Methyl 5-bromo-2-[meth-yl(methyl-sulfon-yl)amino]benzoate.

The title compound, C(10)H(12)BrNO(4)S, is an inter-mediate in the synthesis of benzothia-zine. The planar methyl ester group (maximum deviation is 0.0065 Å) is oriented at a dihedral angle of 39.09 (13)° with respect to the aromatic ring. In the crystal structure, weak inter-molecular C-H⋯O inter-actions link the mol-ecules into centrosymmetric dimers, through R(2) (2)(10) ring motifs.

Related literature

For related structures, see: Arshad et al. (2008 ▶); Shafiq et al. (2009 ▶); Tahir et al. (2008 ▶). For bond-length data, see: Allen et al. (1987 ▶). For ring-motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C10H12BrNO4S

M = 322.18

Monoclinic,

a = 6.0798 (1) Å

b = 10.7853 (3) Å

c = 19.5206 (4) Å

β = 90.306 (1)°

V = 1280.00 (5) Å3

Z = 4

Mo Kα radiation

μ = 3.38 mm−1

T = 296 K

0.28 × 0.10 × 0.08 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.675, T max = 0.766

13682 measured reflections

3170 independent reflections

2215 reflections with I > 2σ(I)

R int = 0.032

Refinement

R[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.084

S = 1.04

3170 reflections

157 parameters

H-atom parameters constrained

Δρmax = 0.50 e Å−3

Δρmin = −0.43 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: ORTEP-3 for Windows (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809011829/hk2657sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809011829/hk2657Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C10H12BrNO4S	F(000) = 648
Mr = 322.18	Dx = 1.672 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3094 reflections
a = 6.0798 (1) Å	θ = 2.1–28.3°
b = 10.7853 (3) Å	µ = 3.38 mm−1
c = 19.5206 (4) Å	T = 296 K
β = 90.306 (1)°	Needle, yellow
V = 1280.00 (5) Å3	0.28 × 0.10 × 0.08 mm
Z = 4

Bruker Kappa APEXII CCD area-detector diffractometer	3170 independent reflections
Radiation source: fine-focus sealed tube	2215 reflections with I > 2σ(I)
graphite	Rint = 0.032
Detector resolution: 7.40 pixels mm-1	θmax = 28.3°, θmin = 2.1°
ω scans	h = −7→8
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −11→14
Tmin = 0.675, Tmax = 0.766	l = −26→18
13682 measured reflections

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.084	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0383P)2 + 0.314P] where P = (Fo2 + 2Fc2)/3
3170 reflections	(Δ/σ)max = 0.001
157 parameters	Δρmax = 0.50 e Å−3
0 restraints	Δρmin = −0.43 e Å−3

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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.

	x	y	z	Uiso*/Ueq
Br1	0.87436 (5)	0.17725 (3)	−0.05236 (1)	0.0593 (1)
S1	0.31436 (11)	0.27222 (6)	0.25490 (3)	0.0430 (2)
O1	0.0398 (3)	0.36804 (16)	0.10645 (9)	0.0480 (6)
O2	0.3103 (3)	0.49394 (17)	0.07246 (10)	0.0615 (7)
O3	0.1288 (3)	0.2765 (2)	0.29944 (10)	0.0705 (8)
O4	0.3995 (4)	0.38536 (16)	0.22837 (9)	0.0626 (8)
N1	0.2453 (3)	0.18507 (17)	0.18980 (10)	0.0405 (7)
C1	0.3871 (4)	0.2795 (2)	0.08386 (11)	0.0351 (7)
C2	0.3870 (4)	0.1830 (2)	0.13144 (11)	0.0361 (7)
C3	0.5263 (4)	0.0825 (2)	0.12135 (13)	0.0485 (9)
C4	0.6658 (4)	0.0783 (3)	0.06623 (13)	0.0514 (9)
C5	0.6714 (4)	0.1765 (2)	0.02093 (12)	0.0400 (8)
C6	0.5328 (4)	0.2764 (2)	0.02934 (12)	0.0392 (8)
C7	0.2441 (4)	0.3927 (2)	0.08770 (11)	0.0397 (8)
C8	−0.1053 (5)	0.4740 (3)	0.11019 (16)	0.0633 (11)
C9	0.1119 (5)	0.0733 (3)	0.20332 (15)	0.0638 (11)
C10	0.5280 (6)	0.1954 (3)	0.29790 (17)	0.0701 (12)
H3	0.52509	0.01710	0.15239	0.0581*
H4	0.75581	0.00965	0.05948	0.0616*
H6	0.53683	0.34191	−0.00159	0.0470*
H8A	−0.03451	0.53922	0.13547	0.0948*
H8B	−0.23879	0.45063	0.13284	0.0948*
H8C	−0.13892	0.50247	0.06473	0.0948*
H9A	0.05001	0.04344	0.16109	0.0955*
H9B	−0.00446	0.09371	0.23442	0.0955*
H9C	0.20333	0.01021	0.22325	0.0955*
H10A	0.65597	0.19335	0.26931	0.1052*
H10B	0.48324	0.11214	0.30829	0.1052*
H10C	0.56198	0.23847	0.33966	0.1052*

