2-(4-Bromo­benzene­sulfonamido)acetic acid

Arshad, M.N.; Khan, I.U.; Shafiq, M.; Khan, M.N.; Stoeckli-Evans, H.

doi:10.1107/S160053680902604X

organic compounds

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ISSN: 2056-9890

Volume 65| Part 8| August 2009| Page o1816

doi:10.1107/S160053680902604X

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2-(4-Bromobenzenesulfonamido)acetic acid

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

^aMaterials Chemistry Laboratory, Department of Chemistry, GC University, Lahore, Pakistan, ^bPCSIR, Laboratories Complex, Ferozpur Road, Lahore, Pakistan, and ^cInstitute of Physics, Université of Neuchâtel, Rue Emile-Argand 11, CH-2009 Neuchâtel, Switzerland
^*Correspondence e-mail: mnachemist@hotmail.com

(Received 30 June 2009; accepted 4 July 2009; online 11 July 2009)

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, $[P \overline 1]$
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[F² > 2σ(F²)] = 0.058
wR(F²) = 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

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
Symmetry codes: (i) -x+1, -y-1, -z+1; (ii) -x+1, -y, -z+1; (iii) x, y+1, z; (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: PLATON (Spek, 2009 ) and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: SHELXL97.

Supporting information

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

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

checkCIF report

Comment top

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.

Related literature top

For background information, see: Arshad et al. (2008b). For details of 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 top

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.

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: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I), with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. A view along the a axis of the crystal packing of compound (I), with O—H···O and N—H···O hydrogen bonds drawn as dashed lines [see Table 1 for details; H atoms not involved in hydrogen bonding have been omitted for clarity].
	Fig. 3. A view along the b axis of the crystal packing of (I), with O—H···O, N—H···O and C—H···O hydrogen bonds drawn as dashed lines [see Table 1 for details; H atoms not involved in hydrogen bonding have been omitted for clarity].
	Fig. 4. A view of the hydrogen bonding patterns in the three acid compounds: (I), (III) and (IV). The hydrogen bonds are shown as pale-blue lines.

2-(4-Bromobenzenesulfonamido)acetic acid top

Crystal data top

C₈H₈BrNO₄S	Z = 2
M_r = 294.12	F(000) = 292
Triclinic, P1	D_x = 1.896 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.0042 (4) Å	Cell parameters from 1869 reflections
b = 7.9997 (6) Å	θ = 2.2–21.8°
c = 13.2289 (11) Å	µ = 4.18 mm⁻¹
α = 79.691 (4)°	T = 296 K
β = 88.667 (5)°	Needle, colorless
γ = 81.404 (4)°	0.28 × 0.17 × 0.11 mm
V = 515.18 (7) Å³

Data collection top

Bruker Kappa APEXII CCD diffractometer	2557 independent reflections
Radiation source: fine-focus sealed tube	1243 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.056
ϕ and ω scans	θ_max = 28.3°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −6→6
T_min = 0.612, T_max = 0.632	k = −10→10
10359 measured reflections	l = −17→17

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)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.168	H-atom parameters constrained
S = 0.95	w = 1/[σ²(F_o²) + (0.0872P)² + 0.2177P] where P = (F_o² + 2F_c²)/3
2557 reflections	(Δ/σ)_max < 0.001
137 parameters	Δρ_max = 1.15 e Å⁻³
0 restraints	Δρ_min = −0.38 e Å⁻³

Crystal data top

C₈H₈BrNO₄S	γ = 81.404 (4)°
M_r = 294.12	V = 515.18 (7) Å³
Triclinic, P1	Z = 2
a = 5.0042 (4) Å	Mo Kα radiation
b = 7.9997 (6) Å	µ = 4.18 mm⁻¹
c = 13.2289 (11) Å	T = 296 K
α = 79.691 (4)°	0.28 × 0.17 × 0.11 mm
β = 88.667 (5)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	2557 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2007)	1243 reflections with I > 2σ(I)
T_min = 0.612, T_max = 0.632	R_int = 0.056
10359 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.058	0 restraints
wR(F²) = 0.168	H-atom parameters constrained
S = 0.95	Δρ_max = 1.15 e Å⁻³
2557 reflections	Δρ_min = −0.38 e Å⁻³
137 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
Br1	0.70371 (17)	0.78972 (8)	0.05167 (5)	0.0774 (4)
S1	0.3354 (2)	0.11701 (17)	0.32101 (10)	0.0365 (4)
O1	0.2650 (7)	0.0106 (5)	0.2528 (3)	0.0486 (10)
O2	0.1387 (7)	0.1738 (5)	0.3930 (3)	0.0492 (10)
O3	0.7775 (7)	−0.4424 (5)	0.4169 (3)	0.0505 (10)
H3O	0.7174	−0.5221	0.4536	0.076*
O4	0.4156 (7)	−0.2871 (4)	0.4743 (3)	0.0427 (9)
N1	0.5998 (8)	0.0162 (5)	0.3816 (3)	0.0389 (10)
H1	0.6632	0.0630	0.4278	0.047*
C1	0.5927 (12)	0.5917 (7)	0.1309 (4)	0.0456 (14)
C2	0.3808 (12)	0.6089 (7)	0.1979 (5)	0.0495 (15)
H2	0.2914	0.7172	0.2039	0.059*
C3	0.3022 (11)	0.4635 (7)	0.2560 (5)	0.0453 (14)
H3	0.1575	0.4737	0.3010	0.054*
C4	0.4368 (10)	0.3039 (7)	0.2478 (4)	0.0355 (12)
C5	0.6490 (11)	0.2867 (7)	0.1801 (4)	0.0489 (15)
H5	0.7386	0.1784	0.1742	0.059*
C6	0.7271 (13)	0.4320 (8)	0.1211 (5)	0.0584 (17)
H6	0.8695	0.4221	0.0751	0.070*
C7	0.7389 (10)	−0.1470 (6)	0.3652 (4)	0.0410 (13)
H7A	0.9274	−0.1559	0.3839	0.049*
H7B	0.7316	−0.1519	0.2925	0.049*
C8	0.6253 (10)	−0.2978 (7)	0.4249 (4)	0.0368 (12)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.1144 (7)	0.0372 (4)	0.0728 (6)	−0.0176 (4)	0.0098 (4)	0.0154 (3)
S1	0.0376 (7)	0.0264 (7)	0.0458 (8)	−0.0085 (5)	0.0029 (5)	−0.0043 (6)
O1	0.053 (2)	0.037 (2)	0.060 (3)	−0.0124 (18)	−0.0073 (18)	−0.0143 (19)
O2	0.045 (2)	0.046 (2)	0.058 (2)	−0.0118 (18)	0.0163 (18)	−0.011 (2)
O3	0.050 (2)	0.027 (2)	0.069 (3)	0.0001 (18)	0.0167 (19)	−0.001 (2)
O4	0.0398 (19)	0.027 (2)	0.059 (2)	−0.0058 (16)	0.0127 (17)	−0.0008 (17)
N1	0.050 (2)	0.019 (2)	0.046 (3)	−0.0062 (19)	−0.002 (2)	−0.001 (2)
C1	0.064 (4)	0.026 (3)	0.044 (3)	−0.009 (3)	−0.004 (3)	0.002 (3)
C2	0.059 (3)	0.017 (3)	0.068 (4)	0.003 (3)	0.000 (3)	−0.006 (3)
C3	0.045 (3)	0.025 (3)	0.065 (4)	−0.002 (2)	0.008 (3)	−0.007 (3)
C4	0.041 (3)	0.027 (3)	0.038 (3)	−0.003 (2)	−0.001 (2)	−0.005 (2)
C5	0.064 (4)	0.022 (3)	0.054 (4)	0.001 (3)	0.013 (3)	0.004 (3)
C6	0.073 (4)	0.040 (4)	0.054 (4)	−0.001 (3)	0.021 (3)	0.006 (3)
C7	0.039 (3)	0.032 (3)	0.049 (3)	−0.010 (2)	0.009 (2)	0.001 (3)
C8	0.035 (3)	0.033 (3)	0.042 (3)	−0.007 (2)	0.000 (2)	−0.003 (2)

Geometric parameters (Å, º) top

Br1—C1	1.886 (5)	C2—C3	1.379 (7)
S1—O1	1.429 (4)	C2—H2	0.9300
S1—O2	1.436 (4)	C3—C4	1.374 (7)
S1—N1	1.594 (4)	C3—H3	0.9300
S1—C4	1.765 (5)	C4—C5	1.380 (7)
O3—C8	1.306 (6)	C5—C6	1.382 (7)
O3—H3O	0.8200	C5—H5	0.9300
O4—C8	1.223 (6)	C6—H6	0.9300
N1—C7	1.436 (6)	C7—C8	1.499 (6)
N1—H1	0.8600	C7—H7A	0.9700
C1—C2	1.373 (8)	C7—H7B	0.9700
C1—C6	1.379 (8)

O1—S1—O2	119.3 (2)	C3—C4—C5	120.5 (5)
O1—S1—N1	106.7 (2)	C3—C4—S1	120.6 (4)
O2—S1—N1	109.3 (2)	C5—C4—S1	118.9 (4)
O1—S1—C4	108.9 (2)	C4—C5—C6	119.4 (5)
O2—S1—C4	106.5 (2)	C4—C5—H5	120.3
N1—S1—C4	105.3 (2)	C6—C5—H5	120.3
C8—O3—H3O	109.5	C1—C6—C5	119.6 (5)
C7—N1—S1	124.8 (4)	C1—C6—H6	120.2
C7—N1—H1	117.6	C5—C6—H6	120.2
S1—N1—H1	117.5	N1—C7—C8	113.8 (4)
C2—C1—C6	121.0 (5)	N1—C7—H7A	108.8
C2—C1—Br1	119.6 (4)	C8—C7—H7A	108.8
C6—C1—Br1	119.4 (4)	N1—C7—H7B	108.8
C1—C2—C3	119.2 (5)	C8—C7—H7B	108.8
C1—C2—H2	120.4	H7A—C7—H7B	107.7
C3—C2—H2	120.4	O4—C8—O3	124.3 (5)
C4—C3—C2	120.2 (5)	O4—C8—C7	124.4 (5)
C4—C3—H3	119.9	O3—C8—C7	111.4 (4)
C2—C3—H3	119.9

O1—S1—N1—C7	2.2 (4)	O1—S1—C4—C5	−57.6 (5)
O2—S1—N1—C7	132.5 (4)	O2—S1—C4—C5	172.6 (4)
C4—S1—N1—C7	−113.5 (4)	N1—S1—C4—C5	56.6 (5)
C6—C1—C2—C3	0.0 (9)	C3—C4—C5—C6	0.6 (9)
Br1—C1—C2—C3	−179.5 (4)	S1—C4—C5—C6	178.9 (5)
C1—C2—C3—C4	0.8 (9)	C2—C1—C6—C5	−0.5 (10)
C2—C3—C4—C5	−1.1 (8)	Br1—C1—C6—C5	179.1 (5)
C2—C3—C4—S1	−179.4 (4)	C4—C5—C6—C1	0.2 (9)
O1—S1—C4—C3	120.7 (5)	S1—N1—C7—C8	−85.5 (5)
O2—S1—C4—C3	−9.1 (5)	N1—C7—C8—O4	8.2 (8)
N1—S1—C4—C3	−125.2 (5)	N1—C7—C8—O3	−172.4 (4)

Hydrogen-bond geometry (Å, º) top

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
C3—H3···O2	0.93	2.50	2.884 (7)	105

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

Experimental details

Crystal data
Chemical formula	C₈H₈BrNO₄S
M_r	294.12
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	5.0042 (4), 7.9997 (6), 13.2289 (11)
α, β, γ (°)	79.691 (4), 88.667 (5), 81.404 (4)
V (Å³)	515.18 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	4.18
Crystal size (mm)	0.28 × 0.17 × 0.11

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2007)
T_min, T_max	0.612, 0.632
No. of measured, independent and observed [I > 2σ(I)] reflections	10359, 2557, 1243
R_int	0.056
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.168, 0.95
No. of reflections	2557
No. of parameters	137
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.15, −0.38

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

Hydrogen-bond geometry (Å, º) top

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

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

Acknowledgements

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

References

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