Ethyl 2-(5-fluoro-3-methyl-sulfinyl-1-benzofuran-2-yl)acetate.

In the title compound, C(13)H(13)FO(4)S, the O atom and the methyl group of the methyl-sulfinyl substituent lie on opposite sides of the plane through the benzofuran fragment. The crystal structure exhibits four inter-molecular non-classical C-H⋯O hydrogen bonds. In addition, the crystal structure contains aromatic π-π inter-actions between the furan and benzene rings of adjacent mol-ecules [centroid-centroid distance = 3.743 (2) Å], and two inter-molecular C-H⋯π inter-actions.

Related literature

For the crystal structures of similar ethyl 2-(5-halo-3-methyl­sulfinyl-1-benzofuran-2-yl)acetate derivatives. see: Choi et al. (2007a ▶,b ▶,c ▶). For the pharmacological activity of benzofuran compounds, see: Howlett et al. (1999 ▶); Twyman & Allsop (1999 ▶).

Experimental

Crystal data

C13H13FO4S

M = 284.29

Triclinic,

a = 7.8821 (5) Å

b = 9.0922 (5) Å

c = 10.4354 (6) Å

α = 73.682 (1)°

β = 79.155 (1)°

γ = 66.622 (1)°

V = 656.31 (7) Å3

Z = 2

Mo Kα radiation

μ = 0.27 mm−1

T = 273 K

0.40 × 0.40 × 0.10 mm

Data collection

Bruker SMART CCD diffractometer

Absorption correction: none

5673 measured reflections

2805 independent reflections

2512 reflections with I > 2σ(I)

R int = 0.063

Refinement

R[F 2 > 2σ(F 2)] = 0.036

wR(F 2) = 0.101

S = 1.04

2805 reflections

173 parameters

H-atom parameters constrained

Δρmax = 0.40 e Å−3

Δρmin = −0.35 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/S1600536809025938/ez2175sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809025938/ez2175Isup2.hkl

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

C13H13FO4S	Z = 2
Mr = 284.29	F(000) = 296
Triclinic, P1	Dx = 1.439 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.8821 (5) Å	Cell parameters from 4105 reflections
b = 9.0922 (5) Å	θ = 2.5–27.5°
c = 10.4354 (6) Å	µ = 0.27 mm−1
α = 73.682 (1)°	T = 273 K
β = 79.155 (1)°	Block, colourless
γ = 66.622 (1)°	0.40 × 0.40 × 0.10 mm
V = 656.31 (7) Å3

Bruker SMART CCD diffractometer	2512 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.063
graphite	θmax = 27.0°, θmin = 2.0°
Detector resolution: 10.0 pixels mm-1	h = −10→10
φ and ω scans	k = −11→11
5673 measured reflections	l = −13→13
2805 independent 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)] = 0.036	Hydrogen site location: difference Fourier map
wR(F2) = 0.101	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0465P)2 + 0.2336P] where P = (Fo2 + 2Fc2)/3
2805 reflections	(Δ/σ)max < 0.001
173 parameters	Δρmax = 0.40 e Å−3
0 restraints	Δρmin = −0.34 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
S	0.72668 (5)	0.63168 (5)	0.54574 (3)	0.02919 (13)
F	0.32177 (16)	0.21796 (16)	0.88301 (12)	0.0529 (3)
O1	0.84077 (14)	0.45046 (13)	0.92200 (9)	0.0247 (2)
O2	1.01504 (16)	0.88467 (14)	0.73052 (13)	0.0368 (3)
O3	0.73837 (17)	0.89429 (16)	0.69571 (14)	0.0428 (3)
O4	0.74634 (18)	0.50040 (17)	0.47717 (11)	0.0422 (3)
C7	0.7124 (2)	0.38103 (18)	0.92490 (14)	0.0246 (3)
C1	0.7324 (2)	0.53985 (18)	0.71812 (13)	0.0235 (3)
C2	0.6385 (2)	0.43348 (18)	0.80110 (14)	0.0236 (3)
C3	0.5036 (2)	0.3785 (2)	0.78410 (16)	0.0296 (3)
H3	0.4504	0.4109	0.7035	0.036*
C4	0.4545 (2)	0.2735 (2)	0.89391 (18)	0.0342 (4)
C5	0.5303 (2)	0.2183 (2)	1.01700 (17)	0.0350 (4)
H5	0.4925	0.1450	1.0866	0.042*
C6	0.6629 (2)	0.2741 (2)	1.03413 (15)	0.0301 (3)
H6	0.7157	0.2412	1.1149	0.036*
C8	0.8506 (2)	0.54532 (18)	0.79478 (13)	0.0228 (3)
C9	0.9836 (2)	0.63165 (18)	0.76654 (14)	0.0254 (3)
H9A	1.0746	0.5942	0.6946	0.030*
H9B	1.0489	0.6012	0.8456	0.030*
C10	0.8940 (2)	0.81678 (19)	0.72758 (14)	0.0268 (3)
C11	0.9500 (3)	1.0649 (2)	0.6923 (2)	0.0499 (5)
H11A	0.8265	1.1120	0.7346	0.060*
H11B	0.9456	1.1029	0.5959	0.060*
C12	1.0827 (3)	1.1155 (2)	0.7373 (2)	0.0458 (4)
H12A	1.2045	1.0677	0.6952	0.055*
H12B	1.0850	1.0781	0.8329	0.055*
H12C	1.0441	1.2333	0.7130	0.055*
C13	0.4872 (2)	0.7641 (2)	0.54508 (17)	0.0385 (4)
H13A	0.4622	0.8305	0.4563	0.058*
H13B	0.4603	0.8341	0.6059	0.058*
H13C	0.4108	0.6988	0.5727	0.058*

