Methyl 2-(benzene­sulfonamido)acetate

Abstract

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,

• a = 9.7268 (8) Å

• b = 5.0781 (4) Å

• c = 10.9286 (9) Å

• β = 100.087 (3)°

• V = 531.46 (7) ų

• 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[F ² > 2σ(F ²)] = 0.036

• wR(F ²) = 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)

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.

Supplementary Material

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
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) ; (ii) .

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

H atoms were placed in geometric positions (C—H = 0.93-0.97 Å; N—H = 0.86 Å) using a riding model with U_iso(H) = 1.2 U_eq(C,N) or U_iso(H) = 1.5 U_eq(C_methyl).

Figures

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.

Crystal data

C9H11NO4S	F(000) = 240
Mr = 229.26	Dx = 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

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

Refinement

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(Fo2) + (0.0526P)2 + 0.0105P] where P = (Fo2 + 2Fc2)/3
S = 1.07	(Δ/σ)max < 0.001
2216 reflections	Δρmax = 0.25 e Å−3
137 parameters	Δρmin = −0.26 e Å−3
1 restraint	Absolute structure: Flack (1983), 394 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.089 (8)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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.