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

In the title compound, C(13)H(12)BrClO(4)S, the O atom and the methyl group of the methyl-sulfinyl substituent lie on opposite sides of the plane of the benzofuran fragment. There is a mean deviation of 0.016 (4) Å from the least-squares plane defined by the nine constituent benzofuran atoms. The crystal structure is stabilized by aromatic π-π inter-actions between the benzene rings of neighbouring mol-ecules [centroid-centroid distance = 3.689 (7) Å]and by a weak C-H⋯π interaction between an H atom of the methylene group bonded to the carboxylate O atom and the benzene ring of an adjacent molecule. In addition, the crystal structure exhibits weak non-classical inter-molecular C-H⋯O hydrogen bonds. The chloro-ethyl group is disordered over two positions, with refined site-occupancy factors of 0.767 (6) and 0.233 (6).

Related literature

For the crystal structures of similar alkyl 2-(5-bromo-3-methyl­sulfinyl-1-benzofuran-2-yl)acetate derivatives. see: Choi et al. (2008a ▶,b ▶).

Experimental

Crystal data

C13H12BrClO4S

M = 379.65

Triclinic,

a = 8.495 (1) Å

b = 9.882 (2) Å

c = 10.277 (2) Å

α = 71.095 (3)°

β = 80.331 (3)°

γ = 65.012 (2)°

V = 739.3 (2) Å3

Z = 2

Mo Kα radiation

μ = 3.11 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 = 0.475, T max = 0.736

5479 measured reflections

2575 independent reflections

1972 reflections with I > 2σ(I)

R int = 0.027

Refinement

R[F 2 > 2σ(F 2)] = 0.055

wR(F 2) = 0.133

S = 1.07

2575 reflections

192 parameters

57 restraints

H-atom parameters constrained

Δρmax = 0.80 e Å−3

Δρmin = −0.81 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/S1600536809012847/sj2602sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809012847/sj2602Isup2.hkl

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

C13H12BrClO4S	Z = 2
Mr = 379.65	F(000) = 380
Triclinic, P1	Dx = 1.705 Mg m−3
Hall symbol: -p 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.495 (1) Å	Cell parameters from 2253 reflections
b = 9.882 (2) Å	θ = 2.7–25.7°
c = 10.277 (2) Å	µ = 3.11 mm−1
α = 71.095 (3)°	T = 298 K
β = 80.331 (3)°	Block, colorless
γ = 65.012 (2)°	0.30 × 0.20 × 0.10 mm
V = 739.3 (2) Å3

