-[(methylsulfonyl)amino]benzoic acid has been determined as a part of a research program involving the synthesis and biological evaluation of sulfur containing heterocyclic compounds (Zia-ur-Rehman et al., 2005, 2006, 2009). In the molecule of (Fig. 1), bond lengths and bond angles are are almost similar to those in related molecules (Gowda et al., 2007; Arshad et al., 2008) and are within normal ranges. Each molecule exhibits an intramolecular N—H···O hydrogen bond which stabilizes the planar conformation and is linked to an adjacent one through head-to-tail pairs of O—H···O intermolecular interactions giving rise to dimeric motifs typical for carboxylic acids. Neighbouring dimers are further linked to each other through C—H···O interactions (Fig. 2).

Related literature top

For the synthesis and biological evaluation of sulfur-containing heterocyclic compounds, see: Zia-ur-Rehman et al. (2005, 2006, 2009); Xiao & Timberlake (2000); Lee & Lee (2002). For biological evaluation of sulfonamides, see: Hanson et al. (1999); Moree et al. (1991); Rough et al. (1998). For related literature on sulfonamides, see: Esteve & Bidal (2002); Soledade et al. (2006). For related structures, see: Gowda et al. (2007); Arshad et al. (2008).

Experimental top

A mixture of methyl 2-[(methylsulfonyl)amino]benzoate (1.0 g; 4.4 mmoles), sodium hydroxide (0.2 g; 5.0 mmoles) and water (30.0 ml) was stirred at room temperature for a period of one hour followed by addition of dilute hydrochloric acid to Congo Red (pH~5). Precipitates formed were filtered, washed with cold water and dried under vacuum followed by recrystallization in ethanol.

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: PLATON (Spek, 2009) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and local programs.

Figures top

Fig. 1. The molecular structure of the title compound, with displacement ellipsoids at the 50% probability level.

2-Methanesulfonamidobenzoic acid top

Crystal data top

C₈H₉NO₄S	Z = 2
M_r = 215.23	F(000) = 224
Triclinic, P1	D_x = 1.497 Mg m⁻³
Hall symbol: -P 1	Melting point: 373 K
a = 5.2001 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.6120 (4) Å	Cell parameters from 2313 reflections
c = 11.2314 (5) Å	θ = 2.6–26.6°
α = 72.675 (3)°	µ = 0.33 mm⁻¹
β = 84.155 (3)°	T = 296 K
γ = 86.846 (3)°	Needle, colourless
V = 477.50 (4) Å³	0.19 × 0.09 × 0.02 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	2330 independent reflections
Radiation source: fine-focus sealed tube	1261 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
ϕ and ω scans	θ_max = 28.3°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1997)	h = −6→6
T_min = 0.941, T_max = 0.993	k = −11→11
9379 measured reflections	l = −14→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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.121	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ²(F_o²) + (0.0569P)² + 0.0282P] where P = (F_o² + 2F_c²)/3
2330 reflections	(Δ/σ)_max < 0.001
131 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₈H₉NO₄S	γ = 86.846 (3)°
M_r = 215.23	V = 477.50 (4) Å³
Triclinic, P1	Z = 2
a = 5.2001 (2) Å	Mo Kα radiation
b = 8.6120 (4) Å	µ = 0.33 mm⁻¹
c = 11.2314 (5) Å	T = 296 K
α = 72.675 (3)°	0.19 × 0.09 × 0.02 mm
β = 84.155 (3)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	2330 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1997)	1261 reflections with I > 2σ(I)
T_min = 0.941, T_max = 0.993	R_int = 0.030
9379 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.121	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	Δρ_max = 0.21 e Å⁻³
2330 reflections	Δρ_min = −0.19 e Å⁻³
131 parameters

