Methyl (4-bromo­benzene­sulfonamido)acetate

Arshad, M.N.; Tahir, M.N.; Khan, I.U.; Ahmad, E.; Shafiq, M.

doi:10.1107/S1600536808037550

organic compounds

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ISSN: 2056-9890

Volume 64| Part 12| December 2008| Page o2380

doi:10.1107/S1600536808037550

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Methyl (4-bromobenzenesulfonamido)acetate

Muhammad Nadeem Arshad,^a M. Nawaz Tahir,^b ^* Islam Ullah Khan,^a Ejaz Ahmad ^a and Muhammad Shafiq ^a

^aGovernment College University, Materials Chemistry Laboratory, Department of Chemistry, Lahore, Pakistan, and ^bUniversity of Sargodha, Department of Physics, Sargodha, Pakistan
^*Correspondence e-mail: dmntahir_uos@yahoo.com

(Received 10 November 2008; accepted 12 November 2008; online 20 November 2008)

The title compound, C₉H₁₀BrNO₄S, is an intermediate for the formation of benzothiazines. In the crystal structure, intermolecular N—H⋯O hydrogen bonds link the molecules, forming R₂²(10) ring motifs, which are linked into a two-dimensional polymeric sheet through intermolecular C—H⋯O hydrogen bonds.

Related literature

For general background, see: Arshad et al. (2008 ); Tahir et al. (2008 ). For a related structure, see: Bornaghi et al. (2005 ). For ring motifs, see: Bernstein et al. (1995 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₉H₁₀BrNO₄S
M_r = 308.15
Triclinic, $[P \overline 1]$
a = 6.0451 (2) Å
b = 7.0369 (2) Å
c = 13.8695 (5) Å
α = 83.866 (2)°
β = 81.190 (1)°
γ = 87.027 (2)°
V = 579.31 (3) Å³
Z = 2
Mo Kα radiation
μ = 3.73 mm⁻¹
T = 296 (2) K
0.23 × 0.18 × 0.12 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.449, T_max = 0.639
13148 measured reflections
2846 independent reflections
1893 reflections with I > 2σ(I)
R_int = 0.038

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.116
S = 1.04
2846 reflections
145 parameters
H-atom parameters constrained
Δρ_max = 0.53 e Å⁻³
Δρ_min = −0.59 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2ⁱ	0.86	2.41	2.987 (4)	125
C3—H3A⋯O3ⁱⁱ	0.97	2.50	3.410 (4)	156
Symmetry codes: (i) -x, -y+1, -z; (ii) x+1, y, 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: ORTEP-3 for Windows (Farrugia, 1997 ) and PLATON (Spek, 2003 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ) and PLATON.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808037550/hk2573sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808037550/hk2573Isup2.hkl

checkCIF report

Comment top

The glycine methyl ester is the simplest among the amino acids and the p-bromobenzenesulfonyl chloride is also comercially available. We have synthesized the title compound, (I), from their condensation. It has been prepared as an intermediate for the formation of benzothiazines, which are of our research interest (Arshad et al., 2008; Tahir et al., 2008).

In the molecule of the title compound, (I), (Fig. 1) the bond lengths (Allen et al., 1987) and angles are within normal ranges, and are comparable with the corresponding values in N-(2-nitrophenylsulfonyl)glycine methyl ester, (II), (Bornaghi et al., 2005). Ring A (C4-C9) is, of course, planar, and the Br atom lies slightly out of the ring plane [0.069 (3) Å]. The S1-N1 bond is almost perpendicular to the ring plane, with N1-S1-C4-C5 [-83.4 (3)°] and/or N1/S1/C4/C9 [93.7 (3)°] torsion angles. The (O1/O2/C1-C3) moiety is planar, and it is oriented with respect to ring A at a dihedral angle of 87.74 (3)°.

In the crystal structure, intermolecular N-H···O hydrogen bonds (Table 1) link the molecules to form R₂²(10) ring motifs (Bernstein et al., 1995), in which they are linked to form a two dimensional polymeric sheet through intermolecular C-H···O hydrogen bonds (Table 1, Fig. 2).