Bruker SMART CCD diffractometer	2575 independent reflections
Radiation source: fine-focus sealed tube	1972 reflections with I > 2σ(I)
graphite	Rint = 0.027
Detector resolution: 10.0 pixels mm-1	θmax = 25.0°, θmin = 2.1°
φ and ω scans	h = −10→10
Absorption correction: multi-scan (SADABS; Sheldrick, 1999)	k = −11→11
Tmin = 0.475, Tmax = 0.736	l = −12→12
5479 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)] = 0.055	Hydrogen site location: difference Fourier map
wR(F2) = 0.133	H-atom parameters constrained
S = 1.07	w = 1/[σ2(Fo2) + (0.054P)2 + 1.6319P] where P = (Fo2 + 2Fc2)/3
2575 reflections	(Δ/σ)max < 0.000
192 parameters	Δρmax = 0.80 e Å−3
57 restraints	Δρmin = −0.80 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	Occ. (<1)
Br	0.68390 (9)	0.78885 (8)	0.10766 (7)	0.0571 (3)
ClA	−0.1810 (4)	−0.0480 (3)	0.3580 (3)	0.0928 (12)	0.764 (6)
ClB	−0.0308 (13)	−0.0729 (11)	0.1579 (12)	0.0928 (12)	0.24
S	0.25778 (18)	0.40156 (16)	0.46589 (13)	0.0391 (4)
O1	0.1648 (4)	0.5435 (4)	0.0705 (3)	0.0355 (8)
O2	0.0404 (6)	0.1375 (5)	0.2446 (7)	0.0824 (18)
O3	0.2843 (6)	0.1340 (5)	0.2991 (5)	0.0622 (12)
O4	0.2572 (6)	0.5265 (5)	0.5185 (4)	0.0537 (11)
C1	0.2533 (6)	0.4767 (6)	0.2849 (5)	0.0313 (11)
C2	0.3429 (6)	0.5699 (5)	0.1946 (5)	0.0287 (11)
C3	0.4664 (7)	0.6219 (6)	0.2093 (6)	0.0362 (12)
H3	0.5126	0.5960	0.2941	0.043*
C4	0.5167 (7)	0.7138 (6)	0.0920 (6)	0.0379 (13)
C5	0.4497 (7)	0.7563 (6)	−0.0359 (6)	0.0395 (13)
H5	0.4849	0.8216	−0.1110	0.047*
C6	0.3306 (7)	0.7020 (6)	−0.0522 (6)	0.0382 (13)
H6	0.2860	0.7271	−0.1375	0.046*
C7	0.2815 (6)	0.6090 (6)	0.0641 (5)	0.0326 (12)
C8	0.1505 (7)	0.4640 (6)	0.2065 (5)	0.0328 (11)
C9	0.0354 (7)	0.3767 (6)	0.2371 (6)	0.0377 (13)
H9A	−0.0383	0.4141	0.1598	0.045*
H9B	−0.0392	0.3968	0.3170	0.045*
C10	0.1380 (8)	0.2042 (7)	0.2639 (6)	0.0446 (14)
C11A	0.1269 (13)	−0.0271 (11)	0.2556 (12)	0.069 (3)	0.764 (6)
H11A	0.2031	−0.0798	0.3329	0.083*	0.764 (6)
H11B	0.1968	−0.0422	0.1725	0.083*	0.764 (6)
C12A	−0.004 (3)	−0.092 (3)	0.275 (2)	0.162 (6)	0.764 (6)
H12A	0.0570	−0.2031	0.3143	0.195*	0.764 (6)
