Methyl 2-(5-bromo-3-methyl-sulfinyl-1-benzofuran-2-yl)acetate.

The title compound, C(12)H(11)BrO(4)S, was synthesized by the oxidation of methyl 2-(5-bromo-3-methyl-sulfanyl-1-benzofuran-2-yl)acetate with 3-chloro-peroxy-benzoic acid. The O atom and the methyl group of the methyl-sulfinyl substituent lie on opposite sides of the plane of the benzofuran ring system. The crystal structure is stabilized by C-H⋯π inter-actions, involving a methyl H atom and the benzene ring of a neighbouring mol-ecule, and by weak inter-molecular C-H⋯O hydrogen bonds.

Related literature

For the crystal structures of similar methyl 2-(3-methyl­sulfinyl-1-benzofuran-2-yl)acetate derivatives, see: Choi et al. (2008a ▶,b ▶).

Experimental

Crystal data

C12H11BrO4S

M = 331.18

Triclinic,

a = 7.9696 (5) Å

b = 9.1146 (6) Å

c = 10.3100 (7) Å

α = 72.587 (1)°

β = 78.716 (1)°

γ = 69.082 (1)°

V = 664.17 (8) Å3

Z = 2

Mo Kα radiation

μ = 3.25 mm−1

T = 298 (2) K

0.40 × 0.30 × 0.20 mm

Data collection

Bruker SMART CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1999 ▶) T min = 0.327, T max = 0.530

3786 measured reflections

2560 independent reflections

2084 reflections with I > 2σ(I)

R int = 0.015

Refinement

R[F 2 > 2σ(F 2)] = 0.035

wR(F 2) = 0.099

S = 0.98

2560 reflections

164 parameters

H-atom parameters constrained

Δρmax = 0.35 e Å−3

Δρmin = −0.80 e Å−3

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); 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 (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 1998 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I. DOI: 10.1107/S1600536808037768/su2077sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808037768/su2077Isup2.hkl

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

C12H11BrO4S	Z = 2
Mr = 331.18	F000 = 332
Triclinic, P1	Dx = 1.656 Mg m−3
Hall symbol: -P 1	Melting point = 405–406 K
a = 7.9696 (5) Å	Mo Kα radiation λ = 0.71073 Å
b = 9.1146 (6) Å	Cell parameters from 1892 reflections
c = 10.3100 (7) Å	θ = 2.1–27.8º
α = 72.587 (1)º	µ = 3.25 mm−1
β = 78.716 (1)º	T = 298 (2) K
γ = 69.082 (1)º	Block, colourless
V = 664.17 (8) Å3	0.40 × 0.30 × 0.20 mm

Bruker SMART CCD diffractometer	2560 independent reflections
Radiation source: fine-focus sealed tube	2084 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.015
Detector resolution: 10.0 pixels mm-1	θmax = 26.0º
T = 298(2) K	θmin = 2.5º
φ and ω scans	h = −9→5
Absorption correction: multi-scan(SADABS; Sheldrick, 1999)	k = −11→11
Tmin = 0.327, Tmax = 0.530	l = −12→12
3786 measured reflections

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)] = 0.035	H-atom parameters constrained
wR(F2) = 0.099	w = 1/[σ2(Fo2) + (0.0506P)2 + 0.5362P] where P = (Fo2 + 2Fc2)/3
S = 0.98	(Δ/σ)max = 0.001
2560 reflections	Δρmax = 0.35 e Å−3
164 parameters	Δρmin = −0.80 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

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.