	U11	U22	U33	U12	U13	U23
Br1	0.0607 (2)	0.0684 (2)	0.0489 (2)	0.0212 (1)	0.0172 (1)	−0.0024 (1)
S1	0.0595 (4)	0.0354 (3)	0.0342 (3)	0.0018 (3)	0.0066 (3)	−0.0019 (3)
O1	0.0388 (10)	0.0460 (10)	0.0593 (11)	0.0085 (8)	0.0031 (8)	−0.0053 (9)
O2	0.0691 (14)	0.0389 (10)	0.0769 (13)	0.0149 (9)	0.0276 (11)	0.0158 (10)
O3	0.0828 (16)	0.0770 (14)	0.0520 (12)	0.0100 (12)	0.0257 (11)	−0.0111 (11)
O4	0.1016 (17)	0.0352 (10)	0.0510 (11)	−0.0133 (10)	0.0043 (11)	−0.0036 (9)
N1	0.0501 (13)	0.0370 (11)	0.0343 (10)	−0.0033 (9)	0.0034 (9)	0.0001 (9)
C1	0.0374 (13)	0.0351 (12)	0.0327 (11)	0.0055 (10)	−0.0008 (10)	−0.0006 (10)
C2	0.0418 (14)	0.0350 (13)	0.0315 (11)	0.0009 (10)	0.0003 (10)	−0.0019 (10)
C3	0.0645 (18)	0.0357 (14)	0.0452 (14)	0.0104 (12)	0.0036 (12)	0.0063 (11)
C4	0.0591 (18)	0.0456 (15)	0.0495 (15)	0.0225 (13)	0.0059 (13)	−0.0023 (12)
C5	0.0431 (14)	0.0423 (14)	0.0346 (12)	0.0070 (11)	0.0020 (10)	−0.0058 (10)
C6	0.0441 (14)	0.0387 (13)	0.0347 (12)	0.0059 (12)	0.0025 (10)	0.0032 (10)
C7	0.0476 (16)	0.0397 (14)	0.0318 (11)	0.0093 (12)	0.0045 (10)	0.0024 (10)
C8	0.0525 (19)	0.068 (2)	0.0695 (19)	0.0233 (15)	0.0025 (15)	−0.0155 (16)
C9	0.064 (2)	0.0674 (19)	0.0600 (17)	−0.0252 (16)	0.0120 (14)	−0.0095 (15)
C10	0.081 (2)	0.063 (2)	0.066 (2)	0.0056 (17)	−0.0241 (18)	−0.0031 (15)