Related literature top

For general background, see: Arshad et al. (2008); Tahir et al. (2008). For a related structure, see: Bornaghi et al. (2005). For ring motifs, see: Bernstein et al. (1995). For bond-length data, see: Allen et al. (1987).

Experimental top

Glycine methyl ester hydrochloride (0.246 g, 1.95 mmol) was dissolved in water (10 ml) in round bottom flask. The pH of the solution was adjusted to 8–9 using sodium carbonate (1 N), and then 4-bromo benzene sulfonyl chloride (0.5 g, 1.95 mmol) was added. The mixture was stirred for 2 h at room temperature. During the reaction, pH was strictly maintained at 8–9 as HCl produced, which lowers the pH. Colorless solid product obtained was washed, dried and recrystalized from methanol for X-ray analysis (m.p. 393-394 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: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2003).

Figures top

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme.
	Fig. 2. A partial packing diagram. Hydrogen bonds are shown as dashed lines.

Methyl (4-bromobenzenesulfonamido)acetate top

Crystal data top

C₉H₁₀BrNO₄S	Z = 2
M_r = 308.15	F(000) = 308
Triclinic, P1	D_x = 1.767 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.0451 (2) Å	Cell parameters from 2846 reflections
b = 7.0369 (2) Å	θ = 1.5–28.3°
c = 13.8695 (5) Å	µ = 3.73 mm⁻¹
α = 83.866 (2)°	T = 296 K
β = 81.190 (1)°	Prism, colorless
γ = 87.027 (2)°	0.23 × 0.18 × 0.12 mm
V = 579.31 (3) Å³

Data collection top

Bruker Kappa APEXII CCD diffractometer	2846 independent reflections
Radiation source: fine-focus sealed tube	1893 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.038
Detector resolution: 7.40 pixels mm^-1	θ_max = 28.3°, θ_min = 1.5°
ω scans	h = −8→8
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −9→9
T_min = 0.449, T_max = 0.639	l = −18→18
13148 measured reflections

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.116	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0448P)² + 0.5395P] where P = (F_o² + 2F_c²)/3
2846 reflections	(Δ/σ)_max < 0.001
145 parameters	Δρ_max = 0.53 e Å⁻³
0 restraints	Δρ_min = −0.60 e Å⁻³