	x	y	z	Uiso*/Ueq
Br	0.26775 (5)	0.20066 (4)	0.38327 (5)	0.07396 (18)
S	0.73771 (11)	0.63026 (10)	0.03527 (7)	0.0505 (2)
O1	0.8367 (3)	0.4636 (2)	0.42105 (19)	0.0450 (5)
O2	0.7437 (4)	0.4993 (3)	−0.0262 (2)	0.0668 (7)
O3	1.0188 (3)	0.8974 (3)	0.2240 (3)	0.0718 (7)
O4	0.7513 (3)	0.8989 (3)	0.1905 (3)	0.0724 (7)
C1	0.7429 (4)	0.5435 (3)	0.2117 (3)	0.0422 (6)
C2	0.6455 (4)	0.4363 (3)	0.2987 (3)	0.0408 (6)
C3	0.5121 (4)	0.3798 (3)	0.2824 (3)	0.0466 (7)
H3	0.4651	0.4089	0.1993	0.056*
C4	0.4537 (4)	0.2784 (4)	0.3965 (4)	0.0510 (7)
C5	0.5227 (5)	0.2305 (4)	0.5228 (4)	0.0550 (8)
H5	0.4796	0.1604	0.5964	0.066*
C6	0.6542 (4)	0.2870 (4)	0.5381 (3)	0.0526 (8)
H6	0.7023	0.2566	0.6210	0.063*
C7	0.7117 (4)	0.3904 (3)	0.4254 (3)	0.0419 (6)
C8	0.8535 (4)	0.5552 (3)	0.2893 (3)	0.0413 (6)
C9	0.9848 (4)	0.6447 (4)	0.2609 (3)	0.0473 (7)
H9A	1.0742	0.6117	0.1877	0.057*
H9B	1.0470	0.6145	0.3416	0.057*
C10	0.9012 (4)	0.8259 (4)	0.2215 (3)	0.0483 (7)
C11	0.5088 (5)	0.7628 (4)	0.0366 (4)	0.0637 (9)
H11A	0.4834	0.8234	−0.0551	0.096*
H11B	0.4918	0.8363	0.0916	0.096*
H11C	0.4285	0.6997	0.0740	0.096*
C12	0.9545 (7)	1.0738 (5)	0.1880 (7)	0.1065 (18)
H12A	1.0493	1.1133	0.1927	0.160*
H12B	0.8527	1.1114	0.2506	0.160*
H12C	0.9191	1.1131	0.0968	0.160*

	U11	U22	U33	U12	U13	U23
Br	0.0572 (2)	0.0513 (2)	0.1163 (4)	−0.02436 (17)	−0.0138 (2)	−0.0133 (2)
S	0.0535 (5)	0.0626 (5)	0.0392 (4)	−0.0239 (4)	−0.0121 (3)	−0.0067 (3)
O1	0.0450 (11)	0.0494 (11)	0.0411 (10)	−0.0113 (9)	−0.0157 (9)	−0.0094 (9)
O2	0.0746 (17)	0.0842 (17)	0.0506 (13)	−0.0229 (14)	−0.0132 (12)	−0.0286 (12)
O3	0.0615 (15)	0.0579 (14)	0.108 (2)	−0.0253 (12)	−0.0235 (14)	−0.0201 (14)
O4	0.0561 (15)	0.0537 (14)	0.103 (2)	−0.0180 (12)	−0.0308 (14)	0.0016 (13)
C1	0.0433 (15)	0.0454 (15)	0.0412 (14)	−0.0144 (13)	−0.0090 (12)	−0.0122 (12)
C2	0.0431 (15)	0.0361 (14)	0.0437 (15)	−0.0096 (12)	−0.0107 (12)	−0.0105 (12)
C3	0.0475 (17)	0.0398 (15)	0.0533 (17)	−0.0105 (13)	−0.0115 (13)	−0.0131 (13)
C4	0.0404 (16)	0.0385 (15)	0.073 (2)	−0.0091 (13)	−0.0074 (15)	−0.0153 (15)
C5	0.0507 (18)	0.0400 (16)	0.0600 (19)	−0.0085 (14)	−0.0028 (15)	−0.0010 (14)
C6	0.0524 (18)	0.0459 (17)	0.0472 (17)	−0.0063 (14)	−0.0094 (14)	−0.0025 (13)
C7	0.0393 (15)	0.0379 (14)	0.0455 (15)	−0.0044 (12)	−0.0102 (12)	−0.0117 (12)
C8	0.0424 (16)	0.0395 (14)	0.0429 (15)	−0.0099 (12)	−0.0103 (12)	−0.0116 (12)
C9	0.0423 (16)	0.0534 (17)	0.0510 (16)	−0.0155 (13)	−0.0136 (13)	−0.0142 (14)
C10	0.0496 (18)	0.0541 (17)	0.0458 (16)	−0.0208 (15)	−0.0087 (13)	−0.0116 (14)
C11	0.063 (2)	0.059 (2)	0.066 (2)	−0.0120 (17)	−0.0275 (17)	−0.0062 (17)
C12	0.100 (4)	0.057 (2)	0.175 (5)	−0.034 (2)	−0.038 (4)	−0.019 (3)

