2-(6,7-Dimethyl-3-methyl-sulfanyl-1-benzofuran-2-yl)acetic acid.

In the title compound, C(13)H(14)O(3)S, the methyl group of the methyl-sulfanyl substituent is almost perpendicular to the plane of the benzofuran fragment [80.5 (9)°]. The carboxylic acid 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 a axis by C-H⋯π inter-actions.

Related literature

For related structures, see: Choi et al. (2007 ▶); Seo et al. (2007 ▶).

Experimental

Crystal data

C13H14O3S

M = 250.30

Monoclinic,

a = 18.050 (2) Å

b = 4.9422 (5) Å

c = 13.885 (1) Å

β = 104.451 (2)°

V = 1199.4 (2) Å3

Z = 4

Mo Kα radiation

μ = 0.26 mm−1

T = 173 (2) K

0.40 × 0.20 × 0.10 mm

Data collection

Bruker SMART CCD diffractometer

Absorption correction: none

6673 measured reflections

2595 independent reflections

2269 reflections with I > 2σ(I)

R int = 0.035

Refinement

R[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.119

S = 1.17

2595 reflections

161 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.42 e Å−3

Δρmin = −0.25 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/S1600536808024288/hb2769sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808024288/hb2769Isup2.hkl

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

C13H14O3S	F000 = 528
Mr = 250.30	Dx = 1.386 Mg m−3
Monoclinic, P21/c	Mo Kα radiation λ = 0.71073 Å
Hall symbol: -P_2ybc	Cell parameters from 4188 reflections
a = 18.050 (2) Å	θ = 3.0–28.3º
b = 4.9422 (5) Å	µ = 0.26 mm−1
c = 13.885 (1) Å	T = 173 (2) K
β = 104.451 (2)º	Block, colorless
V = 1199.4 (2) Å3	0.40 × 0.20 × 0.10 mm
Z = 4

Bruker SMART CCD diffractometer	2595 independent reflections
Radiation source: fine-focus sealed tube	2269 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.035
Detector resolution: 10.0 pixels mm-1	θmax = 27.0º
T = 173(2) K	θmin = 1.2º
φ and ω scans	h = −19→23
Absorption correction: none	k = −5→6
6673 measured reflections	l = −17→17

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difmap (O-H) and geom (C-H)
R[F2 > 2σ(F2)] = 0.038	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.119	w = 1/[σ2(Fo2) + (0.0641P)2 + 0.395P] where P = (Fo2 + 2Fc2)/3
S = 1.17	(Δ/σ)max < 0.001
2595 reflections	Δρmax = 0.42 e Å−3
161 parameters	Δρmin = −0.25 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
S	0.36076 (2)	0.71244 (9)	0.66542 (3)	0.02429 (16)
O1	0.22123 (6)	0.3898 (3)	0.81259 (8)	0.0204 (3)
O2	0.40090 (8)	0.3577 (3)	0.94500 (11)	0.0324 (4)
H2O	0.4453 (16)	0.310 (6)	0.970 (2)	0.049 (8)*
O3	0.45128 (7)	0.7710 (3)	0.96729 (10)	0.0284 (3)
C1	0.29079 (9)	0.5385 (3)	0.70833 (12)	0.0189 (4)
C2	0.23677 (9)	0.3392 (4)	0.65574 (12)	0.0189 (4)
C3	0.21948 (10)	0.2279 (4)	0.56064 (13)	0.0235 (4)
H3	0.2463	0.2811	0.5129	0.028*
C4	0.16167 (10)	0.0365 (4)	0.53846 (13)	0.0252 (4)
H4	0.1490	−0.0418	0.4739	0.030*
C5	0.12090 (10)	−0.0469 (4)	0.60716 (13)	0.0229 (4)
C6	0.13800 (9)	0.0629 (4)	0.70363 (13)	0.0209 (4)
C7	0.19588 (9)	0.2551 (3)	0.72277 (12)	0.0187 (4)
C8	0.27891 (9)	0.5601 (4)	0.80010 (12)	0.0192 (4)
C9	0.05928 (11)	−0.2584 (4)	0.57689 (16)	0.0311 (5)
H9A	0.0729	−0.4181	0.6195	0.047*
H9B	0.0543	−0.3097	0.5074	0.047*
H9C	0.0105	−0.1849	0.5841	0.047*
C10	0.09738 (11)	−0.0203 (4)	0.78102 (15)	0.0316 (5)
H10A	0.1197	0.0752	0.8434	0.047*
H10B	0.1029	−0.2159	0.7921	0.047*
H10C	0.0430	0.0256	0.7581	0.047*
C11	0.31794 (10)	0.7259 (4)	0.88784 (13)	0.0221 (4)
H11A	0.2865	0.7255	0.9370	0.026*
H11B	0.3218	0.9152	0.8663	0.026*
C12	0.39713 (10)	0.6221 (4)	0.93705 (12)	0.0197 (4)
C13	0.43420 (11)	0.4564 (4)	0.68607 (16)	0.0315 (4)
H13A	0.4529	0.4230	0.7576	0.047*
H13B	0.4766	0.5183	0.6592	0.047*
H13C	0.4130	0.2887	0.6526	0.047*