Special details top

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
S1	0.13958 (10)	0.86241 (8)	0.36548 (6)	0.0718 (3)
O1	0.7317 (3)	0.9547 (2)	0.09332 (14)	0.0702 (4)
O2	0.9632 (3)	0.7901 (2)	0.00272 (17)	0.0884 (6)
H2	1.047 (6)	0.868 (4)	−0.020 (3)	0.106*
O3	0.1286 (4)	1.0325 (2)	0.3430 (2)	0.1179 (8)
O4	−0.0938 (3)	0.7780 (2)	0.38190 (16)	0.0881 (6)
N1	0.3205 (3)	0.8337 (2)	0.24607 (18)	0.0737 (6)
H1	0.3768	0.9197	0.1899	0.088*
C1	0.6130 (4)	0.6764 (3)	0.14278 (19)	0.0580 (6)
C2	0.3943 (4)	0.6848 (3)	0.22472 (19)	0.0579 (6)
C3	0.2556 (4)	0.5456 (3)	0.2809 (2)	0.0770 (7)
H3	0.1102	0.5498	0.3355	0.092*
C4	0.3279 (5)	0.4020 (3)	0.2577 (3)	0.0826 (7)
H4	0.2305	0.3101	0.2959	0.099*
C5	0.5438 (5)	0.3919 (3)	0.1784 (3)	0.0839 (8)
H5	0.5945	0.2937	0.1635	0.101*
C6	0.6818 (5)	0.5284 (3)	0.1222 (2)	0.0778 (7)
H6	0.8272	0.5219	0.0682	0.093*
C7	0.7712 (4)	0.8198 (3)	0.07879 (19)	0.0617 (6)
C8	0.3072 (5)	0.7722 (4)	0.4963 (3)	0.0931 (9)
H8A	0.4750	0.8186	0.4842	0.140*
H8B	0.3260	0.6573	0.5079	0.140*
H8C	0.2130	0.7910	0.5690	0.140*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0519 (3)	0.0691 (5)	0.0812 (5)	−0.0032 (3)	0.0323 (3)	−0.0144 (3)
O1	0.0596 (9)	0.0739 (11)	0.0679 (10)	−0.0159 (8)	0.0290 (7)	−0.0160 (8)
O2	0.0795 (11)	0.0919 (14)	0.0887 (13)	−0.0233 (9)	0.0491 (9)	−0.0336 (11)
O3	0.1275 (16)	0.0632 (12)	0.1399 (18)	−0.0009 (10)	0.0728 (14)	−0.0229 (11)
O4	0.0469 (8)	0.1114 (14)	0.0933 (13)	−0.0105 (8)	0.0251 (8)	−0.0194 (10)
N1	0.0676 (11)	0.0592 (12)	0.0772 (13)	−0.0082 (9)	0.0391 (10)	−0.0078 (10)
C1	0.0512 (11)	0.0722 (15)	0.0480 (12)	−0.0099 (10)	0.0099 (9)	−0.0167 (11)
C2	0.0486 (11)	0.0615 (14)	0.0558 (13)	−0.0077 (10)	0.0123 (9)	−0.0099 (10)
C3	0.0625 (13)	0.0719 (17)	0.0865 (18)	−0.0136 (12)	0.0254 (12)	−0.0161 (13)
C4	0.0825 (16)	0.0716 (17)	0.0894 (19)	−0.0235 (13)	0.0146 (14)	−0.0207 (14)
C5	0.0952 (19)	0.0732 (17)	0.0866 (18)	−0.0142 (14)	0.0148 (15)	−0.0340 (14)
C6	0.0761 (15)	0.0870 (19)	0.0708 (16)	−0.0099 (14)	0.0227 (13)	−0.0322 (14)
C7	0.0510 (11)	0.0813 (17)	0.0466 (12)	−0.0093 (11)	0.0156 (9)	−0.0146 (12)
C8	0.0601 (14)	0.132 (2)	0.089 (2)	−0.0001 (15)	0.0122 (13)	−0.0406 (18)

Geometric parameters (Å, º) top

S1—O3	1.4091 (18)	C2—C3	1.381 (3)
S1—O4	1.4164 (16)	C3—C4	1.363 (3)
S1—N1	1.6307 (18)	C3—H3	0.9300
S1—C8	1.740 (3)	C4—C5	1.376 (3)
O1—C7	1.223 (3)	C4—H4	0.9300
O2—C7	1.312 (2)	C5—C6	1.361 (3)
O2—H2	0.78 (3)	C5—H5	0.9300
N1—C2	1.400 (3)	C6—H6	0.9300
N1—H1	0.8600	C8—H8A	0.9600
C1—C6	1.384 (3)	C8—H8B	0.9600
C1—C2	1.401 (3)	C8—H8C	0.9600
C1—C7	1.477 (3)