Br—C4	1.898 (3)	C4—C5	1.400 (5)
S—O2	1.493 (3)	C5—C6	1.374 (5)
S—C1	1.755 (3)	C5—H5	0.9300
S—C11	1.793 (4)	C6—C7	1.376 (4)
O1—C7	1.370 (3)	C6—H6	0.9300
O1—C8	1.375 (3)	C8—C9	1.481 (4)
O3—C10	1.327 (4)	C9—C10	1.501 (4)
O3—C12	1.454 (5)	C9—H9A	0.9700
O4—C10	1.195 (4)	C9—H9B	0.9700
C1—C8	1.350 (4)	C11—H11A	0.9600
C1—C2	1.451 (4)	C11—H11B	0.9600
C2—C3	1.391 (4)	C11—H11C	0.9600
C2—C7	1.395 (4)	C12—H12A	0.9600
C3—C4	1.377 (4)	C12—H12B	0.9600
C3—H3	0.9300	C12—H12C	0.9600
O2—S—C1	106.07 (14)	C6—C7—C2	123.2 (3)
O2—S—C11	106.21 (17)	C1—C8—O1	111.1 (2)
C1—S—C11	98.55 (16)	C1—C8—C9	133.3 (3)
C7—O1—C8	106.4 (2)	O1—C8—C9	115.6 (2)
C10—O3—C12	116.0 (3)	C8—C9—C10	114.0 (2)
C8—C1—C2	107.2 (3)	C8—C9—H9A	108.8
C8—C1—S	124.7 (2)	C10—C9—H9A	108.8
C2—C1—S	127.9 (2)	C8—C9—H9B	108.8
C3—C2—C7	120.0 (3)	C10—C9—H9B	108.8
C3—C2—C1	135.6 (3)	H9A—C9—H9B	107.7
C7—C2—C1	104.4 (2)	O4—C10—O3	123.4 (3)
C4—C3—C2	116.2 (3)	O4—C10—C9	126.2 (3)
C4—C3—H3	121.9	O3—C10—C9	110.4 (3)
C2—C3—H3	121.9	S—C11—H11A	109.5
C3—C4—C5	123.5 (3)	S—C11—H11B	109.5
C3—C4—Br	118.6 (3)	H11A—C11—H11B	109.5
C5—C4—Br	117.9 (2)	S—C11—H11C	109.5
C6—C5—C4	119.9 (3)	H11A—C11—H11C	109.5
C6—C5—H5	120.0	H11B—C11—H11C	109.5
C4—C5—H5	120.0	O3—C12—H12A	109.5
C5—C6—C7	117.1 (3)	O3—C12—H12B	109.5
C5—C6—H6	121.5	H12A—C12—H12B	109.5
C7—C6—H6	121.5	O3—C12—H12C	109.5
O1—C7—C6	125.9 (3)	H12A—C12—H12C	109.5
O1—C7—C2	110.9 (2)	H12B—C12—H12C	109.5
O2—S—C1—C8	131.5 (3)	C5—C6—C7—C2	−1.3 (5)
C11—S—C1—C8	−118.8 (3)	C3—C2—C7—O1	−177.8 (2)
O2—S—C1—C2	−42.4 (3)	C1—C2—C7—O1	1.1 (3)
C11—S—C1—C2	67.3 (3)	C3—C2—C7—C6	1.4 (4)
C8—C1—C2—C3	177.9 (3)	C1—C2—C7—C6	−179.7 (3)
S—C1—C2—C3	−7.3 (5)	C2—C1—C8—O1	0.1 (3)
C8—C1—C2—C7	−0.7 (3)	S—C1—C8—O1	−174.9 (2)
S—C1—C2—C7	174.1 (2)	C2—C1—C8—C9	−179.8 (3)
C7—C2—C3—C4	−0.3 (4)	S—C1—C8—C9	5.1 (5)
C1—C2—C3—C4	−178.8 (3)	C7—O1—C8—C1	0.6 (3)
C2—C3—C4—C5	−0.8 (4)	C7—O1—C8—C9	−179.5 (2)
C2—C3—C4—Br	178.5 (2)	C1—C8—C9—C10	63.6 (4)
C3—C4—C5—C6	0.9 (5)	O1—C8—C9—C10	−116.3 (3)
Br—C4—C5—C6	−178.4 (2)	C12—O3—C10—O4	0.8 (5)
C4—C5—C6—C7	0.1 (5)	C12—O3—C10—C9	−179.9 (4)
C8—O1—C7—C6	179.7 (3)	C8—C9—C10—O4	−12.9 (5)
C8—O1—C7—C2	−1.1 (3)	C8—C9—C10—O3	167.7 (3)
C5—C6—C7—O1	177.8 (3)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O2i	0.93	2.43	3.334 (4)	163
C9—H9B···O1ii	0.97	2.59	3.555 (3)	171
C9—H9A···O2iii	0.97	2.22	3.177 (4)	169
C12—H12B···Cgiv	0.96	2.99	3.903 (4)	159

Table 1

Hydrogen-bond geometry (Å, °)

Cg is the centroid of the benzene ring C2–C7.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O2i	0.93	2.43	3.334 (4)	163
C9—H9B⋯O1ii	0.97	2.59	3.555 (3)	171
C9—H9A⋯O2iii	0.97	2.22	3.177 (4)	169
C12—H12B⋯Cgiv	0.96	2.99	3.903 (4)	159

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .