2-(5-Bromo-3-methyl-sulfanyl-1-benzofuran-2-yl)acetic acid.

The title compound, C(11)H(9)BrO(3)S, was prepared by alkaline hydrolysis of ethyl 2-(5-bromo-3-methyl-sulfanyl-1-benzofuran-2-yl)acetate. In the crystal structure, the carboxyl groups are involved in inter-molecular O-H⋯O hydrogen bonds, which link the mol-ecules into centrosymmetric dimers. These dimers are further packed into stacks along the c axis by weak C-H⋯π inter-actions. In addition, the stacked mol-ecules exhibit a Br⋯S inter-action of 3.4787 (7) Å.

Related literature

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

Experimental

Crystal data

C11H9BrO3S

M = 301.15

Monoclinic,

a = 4.9976 (4) Å

b = 29.740 (2) Å

c = 7.6780 (6) Å

β = 92.401 (1)°

V = 1140.17 (15) Å3

Z = 4

Mo Kα radiation

μ = 3.78 mm−1

T = 100 K

0.50 × 0.30 × 0.15 mm

Data collection

Bruker SMART CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2000 ▶) T min = 0.261, T max = 0.562

6872 measured reflections

2483 independent reflections

2178 reflections with I > 2σ(I)

R int = 0.028

Refinement

R[F 2 > 2σ(F 2)] = 0.027

wR(F 2) = 0.072

S = 1.11

2483 reflections

150 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.32 e Å−3

Δρmin = −0.56 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 global, I. DOI: 10.1107/S1600536809005376/fj2195sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809005376/fj2195Isup2.hkl

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

C11H9BrO3S	F(000) = 600
Mr = 301.15	Dx = 1.754 Mg m−3
Monoclinic, P21/c	Melting point = 404–405 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 4.9976 (4) Å	Cell parameters from 3612 reflections
b = 29.740 (2) Å	θ = 2.6–28.3°
c = 7.6780 (6) Å	µ = 3.78 mm−1
β = 92.401 (1)°	T = 100 K
V = 1140.17 (15) Å3	Block, colorless
Z = 4	0.50 × 0.30 × 0.15 mm

Bruker SMART CCD diffractometer	2483 independent reflections
Radiation source: fine-focus sealed tube	2178 reflections with I > 2σ(I)
graphite	Rint = 0.028
Detector resolution: 10.0 pixels mm-1	θmax = 27.0°, θmin = 1.4°
φ and ω scans	h = −6→6
Absorption correction: multi-scan (SADABS; Sheldrick, 2000)	k = −37→19
Tmin = 0.261, Tmax = 0.562	l = −9→9
6872 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)] = 0.027	Hydrogen site location: difference Fourier map
wR(F2) = 0.072	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	w = 1/[σ2(Fo2) + (0.0331P)2 + 0.6004P] where P = (Fo2 + 2Fc2)/3
2483 reflections	(Δ/σ)max < 0.001
150 parameters	Δρmax = 0.32 e Å−3
0 restraints	Δρmin = −0.56 e Å−3

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	−0.17879 (5)	0.275363 (8)	0.83802 (3)	0.02932 (10)
S	0.64485 (11)	0.33767 (2)	0.31284 (8)	0.02358 (14)
O1	0.3933 (3)	0.43916 (5)	0.5972 (2)	0.0218 (3)
O2	0.7696 (3)	0.48334 (6)	0.1003 (2)	0.0262 (4)
O3	0.3598 (3)	0.47267 (7)	0.2002 (2)	0.0276 (4)
H12	0.310 (7)	0.4829 (12)	0.107 (5)	0.057 (11)*
C1	0.4952 (4)	0.37501 (8)	0.4556 (3)	0.0180 (4)
C2	0.2974 (4)	0.36437 (8)	0.5820 (3)	0.0179 (4)
C3	0.1697 (4)	0.32509 (8)	0.6316 (3)	0.0191 (5)
H3	0.2048	0.2976	0.5797	0.023*
C4	−0.0124 (5)	0.32894 (8)	0.7622 (3)	0.0200 (5)
C5	−0.0721 (5)	0.36984 (8)	0.8405 (3)	0.0235 (5)
H5	−0.1987	0.3708	0.9258	0.028*
C6	0.0554 (5)	0.40921 (8)	0.7925 (3)	0.0234 (5)
H6	0.0190	0.4368	0.8438	0.028*
C7	0.2403 (4)	0.40497 (8)	0.6634 (3)	0.0190 (5)
C8	0.5450 (4)	0.41944 (8)	0.4709 (3)	0.0198 (5)
C9	0.7313 (5)	0.44956 (8)	0.3800 (3)	0.0226 (5)
H9A	0.8911	0.4326	0.3554	0.027*
H9B	0.7847	0.4737	0.4588	0.027*
C10	0.6219 (4)	0.47002 (8)	0.2118 (3)	0.0192 (5)
C11	0.3591 (6)	0.32394 (13)	0.1715 (4)	0.0455 (8)
H11A	0.2212	0.3110	0.2391	0.068*
H11B	0.4113	0.3027	0.0850	0.068*
H11C	0.2925	0.3508	0.1152	0.068*

	U11	U22	U33	U12	U13	U23
Br	0.03467 (16)	0.02278 (15)	0.03138 (16)	−0.00670 (10)	0.01158 (10)	0.00524 (10)
S	0.0194 (3)	0.0267 (3)	0.0250 (3)	0.0028 (2)	0.0052 (2)	−0.0036 (3)
O1	0.0273 (8)	0.0150 (8)	0.0234 (8)	−0.0025 (7)	0.0048 (7)	0.0025 (7)
O2	0.0198 (8)	0.0332 (10)	0.0260 (9)	0.0008 (7)	0.0053 (7)	0.0115 (8)
O3	0.0169 (8)	0.0398 (11)	0.0262 (9)	−0.0008 (7)	0.0004 (7)	0.0135 (8)
C1	0.0180 (10)	0.0203 (11)	0.0159 (10)	0.0017 (9)	0.0022 (8)	0.0024 (9)
C2	0.0176 (10)	0.0206 (11)	0.0156 (10)	0.0014 (9)	0.0013 (8)	0.0023 (9)
C3	0.0234 (11)	0.0161 (11)	0.0178 (11)	−0.0001 (9)	0.0010 (9)	−0.0008 (9)
C4	0.0234 (11)	0.0186 (11)	0.0180 (11)	−0.0037 (9)	0.0007 (9)	0.0048 (9)
C5	0.0263 (12)	0.0265 (13)	0.0183 (11)	0.0000 (10)	0.0066 (9)	0.0001 (10)
C6	0.0294 (12)	0.0201 (12)	0.0210 (12)	0.0019 (10)	0.0043 (9)	−0.0021 (10)
C7	0.0208 (11)	0.0162 (11)	0.0199 (11)	−0.0012 (9)	0.0003 (9)	0.0037 (9)
C8	0.0194 (10)	0.0224 (12)	0.0176 (11)	0.0014 (9)	0.0010 (8)	0.0036 (9)
C9	0.0196 (11)	0.0232 (12)	0.0250 (12)	−0.0020 (9)	0.0003 (9)	0.0084 (10)
C10	0.0201 (11)	0.0149 (11)	0.0226 (11)	0.0002 (9)	0.0027 (9)	0.0017 (9)
C11	0.0288 (14)	0.073 (2)	0.0341 (15)	0.0025 (15)	−0.0009 (12)	−0.0262 (16)