Br1—C5	1.894 (2)	C4—C5	1.380 (4)
S1—O3	1.429 (2)	C5—C6	1.378 (3)
S1—O4	1.424 (2)	C3—H3	0.9300
S1—N1	1.634 (2)	C4—H4	0.9300
S1—C10	1.751 (4)	C6—H6	0.9300
O1—C7	1.324 (3)	C8—H8A	0.9600
O1—C8	1.446 (4)	C8—H8B	0.9600
O2—C7	1.202 (3)	C8—H8C	0.9600
N1—C2	1.432 (3)	C9—H9A	0.9600
N1—C9	1.478 (4)	C9—H9B	0.9600
C1—C2	1.395 (3)	C9—H9C	0.9600
C1—C6	1.389 (3)	C10—H10A	0.9600
C1—C7	1.501 (3)	C10—H10B	0.9600
C2—C3	1.390 (3)	C10—H10C	0.9600
C3—C4	1.374 (4)
Br1···O3i	3.3255 (19)	C1···H8Bx	3.0800
Br1···H4ii	3.0200	C3···H9C	2.9100
Br1···H9Aiii	3.2200	C3···H9A	3.0300
Br1···H10Civ	2.9700	C4···H9Ax	3.0000
S1···O1	3.4929 (19)	C6···H8Bx	3.0800
S1···C7	3.537 (2)	C9···H3	2.7700
O1···S1	3.4929 (19)	C9···H10B	3.0700
O1···O4	3.229 (3)	H3···C9	2.7700
O1···N1	2.843 (3)	H3···H9C	2.4000
O2···C6v	3.319 (3)	H3···O4xii	2.7600
O3···Br1vi	3.3255 (19)	H4···Br1ii	3.0200
O4···O1	3.229 (3)	H6···O2	2.5900
O4···C7	2.900 (3)	H6···O2v	2.4300
O4···C10vii	3.412 (4)	H8A···O2	2.4800
O4···C1	3.044 (3)	H8A···O3xiii	2.9200
O2···H6	2.5900	H8B···C1xi	3.0800
O2···H8C	2.7400	H8B···C6xi	3.0800
O2···H8A	2.4800	H8B···H10Bxiii	2.5700
O2···H8Cviii	2.8700	H8C···O2	2.7400
O2···H6v	2.4300	H8C···O2viii	2.8700
O3···H8Aix	2.9200	H9A···C3	3.0300
O3···H9B	2.4800	H9A···C4xi	3.0000
O4···H3vii	2.7600	H9A···Br1iii	3.2200
O4···H9Cvii	2.9200	H9B···O3	2.4800
O4···H10Bvii	2.6500	H9B···H10Axi	2.4300
N1···O1	2.843 (3)	H9C···C3	2.9100
C1···O4	3.044 (3)	H9C···H3	2.4000
C6···O2v	3.319 (3)	H9C···O4xii	2.9200
C6···C8x	3.441 (4)	H10A···H9Bx	2.4300
C7···S1	3.537 (2)	H10B···C9	3.0700
C7···O4	2.900 (3)	H10B···O4xii	2.6500
C8···C6xi	3.441 (4)	H10B···H8Bix	2.5700
C10···O4xii	3.412 (4)	H10C···Br1xiv	2.9700
O3—S1—O4	118.90 (13)	C2—C3—H3	119.00
O3—S1—N1	106.95 (11)	C4—C3—H3	119.00
O3—S1—C10	108.04 (14)	C3—C4—H4	120.00
O4—S1—N1	107.61 (10)	C5—C4—H4	120.00
O4—S1—C10	108.04 (15)	C1—C6—H6	120.00
N1—S1—C10	106.71 (13)	C5—C6—H6	120.00
C7—O1—C8	115.4 (2)	O1—C8—H8A	109.00
S1—N1—C2	118.33 (15)	O1—C8—H8B	109.00
S1—N1—C9	118.00 (17)	O1—C8—H8C	109.00
C2—N1—C9	117.55 (19)	H8A—C8—H8B	109.00
C2—C1—C6	119.7 (2)	H8A—C8—H8C	109.00
C2—C1—C7	124.8 (2)	H8B—C8—H8C	109.00
C6—C1—C7	115.46 (19)	N1—C9—H9A	109.00
N1—C2—C1	121.4 (2)	N1—C9—H9B	109.00
N1—C2—C3	119.6 (2)	N1—C9—H9C	109.00
C1—C2—C3	119.0 (2)	H9A—C9—H9B	109.00
C2—C3—C4	121.0 (2)	H9A—C9—H9C	109.00
C3—C4—C5	119.6 (3)	H9B—C9—H9C	109.00
Br1—C5—C4	120.37 (18)	S1—C10—H10A	109.00
Br1—C5—C6	119.20 (17)	S1—C10—H10B	109.00
C4—C5—C6	120.4 (2)	S1—C10—H10C	110.00
C1—C6—C5	120.2 (2)	H10A—C10—H10B	109.00
O1—C7—O2	124.5 (2)	H10A—C10—H10C	109.00
O1—C7—C1	113.27 (19)	H10B—C10—H10C	109.00
O2—C7—C1	122.1 (2)
O3—S1—N1—C2	169.01 (17)	C7—C1—C2—C3	179.3 (2)
O3—S1—N1—C9	−39.1 (2)	C2—C1—C6—C5	2.2 (3)
O4—S1—N1—C2	40.2 (2)	C7—C1—C6—C5	−179.9 (2)
O4—S1—N1—C9	−167.94 (19)	C2—C1—C7—O1	−41.7 (3)
C10—S1—N1—C2	−75.6 (2)	C2—C1—C7—O2	141.0 (2)
C10—S1—N1—C9	76.3 (2)	C6—C1—C7—O1	140.6 (2)
C8—O1—C7—O2	−2.1 (3)	C6—C1—C7—O2	−36.8 (3)
C8—O1—C7—C1	−179.4 (2)	N1—C2—C3—C4	−179.4 (2)
S1—N1—C2—C1	−77.8 (3)	C1—C2—C3—C4	1.2 (4)
S1—N1—C2—C3	102.8 (2)	C2—C3—C4—C5	1.4 (4)
C9—N1—C2—C1	130.3 (2)	C3—C4—C5—Br1	176.30 (19)
C9—N1—C2—C3	−49.2 (3)	C3—C4—C5—C6	−2.3 (4)
C6—C1—C2—N1	177.6 (2)	Br1—C5—C6—C1	−178.13 (18)
C6—C1—C2—C3	−3.0 (3)	C4—C5—C6—C1	0.5 (4)
C7—C1—C2—N1	−0.2 (4)

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O2v	0.93	2.43	3.319 (3)	159

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6⋯O2i	0.93	2.43	3.319 (3)	159

Symmetry code: (i) .