O3—S1—O4	119.14 (12)	C3—C4—C5	120.6 (2)
O3—S1—N1	104.71 (10)	C3—C4—H4	119.7
O4—S1—N1	109.48 (11)	C5—C4—H4	119.7
O3—S1—C8	109.48 (15)	C6—C5—C4	118.8 (2)
O4—S1—C8	107.25 (12)	C6—C5—H5	120.6
N1—S1—C8	106.10 (11)	C4—C5—H5	120.6
C7—O2—H2	107 (2)	C5—C6—C1	122.2 (2)
C2—N1—S1	127.27 (14)	C5—C6—H6	118.9
C2—N1—H1	116.4	C1—C6—H6	118.9
S1—N1—H1	116.4	O1—C7—O2	121.91 (19)
C6—C1—C2	118.5 (2)	O1—C7—C1	124.62 (18)
C6—C1—C7	119.46 (19)	O2—C7—C1	113.5 (2)
C2—C1—C7	122.1 (2)	S1—C8—H8A	109.5
C3—C2—N1	121.92 (19)	S1—C8—H8B	109.5
C3—C2—C1	118.7 (2)	H8A—C8—H8B	109.5
N1—C2—C1	119.34 (18)	S1—C8—H8C	109.5
C4—C3—C2	121.2 (2)	H8A—C8—H8C	109.5
C4—C3—H3	119.4	H8B—C8—H8C	109.5
C2—C3—H3	119.4

O3—S1—N1—C2	179.0 (2)	C1—C2—C3—C4	−0.1 (4)
O4—S1—N1—C2	−52.2 (2)	C2—C3—C4—C5	0.7 (4)
C8—S1—N1—C2	63.2 (2)	C3—C4—C5—C6	−0.9 (4)
S1—N1—C2—C3	22.1 (3)	C4—C5—C6—C1	0.4 (4)
S1—N1—C2—C1	−158.81 (18)	C2—C1—C6—C5	0.3 (4)
C6—C1—C2—C3	−0.4 (3)	C7—C1—C6—C5	180.0 (2)
C7—C1—C2—C3	179.9 (2)	C6—C1—C7—O1	−177.7 (2)
C6—C1—C2—N1	−179.6 (2)	C2—C1—C7—O1	2.0 (4)
C7—C1—C2—N1	0.7 (3)	C6—C1—C7—O2	2.3 (3)
N1—C2—C3—C4	179.1 (2)	C2—C1—C7—O2	−177.9 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1ⁱ	0.78 (3)	1.89 (3)	2.671 (2)	172 (4)
N1—H1···O1	0.86	2.03	2.652 (2)	128
C4—H4···O3ⁱⁱ	0.93	2.37	3.235 (3)	155

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

Experimental details

Crystal data
Chemical formula	C₈H₉NO₄S
M_r	215.23
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	5.2001 (2), 8.6120 (4), 11.2314 (5)
α, β, γ (°)	72.675 (3), 84.155 (3), 86.846 (3)
V (Å³)	477.50 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.33
Crystal size (mm)	0.19 × 0.09 × 0.02

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1997)
T_min, T_max	0.941, 0.993
No. of measured, independent and observed [I > 2σ(I)] reflections	9379, 2330, 1261
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.121, 1.01
No. of reflections	2330
No. of parameters	131
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.19

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and Mercury (Macrae et al., 2006), SHELXTL (Sheldrick, 2008) and local programs.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1ⁱ	0.78 (3)	1.89 (3)	2.671 (2)	172 (4)
N1—H1···O1	0.8600	2.0300	2.652 (2)	128.00
C4—H4···O3ⁱⁱ	0.9300	2.3700	3.235 (3)	155.0

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

Acknowledgements

The authors are grateful to the Higher Education Commission for a grant to purchase he X-ray diffractometer.

References

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