H12B	−0.0332	−0.0779	0.1832	0.195*	0.764 (6)
C11B	0.107 (4)	−0.044 (3)	0.343 (4)	0.069 (3)	0.24
H11C	0.2242	−0.1045	0.3153	0.083*	0.236 (6)
H11D	0.1055	−0.0480	0.4385	0.083*	0.236 (6)
C12B	−0.013 (10)	−0.105 (10)	0.324 (4)	0.162 (6)	0.24
H12C	−0.1259	−0.0542	0.3648	0.195*	0.236 (6)
H12D	0.0286	−0.2156	0.3696	0.195*	0.236 (6)
C13	0.4757 (8)	0.2580 (7)	0.4793 (7)	0.0566 (17)
H13A	0.5553	0.3084	0.4440	0.085*
H13B	0.4904	0.1885	0.4269	0.085*
H13C	0.4983	0.2002	0.5740	0.085*

	U11	U22	U33	U12	U13	U23
Br	0.0555 (4)	0.0544 (4)	0.0722 (5)	−0.0345 (3)	−0.0077 (3)	−0.0112 (3)
ClA	0.086 (2)	0.0646 (16)	0.118 (2)	−0.0415 (14)	0.0202 (16)	−0.0107 (14)
ClB	0.086 (2)	0.0646 (16)	0.118 (2)	−0.0415 (14)	0.0202 (16)	−0.0107 (14)
S	0.0433 (8)	0.0443 (8)	0.0292 (7)	−0.0198 (7)	−0.0030 (6)	−0.0056 (6)
O1	0.039 (2)	0.041 (2)	0.0288 (19)	−0.0193 (17)	−0.0074 (16)	−0.0062 (16)
O2	0.044 (3)	0.040 (3)	0.174 (6)	−0.012 (2)	−0.022 (3)	−0.040 (3)
O3	0.045 (3)	0.046 (3)	0.087 (3)	−0.014 (2)	−0.021 (2)	−0.006 (2)
O4	0.061 (3)	0.065 (3)	0.041 (2)	−0.022 (2)	−0.001 (2)	−0.027 (2)
C1	0.033 (3)	0.033 (3)	0.030 (3)	−0.013 (2)	−0.005 (2)	−0.009 (2)
C2	0.030 (3)	0.023 (2)	0.029 (3)	−0.005 (2)	−0.002 (2)	−0.009 (2)
C3	0.039 (3)	0.033 (3)	0.038 (3)	−0.012 (2)	−0.004 (2)	−0.014 (2)
C4	0.039 (3)	0.033 (3)	0.049 (3)	−0.017 (2)	−0.002 (3)	−0.015 (3)
C5	0.040 (3)	0.035 (3)	0.040 (3)	−0.015 (2)	0.001 (3)	−0.007 (2)
C6	0.042 (3)	0.039 (3)	0.030 (3)	−0.014 (3)	−0.004 (2)	−0.007 (2)
C7	0.029 (3)	0.028 (3)	0.039 (3)	−0.007 (2)	−0.006 (2)	−0.012 (2)
C8	0.033 (3)	0.031 (3)	0.033 (3)	−0.012 (2)	−0.001 (2)	−0.009 (2)
C9	0.036 (3)	0.045 (3)	0.037 (3)	−0.020 (3)	−0.005 (2)	−0.012 (3)
C10	0.045 (4)	0.041 (3)	0.048 (4)	−0.016 (3)	−0.003 (3)	−0.012 (3)
C11A	0.059 (4)	0.062 (4)	0.090 (5)	−0.019 (3)	−0.002 (4)	−0.032 (4)
C12A	0.170 (8)	0.120 (7)	0.171 (9)	−0.051 (6)	0.035 (7)	−0.037 (7)
C11B	0.059 (4)	0.062 (4)	0.090 (5)	−0.019 (3)	−0.002 (4)	−0.032 (4)
C12B	0.170 (8)	0.120 (7)	0.171 (9)	−0.051 (6)	0.035 (7)	−0.037 (7)
C13	0.055 (4)	0.051 (4)	0.057 (4)	−0.010 (3)	−0.017 (3)	−0.012 (3)