	U11	U22	U33	U12	U13	U23
S	0.0226 (3)	0.0218 (3)	0.0288 (3)	−0.00298 (17)	0.00704 (18)	0.00404 (18)
O1	0.0180 (6)	0.0248 (7)	0.0181 (6)	−0.0020 (5)	0.0039 (4)	−0.0033 (5)
O2	0.0245 (7)	0.0204 (7)	0.0432 (8)	0.0008 (5)	−0.0081 (6)	0.0012 (6)
O3	0.0204 (6)	0.0229 (7)	0.0377 (7)	−0.0021 (5)	−0.0005 (5)	−0.0019 (6)
C1	0.0161 (8)	0.0183 (8)	0.0211 (8)	0.0002 (6)	0.0021 (6)	0.0017 (7)
C2	0.0157 (8)	0.0201 (9)	0.0192 (8)	0.0011 (6)	0.0009 (6)	0.0004 (7)
C3	0.0239 (9)	0.0265 (10)	0.0196 (8)	−0.0009 (7)	0.0041 (7)	−0.0021 (7)
C4	0.0266 (9)	0.0251 (10)	0.0206 (8)	−0.0013 (7)	−0.0002 (7)	−0.0060 (7)
C5	0.0179 (8)	0.0190 (9)	0.0277 (9)	0.0006 (6)	−0.0019 (7)	−0.0017 (7)
C6	0.0165 (8)	0.0190 (9)	0.0258 (9)	0.0008 (6)	0.0027 (6)	0.0019 (7)
C7	0.0171 (8)	0.0195 (9)	0.0178 (8)	0.0019 (6)	0.0009 (6)	−0.0014 (7)
C8	0.0153 (8)	0.0186 (9)	0.0218 (8)	0.0012 (6)	0.0011 (6)	−0.0010 (7)
C9	0.0256 (10)	0.0243 (10)	0.0384 (11)	−0.0052 (7)	−0.0012 (8)	−0.0028 (8)
C10	0.0259 (10)	0.0350 (11)	0.0354 (10)	−0.0061 (8)	0.0106 (8)	0.0015 (9)
C11	0.0206 (9)	0.0203 (9)	0.0221 (8)	0.0014 (7)	−0.0006 (7)	−0.0047 (7)
C12	0.0218 (9)	0.0209 (9)	0.0156 (7)	−0.0002 (7)	0.0032 (6)	−0.0027 (7)
C13	0.0258 (10)	0.0310 (11)	0.0402 (11)	0.0012 (8)	0.0127 (8)	0.0018 (9)

S—C1	1.7506 (17)	C5—C9	1.507 (2)
S—C13	1.803 (2)	C6—C7	1.388 (2)
O1—C8	1.383 (2)	C6—C10	1.502 (2)
O1—C7	1.387 (2)	C8—C11	1.491 (2)
O2—C12	1.312 (2)	C9—H9A	0.9800
O2—H2O	0.83 (3)	C9—H9B	0.9800
O3—C12	1.212 (2)	C9—H9C	0.9800
C1—C8	1.348 (2)	C10—H10A	0.9800
C1—C2	1.449 (2)	C10—H10B	0.9800
C2—C7	1.388 (2)	C10—H10C	0.9800
C2—C3	1.392 (2)	C11—C12	1.512 (2)
C3—C4	1.385 (3)	C11—H11A	0.9900
C3—H3	0.9500	C11—H11B	0.9900
C4—C5	1.404 (3)	C13—H13A	0.9800
C4—H4	0.9500	C13—H13B	0.9800
C5—C6	1.407 (2)	C13—H13C	0.9800
C1—S—C13	99.52 (9)	C5—C9—H9A	109.5
C8—O1—C7	105.6 (1)	C5—C9—H9B	109.5
C12—O2—H2O	110 (2)	H9A—C9—H9B	109.5
C8—C1—C2	106.5 (2)	C5—C9—H9C	109.5
C8—C1—S	125.5 (1)	H9A—C9—H9C	109.5
C2—C1—S	127.9 (1)	H9B—C9—H9C	109.5
C7—C2—C3	119.2 (2)	C6—C10—H10A	109.5
C7—C2—C1	105.6 (1)	C6—C10—H10B	109.5
C3—C2—C1	135.3 (2)	H10A—C10—H10B	109.5
C4—C3—C2	117.3 (2)	C6—C10—H10C	109.5
C4—C3—H3	121.3	H10A—C10—H10C	109.5
C2—C3—H3	121.3	H10B—C10—H10C	109.5
C3—C4—C5	122.9 (2)	C8—C11—C12	112.5 (1)
C3—C4—H4	118.6	C8—C11—H11A	109.1
C5—C4—H4	118.6	C12—C11—H11A	109.1
C4—C5—C6	120.4 (2)	C8—C11—H11B	109.1
C4—C5—C9	119.3 (2)	C12—C11—H11B	109.1
C6—C5—C9	120.3 (2)	H11A—C11—H11B	107.8
C7—C6—C5	115.0 (2)	O3—C12—O2	123.7 (2)
C7—C6—C10	121.9 (2)	O3—C12—C11	122.7 (2)
C5—C6—C10	123.1 (2)	O2—C12—C11	113.5 (2)
O1—C7—C6	124.4 (2)	S—C13—H13A	109.5
O1—C7—C2	110.4 (1)	S—C13—H13B	109.5
C6—C7—C2	125.3 (2)	H13A—C13—H13B	109.5
C1—C8—O1	111.9 (2)	S—C13—H13C	109.5
C1—C8—C11	131.4 (2)	H13A—C13—H13C	109.5
O1—C8—C11	116.7 (2)	H13B—C13—H13C	109.5
C13—S—C1—C8	96.66 (17)	C10—C6—C7—O1	−0.7 (3)
C13—S—C1—C2	−80.90 (17)	C5—C6—C7—C2	−0.8 (3)
C8—C1—C2—C7	−0.11 (19)	C10—C6—C7—C2	178.93 (17)
S—C1—C2—C7	177.82 (13)	C3—C2—C7—O1	−179.69 (15)
C8—C1—C2—C3	179.6 (2)	C1—C2—C7—O1	0.06 (18)
S—C1—C2—C3	−2.5 (3)	C3—C2—C7—C6	0.6 (3)
C7—C2—C3—C4	−0.1 (3)	C1—C2—C7—C6	−179.65 (16)
C1—C2—C3—C4	−179.80 (19)	C2—C1—C8—O1	0.13 (19)
C2—C3—C4—C5	0.0 (3)	S—C1—C8—O1	−177.87 (12)
C3—C4—C5—C6	−0.3 (3)	C2—C1—C8—C11	178.24 (17)
C3—C4—C5—C9	−179.47 (17)	S—C1—C8—C11	0.2 (3)
C4—C5—C6—C7	0.7 (2)	C7—O1—C8—C1	−0.09 (18)
C9—C5—C6—C7	179.84 (16)	C7—O1—C8—C11	−178.51 (14)
C4—C5—C6—C10	−179.11 (17)	C1—C8—C11—C12	−72.5 (2)
C9—C5—C6—C10	0.1 (3)	O1—C8—C11—C12	105.56 (17)
C8—O1—C7—C6	179.73 (16)	C8—C11—C12—O3	138.89 (18)
C8—O1—C7—C2	0.01 (18)	C8—C11—C12—O2	−42.1 (2)
C5—C6—C7—O1	179.48 (15)

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9A···Cgi	0.98	2.86	3.617 (2)	135
O2—H2O···O3ii	0.83 (3)	1.89 (3)	2.717 (2)	175 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9A⋯Cgi	0.98	2.86	3.617 (2)	135
O2—H2O⋯O3ii	0.83 (3)	1.89 (3)	2.717 (2)	175 (3)

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