2-(4-Bromo­benzene­sulfonamido)acetic acid

Muhammad Nadeem Arshad; Islam Ullah Khan; Muhammad Shafiq; Muhammad Naeem Khan; Helen Stoeckli-Evans

doi:10.1107/S160053680902604X

. 2009 Jul 11;65(Pt 8):o1816. doi: 10.1107/S160053680902604X

2-(4-Bromobenzenesulfonamido)acetic acid

Muhammad Nadeem Arshad ^a,^*, Islam Ullah Khan ^a, Muhammad Shafiq ^a, Muhammad Naeem Khan ^b, Helen Stoeckli-Evans ^c

PMCID: PMC2977417 PMID: 21583519

Abstract

The title compound, C₈H₈BrNO₄S, a halogenated sulfonamide, was prepared by basic hydrolysis of the methyl ester. In the crystal, molecules form centrosymmetric hydrogen-bonded dimers via the carboxyl groups. These dimers are further linked by N—H⋯O interactions involving the carbonyl O and amide H atoms, forming a ribbon-like structure propagating in [010]. These ribbons are further linked via C—H⋯O interactions, forming a three-dimensional network.

Related literature

For details of the crystal structure of the methyl ester of the title compound, see: Arshad et al. (2008b ▶). For related structures, see: Arshad et al. (2008a ▶); Arshad et al. (2009 ▶). For related thiazine heterocycles, see: Arshad et al. (2008c ▶). For hydrogen-bonding patterns, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₈H₈BrNO₄S
M _r = 294.12
Triclinic,
a = 5.0042 (4) Å
b = 7.9997 (6) Å
c = 13.2289 (11) Å
α = 79.691 (4)°
β = 88.667 (5)°
γ = 81.404 (4)°
V = 515.18 (7) Å³
Z = 2
Mo Kα radiation
μ = 4.18 mm⁻¹
T = 296 K
0.28 × 0.17 × 0.11 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ▶) T _min = 0.612, T _max = 0.632
10359 measured reflections
2557 independent reflections
1243 reflections with I > 2σ(I)
R _int = 0.056

Refinement

R[F ² > 2σ(F ²)] = 0.058
wR(F ²) = 0.168
S = 0.95
2557 reflections
137 parameters
H-atom parameters constrained
Δρ_max = 1.15 e Å⁻³
Δρ_min = −0.38 e Å⁻³

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: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680902604X/tk2493sup1.cif

e-65-o1816-sup1.cif^{(15.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053680902604X/tk2493Isup2.hkl

e-65-o1816-Isup2.hkl^{(125.6KB, hkl)}

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
O3—H3O⋯O4ⁱ	0.82	1.85	2.671 (5)	174
N1—H1⋯O4ⁱⁱ	0.86	2.38	3.124 (5)	146
C2—H2⋯O1ⁱⁱⁱ	0.93	2.53	3.384 (7)	153
C3—H3⋯O3^iv	0.93	2.50	3.423 (7)	170

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

Acknowledgments

MNA acknowledges the Higher Education Commission of Pakistan for providing a PhD Scholarship under PIN 042–120607-PS2–183.

supplementary crystallographic information

Comment

The title compound, (I), was prepared by basic hydrolysis of methyl (4-bromobenzenesulfonamido)acetate (II) (Arshad et al., 2008b), in a continuation of our studies on the synthesis of thiazine related heterocycles (Arshad et al., 2008c). We have previously reported the crystal structures of 2-(benzenesulfonamido)acetic acid (III) (Arshad et al., 2008a) and 2-(2-iodobenzenesulfonamido)acetic acid (IV) (Arshad et al., 2009).

The molecular structure of (I), Fig. 1, reveals the bond lengths and angles are similar to those found for compounds (II), (III) and (IV).

The presence of the carboxylic acid group leads to the formation of characteristic O—H···O hydrogen-bonded centrosymmetric dimers (Table 1 and Fig. 2). These dimers are linked via N1—H1···O4 interactions, involving the carbonyl O-atom and the H-atom of the amido group, to form a ribbon-like structure propagating in the [010] direction (Table 1 and Fig. 2). The ribbons are further linked by C—H···O interactions to form a 3-D network (Table 1 and Fig. 3).

It is interesting to compare the hydrogen bonding patterns in the three acids; (I), (III) and (IV). The formation of the hydrogen bonded carboxylic acid dimers is the same in all three compounds, i.e. R²₂(8) (Bernstein et al., 1995). The N—H···O hydrogen-bonding involves the sulfonamido groups in (III) and (IV) [R²₂(8)], while in (I) it involves the carbonyl O-atom (O4) and the H-atom of the amido group (Table 1). This leads to a larger hydrogen-bonded ring of the form [R²₂(10)], as shown in Fig. 4.

Experimental

Methyl (4-bromobenzenesulfonamido)acetate(II) (Arshad et al., 2008b) (1.0 g, 3.247 mmol) was dissolved in an aqueous sodium hydroxide solution (10%, 10 ml). The resulting solution was refluxed for an hour. The reaction mixture was then cooled to room temperature and acidified with 1 N HCl. A white precipitate was obtained. This was filtered off, washed with distilled water and dried. Crystals were obtained by recrystallization from methanol.