Crystal data top

C₉H₁₀BrNO₄S	γ = 87.027 (2)°
M_r = 308.15	V = 579.31 (3) Å³
Triclinic, P1	Z = 2
a = 6.0451 (2) Å	Mo Kα radiation
b = 7.0369 (2) Å	µ = 3.73 mm⁻¹
c = 13.8695 (5) Å	T = 296 K
α = 83.866 (2)°	0.23 × 0.18 × 0.12 mm
β = 81.190 (1)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	2846 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1893 reflections with I > 2σ(I)
T_min = 0.449, T_max = 0.639	R_int = 0.038
13148 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.116	H-atom parameters constrained
S = 1.04	Δρ_max = 0.53 e Å⁻³
2846 reflections	Δρ_min = −0.60 e Å⁻³
145 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	0.31108 (8)	0.18201 (7)	0.47759 (3)	0.0859 (2)
S1	−0.15899 (12)	0.80316 (11)	0.19808 (6)	0.0428 (2)
O1	0.4939 (4)	0.7999 (3)	−0.06466 (17)	0.0535 (6)
O2	0.2102 (5)	0.6116 (4)	−0.06458 (19)	0.0694 (8)
O3	−0.3871 (3)	0.7563 (4)	0.20253 (19)	0.0589 (6)
O4	−0.1032 (4)	0.9893 (3)	0.21559 (19)	0.0602 (6)
N1	−0.0358 (4)	0.7668 (4)	0.08966 (18)	0.0426 (6)
H1	−0.1060	0.7168	0.0497	0.051*
C1	0.6104 (7)	0.7313 (6)	−0.1532 (3)	0.0720 (12)
H1A	0.7505	0.7935	−0.1714	0.108*
H1B	0.5207	0.7589	−0.2048	0.108*
H1C	0.6379	0.5957	−0.1425	0.108*
C2	0.2962 (5)	0.7298 (4)	−0.0293 (2)	0.0411 (7)
C3	0.1966 (5)	0.8203 (5)	0.0605 (2)	0.0427 (7)
H3A	0.2818	0.7791	0.1133	0.051*
H3B	0.2032	0.9583	0.0477	0.051*
C4	−0.0381 (5)	0.6363 (4)	0.2804 (2)	0.0385 (6)
C5	−0.1158 (6)	0.4529 (5)	0.2982 (2)	0.0482 (8)
H5	−0.2363	0.4206	0.2696	0.058*
C6	−0.0151 (6)	0.3180 (5)	0.3582 (2)	0.0534 (8)
H6	−0.0672	0.1944	0.3709	0.064*
C7	0.1645 (6)	0.3690 (6)	0.3992 (2)	0.0528 (9)
C8	0.2420 (6)	0.5515 (6)	0.3828 (3)	0.0549 (9)
H8	0.3625	0.5834	0.4115	0.066*
C9	0.1398 (5)	0.6868 (5)	0.3233 (2)	0.0484 (8)
H9	0.1898	0.8111	0.3121	0.058*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0822 (3)	0.1005 (4)	0.0689 (3)	0.0267 (3)	−0.0172 (2)	0.0133 (2)
S1	0.0313 (4)	0.0443 (5)	0.0512 (5)	−0.0016 (3)	−0.0027 (3)	−0.0019 (3)
O1	0.0403 (12)	0.0621 (15)	0.0588 (14)	−0.0191 (10)	0.0057 (10)	−0.0201 (12)
O2	0.0744 (17)	0.0703 (18)	0.0649 (16)	−0.0429 (14)	0.0103 (13)	−0.0240 (14)
O3	0.0288 (11)	0.0740 (17)	0.0704 (16)	−0.0032 (10)	−0.0048 (10)	0.0059 (13)
O4	0.0603 (15)	0.0420 (14)	0.0770 (18)	0.0016 (11)	−0.0034 (13)	−0.0112 (12)
N1	0.0335 (13)	0.0531 (16)	0.0423 (14)	−0.0158 (11)	−0.0078 (10)	0.0004 (12)
C1	0.060 (2)	0.078 (3)	0.076 (3)	−0.016 (2)	0.020 (2)	−0.031 (2)
C2	0.0409 (16)	0.0361 (16)	0.0465 (17)	−0.0116 (12)	−0.0062 (13)	−0.0003 (13)
C3	0.0363 (16)	0.0476 (18)	0.0453 (17)	−0.0140 (13)	−0.0052 (12)	−0.0053 (14)
C4	0.0320 (14)	0.0470 (17)	0.0359 (15)	−0.0035 (12)	−0.0008 (11)	−0.0067 (13)
C5	0.0478 (18)	0.052 (2)	0.0467 (18)	−0.0114 (15)	−0.0110 (14)	−0.0048 (15)
C6	0.061 (2)	0.050 (2)	0.0488 (19)	−0.0070 (16)	−0.0077 (16)	−0.0017 (15)
C7	0.0484 (19)	0.071 (2)	0.0348 (16)	0.0117 (17)	0.0007 (14)	−0.0016 (15)
C8	0.0398 (17)	0.076 (3)	0.050 (2)	−0.0057 (16)	−0.0110 (14)	−0.0062 (18)
C9	0.0386 (17)	0.055 (2)	0.0524 (19)	−0.0110 (14)	−0.0041 (14)	−0.0102 (16)

Geometric parameters (Å, º) top

Br1—C7	1.889 (3)	C3—N1	1.458 (4)
S1—O4	1.424 (2)	C3—H3A	0.9700
S1—O3	1.425 (2)	C3—H3B	0.9700
S1—N1	1.613 (3)	C4—C5	1.381 (4)
S1—C4	1.759 (3)	C4—C9	1.385 (4)
O1—C2	1.320 (3)	C5—C6	1.374 (5)
O1—C1	1.436 (4)	C5—H5	0.9300
O2—C2	1.188 (4)	C6—C7	1.381 (5)
N1—H1	0.8600	C6—H6	0.9300
C1—H1A	0.9600	C7—C8	1.374 (5)
C1—H1B	0.9600	C8—C9	1.377 (5)
C1—H1C	0.9600	C8—H8	0.9300
C2—C3	1.489 (4)	C9—H9	0.9300

O4—S1—O3	120.49 (15)	N1—C3—H3B	109.6
O4—S1—N1	106.96 (14)	C2—C3—H3B	109.6
O3—S1—N1	106.53 (14)	H3A—C3—H3B	108.1
O4—S1—C4	107.89 (15)	C5—C4—C9	120.5 (3)
O3—S1—C4	107.66 (14)	C5—C4—S1	119.4 (2)
N1—S1—C4	106.55 (14)	C9—C4—S1	120.1 (2)
C2—O1—C1	117.5 (3)	C6—C5—C4	120.1 (3)
C3—N1—S1	118.9 (2)	C6—C5—H5	120.0
C3—N1—H1	120.6	C4—C5—H5	120.0
S1—N1—H1	120.6	C5—C6—C7	118.9 (3)
O1—C1—H1A	109.5	C5—C6—H6	120.6
O1—C1—H1B	109.5	C7—C6—H6	120.6
H1A—C1—H1B	109.5	C8—C7—C6	121.6 (3)
O1—C1—H1C	109.5	C8—C7—Br1	119.2 (3)
H1A—C1—H1C	109.5	C6—C7—Br1	119.2 (3)
H1B—C1—H1C	109.5	C7—C8—C9	119.4 (3)
O2—C2—O1	124.5 (3)	C7—C8—H8	120.3
O2—C2—C3	125.0 (3)	C9—C8—H8	120.3
O1—C2—C3	110.4 (2)	C8—C9—C4	119.5 (3)
N1—C3—C2	110.1 (2)	C8—C9—H9	120.2
N1—C3—H3A	109.6	C4—C9—H9	120.2
C2—C3—H3A	109.6

C1—O1—C2—O2	1.4 (5)	C4—C5—C6—C7	−0.4 (5)
C1—O1—C2—C3	−178.3 (3)	C5—C6—C7—C8	1.1 (5)
O2—C2—C3—N1	−9.3 (5)	C5—C6—C7—Br1	−177.6 (3)
O1—C2—C3—N1	170.5 (3)	C6—C7—C8—C9	−0.5 (5)
O4—S1—C4—C5	162.0 (2)	Br1—C7—C8—C9	178.1 (2)
O3—S1—C4—C5	30.5 (3)	C7—C8—C9—C4	−0.6 (5)
N1—S1—C4—C5	−83.4 (3)	C5—C4—C9—C8	1.2 (5)
O4—S1—C4—C9	−20.8 (3)	S1—C4—C9—C8	−175.9 (2)
O3—S1—C4—C9	−152.3 (3)	C2—C3—N1—S1	165.0 (2)
N1—S1—C4—C9	93.7 (3)	O4—S1—N1—C3	44.2 (3)
C9—C4—C5—C6	−0.7 (5)	O3—S1—N1—C3	174.3 (2)
S1—C4—C5—C6	176.5 (3)	C4—S1—N1—C3	−71.0 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2ⁱ	0.86	2.41	2.987 (4)	125
C3—H3A···O3ⁱⁱ	0.97	2.50	3.410 (4)	156

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

Experimental details

Crystal data
Chemical formula	C₉H₁₀BrNO₄S
M_r	308.15
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	6.0451 (2), 7.0369 (2), 13.8695 (5)
α, β, γ (°)	83.866 (2), 81.190 (1), 87.027 (2)
V (Å³)	579.31 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	3.73
Crystal size (mm)	0.23 × 0.18 × 0.12

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.449, 0.639
No. of measured, independent and observed [I > 2σ(I)] reflections	13148, 2846, 1893
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.116, 1.04
No. of reflections	2846
No. of parameters	145
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.53, −0.60

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003), WinGX (Farrugia, 1999) and PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2ⁱ	0.8600	2.41	2.987 (4)	125
C3—H3A···O3ⁱⁱ	0.9700	2.50	3.410 (4)	156

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

Acknowledgements

MNA gratefully acknowledges the Higher Education Commission, Islamabad, Pakistan, for providing a Scholarship under the Indigenous PhD Programme (PIN 042-120607-PS2-183).

References

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