Br—C4	1.907 (5)	C5—H5	0.9300
ClA—C12A	1.559 (19)	C6—C7	1.375 (7)
ClB—C12B	1.65 (3)	C6—H6	0.9300
S—O4	1.498 (4)	C8—C9	1.494 (7)
S—C1	1.766 (5)	C9—C10	1.505 (8)
S—C13	1.788 (6)	C9—H9A	0.9700
O1—C8	1.377 (6)	C9—H9B	0.9700
O1—C7	1.378 (6)	C11A—C12A	1.459 (15)
O2—C10	1.328 (7)	C11A—H11A	0.9700
O2—C11A	1.448 (9)	C11A—H11B	0.9700
O2—C11B	1.65 (2)	C12A—H12A	0.9700
O3—C10	1.190 (7)	C12A—H12B	0.9700
C1—C8	1.350 (7)	C11B—C12B	1.45 (2)
C1—C2	1.445 (7)	C11B—H11C	0.9700
C2—C3	1.395 (7)	C11B—H11D	0.9700
C2—C7	1.396 (7)	C12B—H12C	0.9700
C3—C4	1.380 (7)	C12B—H12D	0.9700
C3—H3	0.9300	C13—H13A	0.9600
C4—C5	1.385 (8)	C13—H13B	0.9600
C5—C6	1.383 (7)	C13—H13C	0.9600
O4—S—C1	105.9 (2)	C10—C9—H9B	109.2
O4—S—C13	106.1 (3)	H9A—C9—H9B	107.9
C1—S—C13	98.5 (3)	O3—C10—O2	123.5 (5)
C8—O1—C7	106.5 (4)	O3—C10—C9	126.4 (5)
C10—O2—C11A	116.1 (6)	O2—C10—C9	110.0 (5)
C10—O2—C11B	109.4 (13)	O2—C11A—C12A	108.9 (13)
C11A—O2—C11B	31.3 (12)	O2—C11A—H11A	109.9
C8—C1—C2	107.4 (4)	C12A—C11A—H11A	109.9
C8—C1—S	123.8 (4)	O2—C11A—H11B	109.9
C2—C1—S	128.7 (4)	C12A—C11A—H11B	109.9
C3—C2—C7	119.1 (5)	H11A—C11A—H11B	108.3
C3—C2—C1	136.0 (5)	C11A—C12A—ClA	128.4 (16)
C7—C2—C1	104.9 (4)	C11A—C12A—H12A	105.2
C4—C3—C2	116.8 (5)	ClA—C12A—H12A	105.2
C4—C3—H3	121.6	C11A—C12A—H12B	105.2
C2—C3—H3	121.6	ClA—C12A—H12B	105.2
C3—C4—C5	123.3 (5)	H12A—C12A—H12B	105.9
C3—C4—Br	118.2 (4)	C12B—C11B—O2	106 (4)
C5—C4—Br	118.4 (4)	C12B—C11B—H11C	110.5
C6—C5—C4	120.3 (5)	O2—C11B—H11C	110.5
C6—C5—H5	119.9	C12B—C11B—H11D	110.5
C4—C5—H5	119.9	O2—C11B—H11D	110.5
C7—C6—C5	116.6 (5)	H11C—C11B—H11D	108.7
C7—C6—H6	121.7	C11B—C12B—ClB	110 (3)
C5—C6—H6	121.7	C11B—C12B—H12C	109.7
C6—C7—O1	126.0 (5)	ClB—C12B—H12C	109.7
C6—C7—C2	123.8 (5)	C11B—C12B—H12D	109.7
O1—C7—C2	110.3 (4)	ClB—C12B—H12D	109.7
C1—C8—O1	110.9 (4)	H12C—C12B—H12D	108.2
C1—C8—C9	133.1 (5)	S—C13—H13A	109.5
O1—C8—C9	115.9 (4)	S—C13—H13B	109.5
C8—C9—C10	112.0 (4)	H13A—C13—H13B	109.5
C8—C9—H9A	109.2	S—C13—H13C	109.5
C10—C9—H9A	109.2	H13A—C13—H13C	109.5
C8—C9—H9B	109.2	H13B—C13—H13C	109.5
O4—S—C1—C8	−135.7 (5)	C1—C2—C7—O1	−1.1 (5)
C13—S—C1—C8	114.8 (5)	C2—C1—C8—O1	−0.5 (6)
O4—S—C1—C2	39.3 (5)	S—C1—C8—O1	175.4 (3)
C13—S—C1—C2	−70.2 (5)	C2—C1—C8—C9	176.0 (5)
C8—C1—C2—C3	−178.3 (6)	S—C1—C8—C9	−8.1 (9)
S—C1—C2—C3	6.0 (9)	C7—O1—C8—C1	−0.1 (5)
C8—C1—C2—C7	0.9 (5)	C7—O1—C8—C9	−177.3 (4)
S—C1—C2—C7	−174.7 (4)	C1—C8—C9—C10	−71.8 (8)
C7—C2—C3—C4	1.7 (7)	O1—C8—C9—C10	104.6 (5)
C1—C2—C3—C4	−179.1 (5)	C11A—O2—C10—O3	−5.9 (11)
C2—C3—C4—C5	0.7 (8)	C11B—O2—C10—O3	27.3 (16)
C2—C3—C4—Br	179.5 (4)	C11A—O2—C10—C9	175.0 (7)
C3—C4—C5—C6	−2.4 (8)	C11B—O2—C10—C9	−151.7 (14)
Br—C4—C5—C6	178.8 (4)	C8—C9—C10—O3	21.9 (9)
C4—C5—C6—C7	1.5 (8)	C8—C9—C10—O2	−159.1 (5)
C5—C6—C7—O1	179.8 (5)	C10—O2—C11A—C12A	162.3 (11)
C5—C6—C7—C2	0.9 (8)	C11B—O2—C11A—C12A	78 (3)
C8—O1—C7—C6	−178.2 (5)	O2—C11A—C12A—ClA	−36 (3)
C8—O1—C7—C2	0.8 (5)	C10—O2—C11B—C12B	176 (3)
C3—C2—C7—C6	−2.6 (8)	C11A—O2—C11B—C12B	−76 (4)
C1—C2—C7—C6	178.0 (5)	O2—C11B—C12B—ClB	52 (6)
C3—C2—C7—O1	178.4 (4)

D—H···A	D—H	H···A	D···A	D—H···A
C11A—H11B···Cgi	0.97	3.07	3.779 (7)	131
C3—H3···O4ii	0.93	2.60	3.483 (7)	159
C5—H5···O3iii	0.93	2.58	3.423 (7)	150
C9—H9A···O1iv	0.97	2.60	3.545 (6)	165
C9—H9B···O4v	0.97	2.34	3.294 (7)	170

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C11A—H11B⋯Cgi	0.97	3.07	3.779 (7)	131
C3—H3⋯O4ii	0.93	2.60	3.483 (7)	159
C5—H5⋯O3iii	0.93	2.58	3.423 (7)	150
C9—H9A⋯O1iv	0.97	2.60	3.545 (6)	165
C9—H9B⋯O4v	0.97	2.34	3.294 (7)	170

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