Ethyl 2-(5-bromo-3-ethyl-sulfinyl-1-benzofuran-2-yl)acetate.

The title compound, C(14)H(15)BrO(4)S, was prepared by the oxidation of ethyl 2-(5-bromo-3-ethyl-sulfanyl-1-benzofuran-2-yl)acetate with 3-chloro-peroxy-benzoic acid. The crystal structure is stabilized by aromatic π-π inter-actions between the benzene rings of neighbouring mol-ecules [centroid-centroid distance = 3.814 (9) Å], and possibly by weak C-H⋯π inter-actions. In addition, the crystal structure exhibits three inter-molecular C-H⋯O non-classical hydrogen bonds. The ethyl group bonded to carboxyl-ate O atom is disordered over two positions, with refined site-occupancy factors of 0.686 (18) and 0.314 (18).

Related literature

For the crystal structures of similar alkyl 2-(1-benzofuran-2-yl)acetate derivatives, see: Choi et al. (2008a ▶,b ▶, 2009 ▶).

Experimental

Crystal data

C14H15BrO4S

M = 359.23

Triclinic,

a = 8.311 (3) Å

b = 9.800 (3) Å

c = 10.621 (3) Å

α = 69.552 (5)°

β = 77.671 (6)°

γ = 66.259 (5)°

V = 739.3 (4) Å3

Z = 2

Mo Kα radiation

μ = 2.93 mm−1

T = 298 K

0.30 × 0.20 × 0.10 mm

Data collection

Bruker SMART CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1999 ▶) T min = 0.496, T max = 0.750

5330 measured reflections

2562 independent reflections

1790 reflections with I > 2σ(I)

R int = 0.042

Refinement

R[F 2 > 2σ(F 2)] = 0.057

wR(F 2) = 0.168

S = 1.12

2562 reflections

191 parameters

29 restraints

H-atom parameters constrained

Δρmax = 0.65 e Å−3

Δρmin = −0.58 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/S1600536809009775/rk2134sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809009775/rk2134Isup2.hkl

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

C14H15BrO4S	Z = 2
Mr = 359.23	F(000) = 364
Triclinic, P1	Dx = 1.614 Mg m−3
Hall symbol: -P 1	Melting point: 391.5 K
a = 8.311 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.800 (3) Å	Cell parameters from 1919 reflections
c = 10.621 (3) Å	θ = 2.4–25.0°
α = 69.552 (5)°	µ = 2.93 mm−1
β = 77.671 (6)°	T = 298 K
γ = 66.259 (5)°	Block, colourless
V = 739.3 (4) Å3	0.30 × 0.20 × 0.10 mm

Bruker SMART CCD diffractometer	2562 independent reflections
Radiation source: Fine-focus sealed tube	1790 reflections with I > 2σ(I)
Graphite	Rint = 0.042
Detector resolution: 10.0 pixels mm-1	θmax = 25.0°, θmin = 2.1°
φ and ω scans	h = −9→9
Absorption correction: multi-scan (SADABS; Sheldrick, 1999)	k = −11→11
Tmin = 0.496, Tmax = 0.750	l = −12→12
5330 measured reflections

Refinement on F2	Primary atom site location: Direct
Least-squares matrix: Full	Secondary atom site location: Difmap
R[F2 > 2σ(F2)] = 0.057	H-atom parameters constrained
wR(F2) = 0.168	w = 1/[σ2(Fo2) + (0.0738P)2 + 1.336P] where P = (Fo2 + 2Fc2)/3
S = 1.12	(Δ/σ)max < 0.001
2562 reflections	Δρmax = 0.65 e Å−3
191 parameters	Δρmin = −0.58 e Å−3
29 restraints

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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	Occ. (<1)
Br	0.31159 (11)	−0.28976 (10)	0.39050 (8)	0.0551 (3)
S	0.7649 (2)	0.1124 (2)	0.02737 (16)	0.0413 (5)
O1	0.8405 (6)	−0.0339 (5)	0.4145 (4)	0.0363 (11)
O2	0.9901 (7)	0.3669 (6)	0.2625 (6)	0.0560 (14)
O3	0.7412 (8)	0.3819 (6)	0.2043 (7)	0.0694 (17)
O4	0.7327 (7)	0.0002 (6)	−0.0200 (5)	0.0525 (13)
C1	0.7580 (8)	0.0383 (7)	0.2055 (6)	0.0330 (15)
C2	0.6623 (8)	−0.0604 (7)	0.2949 (6)	0.0299 (14)
C3	0.5405 (9)	−0.1172 (8)	0.2829 (6)	0.0355 (15)
H3	0.4975	−0.0921	0.2006	0.043*
C4	0.4856 (9)	−0.2139 (7)	0.4000 (7)	0.0359 (16)
C5	0.5436 (9)	−0.2537 (8)	0.5241 (7)	0.0403 (16)
H5	0.5006	−0.3177	0.5992	0.048*
C6	0.6667 (9)	−0.1981 (8)	0.5368 (6)	0.0412 (17)
H6	0.7107	−0.2254	0.6192	0.049*
C7	0.7211 (8)	−0.1005 (8)	0.4222 (7)	0.0352 (15)
C8	0.8584 (9)	0.0501 (7)	0.2814 (7)	0.0356 (15)
C9	0.9829 (9)	0.1352 (8)	0.2529 (7)	0.0413 (17)
H9A	1.0576	0.0907	0.3267	0.050*
H9B	1.0582	0.1208	0.1716	0.050*
C10	0.8891 (10)	0.3058 (9)	0.2353 (7)	0.0427 (18)
C11A	0.9188 (18)	0.5401 (18)	0.2280 (15)	0.063 (4)	0.686 (18)
H11A	0.9056	0.5869	0.1321	0.076*	0.686 (18)
H11B	0.8046	0.5759	0.2768	0.076*	0.686 (18)
C12A	1.0484 (16)	0.5825 (15)	0.2679 (15)	0.062 (4)	0.686 (18)
H12A	1.0704	0.5257	0.3604	0.093*	0.686 (18)
H12B	1.0023	0.6924	0.2575	0.093*	0.686 (18)
H12C	1.1566	0.5569	0.2117	0.093*	0.686 (18)
C11B	0.907 (4)	0.515 (4)	0.288 (3)	0.063 (4)	0.314 (18)
H11C	0.9183	0.5081	0.3793	0.076*	0.314 (18)
H11D	0.7833	0.5622	0.2708	0.076*	0.314 (18)
C12B	1.014 (4)	0.600 (3)	0.187 (3)	0.062 (4)	0.314 (18)
H12D	0.9653	0.6418	0.1013	0.093*	0.314 (18)
H12E	1.1330	0.5299	0.1792	0.093*	0.314 (18)
H12F	1.0114	0.6839	0.2154	0.093*	0.314 (18)
C13	0.5715 (11)	0.2879 (9)	0.0038 (7)	0.053 (2)
H13A	0.5850	0.3558	0.0456	0.063*
H13B	0.5662	0.3412	−0.0921	0.063*
C14	0.3993 (12)	0.2654 (10)	0.0593 (9)	0.069 (3)
H14A	0.3947	0.1822	0.0339	0.103*
H14B	0.3039	0.3599	0.0236	0.103*
H14C	0.3890	0.2397	0.1558	0.103*

	U11	U22	U33	U12	U13	U23
Br	0.0555 (6)	0.0564 (6)	0.0633 (6)	−0.0350 (4)	−0.0083 (4)	−0.0095 (4)
S	0.0424 (11)	0.0489 (11)	0.0339 (9)	−0.0210 (9)	−0.0021 (8)	−0.0089 (8)
O1	0.032 (3)	0.044 (3)	0.034 (2)	−0.013 (2)	−0.0099 (19)	−0.011 (2)
O2	0.037 (3)	0.039 (3)	0.101 (4)	−0.009 (2)	−0.016 (3)	−0.030 (3)
O3	0.052 (4)	0.045 (3)	0.109 (5)	−0.010 (3)	−0.045 (3)	−0.006 (3)
O4	0.059 (3)	0.060 (3)	0.046 (3)	−0.019 (3)	−0.007 (2)	−0.025 (3)
C1	0.032 (4)	0.026 (3)	0.038 (4)	−0.006 (3)	−0.005 (3)	−0.009 (3)
C2	0.027 (3)	0.026 (3)	0.035 (3)	−0.005 (3)	−0.004 (3)	−0.012 (3)
C3	0.033 (4)	0.036 (4)	0.034 (4)	−0.010 (3)	−0.006 (3)	−0.007 (3)
C4	0.035 (4)	0.029 (4)	0.045 (4)	−0.013 (3)	−0.002 (3)	−0.012 (3)
C5	0.042 (4)	0.033 (4)	0.039 (4)	−0.011 (3)	−0.003 (3)	−0.006 (3)
C6	0.046 (5)	0.045 (4)	0.029 (4)	−0.013 (4)	−0.005 (3)	−0.009 (3)
C7	0.029 (4)	0.034 (4)	0.043 (4)	−0.006 (3)	−0.007 (3)	−0.016 (3)
C8	0.033 (4)	0.032 (4)	0.044 (4)	−0.010 (3)	−0.008 (3)	−0.013 (3)
C9	0.034 (4)	0.045 (4)	0.050 (4)	−0.015 (3)	−0.007 (3)	−0.017 (3)
C10	0.047 (5)	0.049 (5)	0.041 (4)	−0.025 (4)	−0.012 (3)	−0.010 (3)
C11A	0.066 (6)	0.052 (6)	0.081 (8)	−0.023 (4)	−0.014 (5)	−0.024 (5)
C12A	0.061 (6)	0.057 (5)	0.077 (7)	−0.021 (4)	−0.015 (5)	−0.024 (5)
C11B	0.066 (6)	0.052 (6)	0.081 (8)	−0.023 (4)	−0.014 (5)	−0.024 (5)
C12B	0.061 (6)	0.057 (5)	0.077 (7)	−0.021 (4)	−0.015 (5)	−0.024 (5)
C13	0.070 (6)	0.042 (4)	0.045 (4)	−0.018 (4)	−0.016 (4)	−0.007 (3)
C14	0.065 (6)	0.053 (5)	0.058 (5)	−0.004 (5)	−0.002 (4)	−0.003 (4)

Br—C4	1.907 (6)	C9—C10	1.494 (10)
S—O4	1.487 (5)	C9—H9A	0.9700
S—C1	1.771 (6)	C9—H9B	0.9700
S—C13	1.802 (8)	C11A—C12A	1.480 (2)
O1—C7	1.366 (7)	C11A—H11A	0.9700
O1—C8	1.376 (8)	C11A—H11B	0.9700
O2—C10	1.332 (8)	C12A—H12A	0.9600
O2—C11B	1.43 (4)	C12A—H12B	0.9600
O2—C11A	1.489 (16)	C12A—H12C	0.9600
O3—C10	1.199 (9)	C11B—C12B	1.480 (2)
C1—C8	1.338 (9)	C11B—H11C	0.9700
C1—C2	1.458 (8)	C11B—H11D	0.9700
C2—C3	1.382 (9)	C12B—H12D	0.9600
C2—C7	1.405 (9)	C12B—H12E	0.9600
C3—C4	1.391 (9)	C12B—H12F	0.9600
C3—H3	0.9300	C13—C14	1.499 (11)
C4—C5	1.371 (9)	C13—H13A	0.9700
C5—C6	1.387 (9)	C13—H13B	0.9700
C5—H5	0.9300	C14—H14A	0.9600
C6—C7	1.379 (9)	C14—H14B	0.9600
C6—H6	0.9300	C14—H14C	0.9600
C8—C9	1.498 (9)
O4—S—C1	106.2 (3)	C8—C9—H9B	109.1
O4—S—C13	108.0 (3)	H9A—C9—H9B	107.8
C1—S—C13	101.7 (3)	O3—C10—O2	122.3 (7)
C7—O1—C8	106.1 (5)	O3—C10—C9	126.6 (6)
C10—O2—C11B	118.2 (14)	O2—C10—C9	111.2 (6)
C10—O2—C11A	114.9 (6)	C12A—C11A—O2	106.0 (10)
C11B—O2—C11A	23.6 (12)	C12A—C11A—H11A	110.5
C8—C1—C2	107.1 (6)	O2—C11A—H11A	110.5
C8—C1—S	124.6 (5)	C12A—C11A—H11B	110.5
C2—C1—S	127.9 (5)	O2—C11A—H11B	110.5
C3—C2—C7	119.2 (6)	H11A—C11A—H11B	108.7
C3—C2—C1	136.8 (6)	O2—C11B—C12B	99 (2)
C7—C2—C1	103.9 (5)	O2—C11B—H11C	111.9
C2—C3—C4	116.7 (6)	C12B—C11B—H11C	111.9
C2—C3—H3	121.7	O2—C11B—H11D	111.9
C4—C3—H3	121.7	C12B—C11B—H11D	111.9
C5—C4—C3	124.1 (6)	H11C—C11B—H11D	109.6
C5—C4—Br	117.4 (5)	C11B—C12B—H12D	109.5
C3—C4—Br	118.4 (5)	C11B—C12B—H12E	109.5
C4—C5—C6	119.5 (6)	H12D—C12B—H12E	109.5
C4—C5—H5	120.2	C11B—C12B—H12F	109.5
C6—C5—H5	120.2	H12D—C12B—H12F	109.5
C7—C6—C5	117.2 (6)	H12E—C12B—H12F	109.5
C7—C6—H6	121.4	C14—C13—S	115.7 (6)
C5—C6—H6	121.4	C14—C13—H13A	108.4
O1—C7—C6	125.8 (6)	S—C13—H13A	108.4
O1—C7—C2	111.0 (5)	C14—C13—H13B	108.4
C6—C7—C2	123.2 (6)	S—C13—H13B	108.4
C1—C8—O1	112.0 (6)	H13A—C13—H13B	107.4
C1—C8—C9	134.0 (6)	C13—C14—H14A	109.5
O1—C8—C9	114.1 (5)	C13—C14—H14B	109.5
C10—C9—C8	112.5 (6)	H14A—C14—H14B	109.5
C10—C9—H9A	109.1	C13—C14—H14C	109.5
C8—C9—H9A	109.1	H14A—C14—H14C	109.5
C10—C9—H9B	109.1	H14B—C14—H14C	109.5
O4—S—C1—C8	144.9 (6)	C1—C2—C7—C6	−178.0 (6)
C13—S—C1—C8	−102.2 (6)	C2—C1—C8—O1	0.7 (8)
O4—S—C1—C2	−27.1 (7)	S—C1—C8—O1	−172.7 (4)
C13—S—C1—C2	85.8 (6)	C2—C1—C8—C9	−178.5 (7)
C8—C1—C2—C3	179.7 (7)	S—C1—C8—C9	8.1 (12)
S—C1—C2—C3	−7.2 (12)	C7—O1—C8—C1	−0.6 (7)
C8—C1—C2—C7	−0.6 (7)	C7—O1—C8—C9	178.8 (5)
S—C1—C2—C7	172.5 (5)	C1—C8—C9—C10	76.1 (10)
C7—C2—C3—C4	−0.9 (9)	O1—C8—C9—C10	−103.1 (7)
C1—C2—C3—C4	178.8 (7)	C11B—O2—C10—O3	15.7 (16)
C2—C3—C4—C5	0.5 (10)	C11A—O2—C10—O3	−10.5 (12)
C2—C3—C4—Br	177.8 (5)	C11B—O2—C10—C9	−162.7 (14)
C3—C4—C5—C6	−1.0 (11)	C11A—O2—C10—C9	171.2 (8)
Br—C4—C5—C6	−178.3 (5)	C8—C9—C10—O3	−22.6 (10)
C4—C5—C6—C7	1.7 (10)	C8—C9—C10—O2	155.7 (6)
C8—O1—C7—C6	178.4 (6)	C10—O2—C11A—C12A	179.1 (9)
C8—O1—C7—C2	0.2 (7)	C11B—O2—C11A—C12A	75 (4)
C5—C6—C7—O1	179.9 (6)	C10—O2—C11B—C12B	−126 (2)
C5—C6—C7—C2	−2.1 (10)	C11A—O2—C11B—C12B	−38 (2)
C3—C2—C7—O1	180.0 (5)	O4—S—C13—C14	50.4 (7)
C1—C2—C7—O1	0.2 (7)	C1—S—C13—C14	−61.1 (7)
C3—C2—C7—C6	1.7 (10)

D—H···A	D—H	H···A	D···A	D—H···A
C11A—H11B···Cg1i	0.97	3.06	3.806 (9)	135
C12A—H12B···Cg2i	0.96	2.92	3.85 (1)	164
C3—H3···O4ii	0.93	2.67	3.556 (8)	160
C5—H5···O3iii	0.93	2.67	3.528 (9)	155
C9—H9B···O4iv	0.97	2.35	3.277 (9)	161

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12A—H12B⋯Cg2i	0.96	2.92	3.85 (1)	164
C3—H3⋯O4ii	0.93	2.67	3.556 (8)	160
C5—H5⋯O3iii	0.93	2.67	3.528 (9)	155
C9—H9B⋯O4iv	0.97	2.35	3.277 (9)	161

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) . Cg2 is the centroid of the C1/C2/C7/O1/C8 furan ring.