Br—C4	1.900 (2)	C3—H3	0.9300
Br—Si	3.4787 (7)	C4—C5	1.395 (3)
S—C1	1.750 (2)	C5—C6	1.390 (3)
S—C11	1.804 (3)	C5—H5	0.9300
O1—C7	1.382 (3)	C6—C7	1.389 (3)
O1—C8	1.386 (3)	C6—H6	0.9300
O2—C10	1.220 (3)	C8—C9	1.487 (3)
O3—C10	1.312 (3)	C9—C10	1.509 (3)
O3—H12	0.81 (4)	C9—H9A	0.9700
C1—C8	1.349 (3)	C9—H9B	0.9700
C1—C2	1.449 (3)	C11—H11A	0.9600
C2—C3	1.392 (3)	C11—H11B	0.9600
C2—C7	1.395 (3)	C11—H11C	0.9600
C3—C4	1.387 (3)
C4—Br—Si	155.04 (7)	O1—C7—C6	126.2 (2)
C1—S—C11	99.90 (12)	O1—C7—C2	110.21 (19)
C7—O1—C8	105.87 (17)	C6—C7—C2	123.6 (2)
C10—O3—H12	111 (3)	C1—C8—O1	111.8 (2)
C8—C1—C2	106.5 (2)	C1—C8—C9	131.8 (2)
C8—C1—S	126.44 (18)	O1—C8—C9	116.4 (2)
C2—C1—S	127.04 (18)	C8—C9—C10	115.67 (19)
C3—C2—C7	120.0 (2)	C8—C9—H9A	108.4
C3—C2—C1	134.4 (2)	C10—C9—H9A	108.4
C7—C2—C1	105.6 (2)	C8—C9—H9B	108.4
C4—C3—C2	116.8 (2)	C10—C9—H9B	108.4
C4—C3—H3	121.6	H9A—C9—H9B	107.4
C2—C3—H3	121.6	O2—C10—O3	124.4 (2)
C3—C4—C5	122.8 (2)	O2—C10—C9	121.6 (2)
C3—C4—Br	117.46 (18)	O3—C10—C9	114.0 (2)
C5—C4—Br	119.68 (17)	S—C11—H11A	109.5
C6—C5—C4	120.8 (2)	S—C11—H11B	109.5
C6—C5—H5	119.6	H11A—C11—H11B	109.5
C4—C5—H5	119.6	S—C11—H11C	109.5
C7—C6—C5	116.0 (2)	H11A—C11—H11C	109.5
C7—C6—H6	122.0	H11B—C11—H11C	109.5
C5—C6—H6	122.0
C11—S—C1—C8	−113.0 (2)	C5—C6—C7—O1	−178.9 (2)
C11—S—C1—C2	67.9 (2)	C5—C6—C7—C2	0.9 (4)
C8—C1—C2—C3	−178.7 (2)	C3—C2—C7—O1	178.60 (19)
S—C1—C2—C3	0.5 (4)	C1—C2—C7—O1	−1.1 (2)
C8—C1—C2—C7	0.9 (2)	C3—C2—C7—C6	−1.3 (4)
S—C1—C2—C7	−179.91 (17)	C1—C2—C7—C6	179.1 (2)
C7—C2—C3—C4	0.2 (3)	C2—C1—C8—O1	−0.4 (3)
C1—C2—C3—C4	179.8 (2)	S—C1—C8—O1	−179.63 (16)
C2—C3—C4—C5	1.1 (3)	C2—C1—C8—C9	178.6 (2)
C2—C3—C4—Br	−177.68 (16)	S—C1—C8—C9	−0.6 (4)
Si—Br—C4—C3	−12.5 (3)	C7—O1—C8—C1	−0.2 (2)
Si—Br—C4—C5	168.77 (12)	C7—O1—C8—C9	−179.39 (19)
C3—C4—C5—C6	−1.4 (4)	C1—C8—C9—C10	87.7 (3)
Br—C4—C5—C6	177.28 (18)	O1—C8—C9—C10	−93.3 (3)
C4—C5—C6—C7	0.4 (3)	C8—C9—C10—O2	−157.1 (2)
C8—O1—C7—C6	−179.3 (2)	C8—C9—C10—O3	24.1 (3)
C8—O1—C7—C2	0.8 (2)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H12···O2ii	0.81 (4)	1.91 (4)	2.707 (2)	169 (4)
C11—H11C···Cgiii	0.96	3.22	3.904 (3)	129

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H12⋯O2i	0.81 (4)	1.91 (4)	2.707 (2)	169 (4)
C11—H11C⋯Cgii	0.96	3.22	3.904 (3)	129

Symmetry codes: (i) ; (ii) . Cg is the centroid of the C2–C7 benzene ring.