Methyl 2-(benzene­sulfonamido)acetate

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

doi:10.1107/S160053680901616X

organic compounds

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ISSN: 2056-9890

Volume 65| Part 6| June 2009| Page o1204

doi:10.1107/S160053680901616X

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Methyl 2-(benzenesulfonamido)acetate

Muhammad Nadeem Arshad,^a Islam Ullah Khan,^a ^* Muhammad Zia-ur-Rehman ^b and Muhammad Shafiq ^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 27 April 2009; accepted 29 April 2009; online 7 May 2009)

The title compound, C₉H₁₁NO₄S, is of interest as a precursor to biologically active benzothiazines. The crystal structure is stabilized by intermolecular N—H⋯O and C—H⋯O interactions.

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 ); Martinez et al. (2000 ); Berredjem et al. (2000 ); Lee & Lee (2002 ). For related literature on sulfonamides, see: Esteve & Bidal (2002 ); Soledade et al. (2006 ). For related structures, see: Gowda et al. (2007a ,b ,c ).

Experimental

Crystal data

C₉H₁₁NO₄S
M_r = 229.26
Monoclinic, P 2₁
a = 9.7268 (8) Å
b = 5.0781 (4) Å
c = 10.9286 (9) Å
β = 100.087 (3)°
V = 531.46 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.30 mm⁻¹
T = 296 K
0.23 × 0.11 × 0.08 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ) T_min = 0.935, T_max = 0.977
6159 measured reflections
2216 independent reflections
1944 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.092
S = 1.07
2216 reflections
137 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.26 e Å⁻³
Absolute structure: Flack (1983 ), 394 Friedel pairs
Flack parameter: 0.089 (8)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O3ⁱ	0.86	2.28	2.998 (2)	141
C7—H7B⋯O3ⁱⁱ	0.97	2.55	3.503 (4)	168
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z]$ ; (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/S160053680901616X/bt2940sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680901616X/bt2940Isup2.hkl

checkCIF report

Comment top

Sulfonamide is an important functionality found in many naturally occurring as well as synthetic compounds which possess numerous types of biological activities (Soledade et al., 2006; Esteve & Bidal, 2002; Xiao & Timberlake, 2000; Martinez et al., 2000; Berredjem et al., 2000; Lee & Lee, 2002). In the present paper, the structure of the title compound has been determined as a part of our ongoing research on the synthesis and biological evaluation of sulfur containing heterocyclic compounds (Zia-ur-Rehman et al., 2005, 2006, 2009). In the molecule of (I) (Fig. 1), bond lengths and bond angles are almost similar to those in related sulfonamide molecules (Gowda et al., 2007a, 2007b, 2007c) and the bond lengths are within normal ranges. In the crystal structure, each molecule is linked to an adjacent one through C7—H7B···O3 contacts giving rise to chains along b-axis. Each molecule of the chain is further linked to the one of its neighbouring chain along a through intermolecular N—H···O interactions.

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); Martinez et al. (2000); Berredjem et al. (2000); Lee & Lee (2002). For related literature on sulfonamides, see: Esteve & Bidal (2002); Soledade et al. (2006). For rlated structures, see: Gowda et al. (2007a,b,c).

Experimental top

A mixture of benzene sulfonic acid (4.14 g, 23.44 mmoles), glycine methyl ester hydrochloride (2.94 g, 23.44 mmol.) and distilled water (50.0 ml) was stirred for half an hour. pH of the reaction mixture was adjusted to 8.0 with an aqueous sodium carbonate solution. After completion of the reaction, a white solid product was isolated, washed, dried and recrystallized in methanol to get the crystals suitable for for X-ray studies; m.p. 332 K.

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 showing the atom labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Part of the crystal structure, showing hydrogen bond interactions (dashed lines). along the [0 0 1] direction. H atoms not involved in hydrogen bonding have been omitted for clarity.

Methyl 2-(benzenesulfonamido)acetate top

Crystal data top

C₉H₁₁NO₄S	F(000) = 240
M_r = 229.26	D_x = 1.433 Mg m⁻³
Monoclinic, P2₁	Melting point: 332 K
Hall symbol: P 2yb	Mo Kα radiation, λ = 0.71073 Å
a = 9.7268 (8) Å	Cell parameters from 2710 reflections
b = 5.0781 (4) Å	θ = 2.6–26.6°
c = 10.9286 (9) Å	µ = 0.30 mm⁻¹
β = 100.087 (3)°	T = 296 K
V = 531.46 (7) Å³	Plates, colourless
Z = 2	0.23 × 0.11 × 0.08 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	2216 independent reflections
Radiation source: fine-focus sealed tube	1944 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
ϕ and ω scans	θ_max = 29.3°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −12→13
T_min = 0.935, T_max = 0.977	k = −4→6
6159 measured reflections	l = −11→15

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.036	H-atom parameters constrained
wR(F²) = 0.092	w = 1/[σ²(F_o²) + (0.0526P)² + 0.0105P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max < 0.001
2216 reflections	Δρ_max = 0.25 e Å⁻³
137 parameters	Δρ_min = −0.26 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 394 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.089 (8)

Crystal data top

C₉H₁₁NO₄S	V = 531.46 (7) Å³
M_r = 229.26	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 9.7268 (8) Å	µ = 0.30 mm⁻¹
b = 5.0781 (4) Å	T = 296 K
c = 10.9286 (9) Å	0.23 × 0.11 × 0.08 mm
β = 100.087 (3)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	2216 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2007)	1944 reflections with I > 2σ(I)
T_min = 0.935, T_max = 0.977	R_int = 0.028
6159 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	H-atom parameters constrained
wR(F²) = 0.092	Δρ_max = 0.25 e Å⁻³
S = 1.07	Δρ_min = −0.26 e Å⁻³
2216 reflections	Absolute structure: Flack (1983), 394 Friedel pairs
137 parameters	Absolute structure parameter: 0.089 (8)
1 restraint

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	0.61607 (5)	0.09862 (10)	0.21011 (5)	0.03580 (15)
O1	0.52527 (16)	−0.0799 (4)	0.25831 (16)	0.0482 (4)
O2	0.72360 (15)	0.0024 (4)	0.14799 (15)	0.0468 (4)
O3	0.27134 (16)	0.0012 (4)	0.03143 (16)	0.0469 (4)
O4	0.16275 (17)	0.2366 (4)	0.15812 (18)	0.0589 (5)
N1	0.51744 (17)	0.2853 (4)	0.11147 (16)	0.0389 (5)
H1	0.5423	0.3294	0.0426	0.047*
C1	0.6962 (2)	0.2993 (5)	0.3344 (2)	0.0366 (5)
C2	0.6546 (3)	0.2854 (7)	0.4486 (2)	0.0537 (7)
H2	0.5847	0.1687	0.4614	0.064*
C3	0.7181 (3)	0.4473 (8)	0.5441 (2)	0.0669 (9)
H3	0.6913	0.4382	0.6216	0.080*
C4	0.8199 (3)	0.6206 (8)	0.5249 (3)	0.0646 (8)
H4	0.8612	0.7303	0.5891	0.078*
C5	0.8614 (3)	0.6333 (7)	0.4113 (3)	0.0602 (7)
H5	0.9317	0.7494	0.3992	0.072*
C6	0.7990 (2)	0.4739 (5)	0.3148 (2)	0.0481 (6)
H6	0.8259	0.4843	0.2374	0.058*
C7	0.3858 (2)	0.3768 (5)	0.1419 (2)	0.0365 (5)
H7B	0.3610	0.5437	0.1008	0.044*
H7A	0.3966	0.4050	0.2309	0.044*
C8	0.2709 (2)	0.1813 (5)	0.10223 (19)	0.0346 (5)
C9	0.0435 (3)	0.0566 (10)	0.1303 (3)	0.0886 (12)
H9A	0.0132	0.0469	0.0419	0.133*
H9B	−0.0315	0.1204	0.1687	0.133*
H9C	0.0709	−0.1155	0.1619	0.133*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0316 (2)	0.0341 (3)	0.0417 (3)	−0.0008 (3)	0.00653 (19)	0.0014 (3)
O1	0.0446 (9)	0.0426 (10)	0.0565 (10)	−0.0084 (8)	0.0069 (8)	0.0094 (9)
O2	0.0390 (8)	0.0496 (11)	0.0525 (10)	0.0075 (8)	0.0099 (7)	−0.0064 (8)
O3	0.0415 (9)	0.0443 (10)	0.0559 (10)	−0.0052 (8)	0.0114 (7)	−0.0095 (9)
O4	0.0329 (8)	0.0774 (14)	0.0701 (11)	−0.0025 (9)	0.0194 (8)	−0.0181 (11)
N1	0.0333 (9)	0.0445 (12)	0.0393 (10)	−0.0014 (9)	0.0074 (8)	0.0040 (9)
C1	0.0292 (10)	0.0377 (13)	0.0412 (11)	0.0037 (9)	0.0014 (8)	0.0020 (10)
C2	0.0461 (14)	0.0662 (19)	0.0502 (14)	−0.0020 (14)	0.0123 (11)	−0.0009 (14)
C3	0.0632 (17)	0.091 (3)	0.0467 (15)	0.0050 (18)	0.0092 (13)	−0.0126 (16)
C4	0.0643 (16)	0.064 (2)	0.0587 (15)	0.0052 (18)	−0.0098 (12)	−0.0190 (18)
C5	0.0537 (14)	0.051 (2)	0.0701 (16)	−0.0110 (15)	−0.0044 (12)	−0.0030 (16)
C6	0.0469 (13)	0.0451 (16)	0.0518 (14)	−0.0052 (12)	0.0071 (11)	0.0017 (12)
C7	0.0352 (11)	0.0327 (13)	0.0423 (11)	0.0031 (10)	0.0082 (9)	0.0019 (10)
C8	0.0295 (10)	0.0394 (14)	0.0342 (10)	0.0059 (9)	0.0038 (8)	0.0031 (10)
C9	0.0397 (14)	0.116 (3)	0.114 (3)	−0.0180 (19)	0.0257 (16)	−0.015 (3)

Geometric parameters (Å, º) top

S1—O1	1.4290 (16)	C3—C4	1.369 (4)
S1—O2	1.4291 (15)	C3—H3	0.9300
S1—N1	1.618 (2)	C4—C5	1.372 (4)
S1—C1	1.767 (2)	C4—H4	0.9300
O3—C8	1.198 (3)	C5—C6	1.383 (4)
O4—C8	1.336 (2)	C5—H5	0.9300
O4—C9	1.466 (4)	C6—H6	0.9300
N1—C7	1.454 (3)	C7—C8	1.501 (3)
N1—H1	0.8600	C7—H7B	0.9700
C1—C2	1.380 (3)	C7—H7A	0.9700
C1—C6	1.381 (3)	C9—H9A	0.9600
C2—C3	1.386 (4)	C9—H9B	0.9600
C2—H2	0.9300	C9—H9C	0.9600

O1—S1—O2	120.61 (11)	C4—C5—C6	120.2 (3)
O1—S1—N1	106.53 (9)	C4—C5—H5	119.9
O2—S1—N1	106.36 (9)	C6—C5—H5	119.9
O1—S1—C1	107.48 (10)	C1—C6—C5	119.4 (2)
O2—S1—C1	107.55 (10)	C1—C6—H6	120.3
N1—S1—C1	107.73 (10)	C5—C6—H6	120.3
C8—O4—C9	115.6 (2)	N1—C7—C8	111.31 (18)
C7—N1—S1	118.54 (14)	N1—C7—H7B	109.4
C7—N1—H1	120.7	C8—C7—H7B	109.4
S1—N1—H1	120.7	N1—C7—H7A	109.4
C2—C1—C6	120.6 (2)	C8—C7—H7A	109.4
C2—C1—S1	120.4 (2)	H7B—C7—H7A	108.0
C6—C1—S1	119.01 (17)	O3—C8—O4	123.2 (2)
C1—C2—C3	119.2 (3)	O3—C8—C7	127.20 (19)
C1—C2—H2	120.4	O4—C8—C7	109.60 (19)
C3—C2—H2	120.4	O4—C9—H9A	109.5
C4—C3—C2	120.3 (3)	O4—C9—H9B	109.5
C4—C3—H3	119.8	H9A—C9—H9B	109.5
C2—C3—H3	119.8	O4—C9—H9C	109.5
C3—C4—C5	120.3 (3)	H9A—C9—H9C	109.5
C3—C4—H4	119.9	H9B—C9—H9C	109.5
C5—C4—H4	119.9

O1—S1—N1—C7	40.2 (2)	C1—C2—C3—C4	0.6 (5)
O2—S1—N1—C7	170.05 (17)	C2—C3—C4—C5	−0.8 (5)
C1—S1—N1—C7	−74.87 (19)	C3—C4—C5—C6	1.0 (5)
O1—S1—C1—C2	−7.1 (2)	C2—C1—C6—C5	0.8 (4)
O2—S1—C1—C2	−138.4 (2)	S1—C1—C6—C5	179.5 (2)
N1—S1—C1—C2	107.3 (2)	C4—C5—C6—C1	−1.0 (4)
O1—S1—C1—C6	174.20 (18)	S1—N1—C7—C8	−86.9 (2)
O2—S1—C1—C6	42.9 (2)	C9—O4—C8—O3	1.7 (3)
N1—S1—C1—C6	−71.3 (2)	C9—O4—C8—C7	−178.5 (2)
C6—C1—C2—C3	−0.6 (4)	N1—C7—C8—O3	−15.8 (3)
S1—C1—C2—C3	−179.2 (2)	N1—C7—C8—O4	164.42 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O3ⁱ	0.86	2.28	2.998 (2)	141
C7—H7B···O3ⁱⁱ	0.97	2.55	3.503 (4)	168

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

Experimental details

Crystal data
Chemical formula	C₉H₁₁NO₄S
M_r	229.26
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	296
a, b, c (Å)	9.7268 (8), 5.0781 (4), 10.9286 (9)
β (°)	100.087 (3)
V (Å³)	531.46 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.30
Crystal size (mm)	0.23 × 0.11 × 0.08

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2007)
T_min, T_max	0.935, 0.977
No. of measured, independent and observed [I > 2σ(I)] reflections	6159, 2216, 1944
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.688

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.092, 1.07
No. of reflections	2216
No. of parameters	137
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.26
Absolute structure	Flack (1983), 394 Friedel pairs
Absolute structure parameter	0.089 (8)

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
N1—H1···O3ⁱ	0.8600	2.2800	2.998 (2)	141.00
C7—H7B···O3ⁱⁱ	0.9700	2.5500	3.503 (4)	168.00

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

Acknowledgements

The authors are grateful to the Higher Education Commission of Pakistan for financial support to purchase the diffractometer. MNA acknowledges the Higher Education Commission, Pakistan, for providing a PhD Scholarship under PIN 042- 120607-PS2–183.

References

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