	U11	U22	U33	U12	U13	U23
S	0.0300 (2)	0.0380 (3)	0.01935 (19)	−0.01155 (17)	−0.00708 (14)	−0.00428 (15)
F	0.0482 (6)	0.0562 (8)	0.0708 (8)	−0.0359 (6)	−0.0137 (6)	−0.0093 (6)
O1	0.0298 (5)	0.0263 (5)	0.0213 (5)	−0.0122 (4)	−0.0090 (4)	−0.0032 (4)
O2	0.0328 (6)	0.0229 (6)	0.0573 (7)	−0.0104 (5)	−0.0141 (5)	−0.0059 (5)
O3	0.0347 (6)	0.0308 (7)	0.0608 (8)	−0.0108 (5)	−0.0202 (6)	0.0016 (6)
O4	0.0430 (7)	0.0561 (9)	0.0291 (6)	−0.0093 (6)	−0.0085 (5)	−0.0218 (5)
C7	0.0259 (7)	0.0238 (7)	0.0261 (7)	−0.0083 (6)	−0.0063 (5)	−0.0073 (5)
C1	0.0262 (7)	0.0247 (7)	0.0208 (6)	−0.0073 (6)	−0.0067 (5)	−0.0065 (5)
C2	0.0241 (7)	0.0229 (7)	0.0245 (7)	−0.0057 (6)	−0.0058 (5)	−0.0082 (5)
C3	0.0274 (7)	0.0308 (8)	0.0346 (8)	−0.0092 (6)	−0.0089 (6)	−0.0118 (6)
C4	0.0297 (8)	0.0324 (9)	0.0480 (9)	−0.0156 (7)	−0.0057 (7)	−0.0126 (7)
C5	0.0360 (9)	0.0291 (8)	0.0397 (9)	−0.0154 (7)	−0.0015 (7)	−0.0035 (7)
C6	0.0349 (8)	0.0271 (8)	0.0275 (7)	−0.0114 (7)	−0.0063 (6)	−0.0024 (6)
C8	0.0259 (7)	0.0219 (7)	0.0209 (6)	−0.0072 (6)	−0.0056 (5)	−0.0050 (5)
C9	0.0248 (7)	0.0252 (8)	0.0275 (7)	−0.0086 (6)	−0.0077 (5)	−0.0052 (5)
C10	0.0285 (7)	0.0274 (8)	0.0258 (7)	−0.0112 (6)	−0.0058 (6)	−0.0043 (6)
C11	0.0485 (11)	0.0228 (9)	0.0790 (14)	−0.0104 (8)	−0.0232 (10)	−0.0047 (9)
C12	0.0414 (10)	0.0269 (9)	0.0701 (13)	−0.0142 (8)	−0.0037 (9)	−0.0109 (8)
C13	0.0342 (8)	0.0366 (10)	0.0365 (9)	−0.0027 (7)	−0.0147 (7)	−0.0031 (7)

S—O4	1.5007 (13)	C5—C6	1.387 (2)
S—C1	1.7583 (14)	C5—H5	0.9300
S—C13	1.7914 (18)	C6—H6	0.9300
F—C4	1.3633 (17)	C8—C9	1.4859 (19)
O1—C8	1.3723 (17)	C9—C10	1.509 (2)
O1—C7	1.3813 (16)	C9—H9A	0.9700
O2—C10	1.3343 (17)	C9—H9B	0.9700
O2—C11	1.466 (2)	C11—C12	1.488 (3)
O3—C10	1.2035 (19)	C11—H11A	0.9700
C7—C6	1.381 (2)	C11—H11B	0.9700
C7—C2	1.3972 (19)	C12—H12A	0.9600
C1—C8	1.3603 (19)	C12—H12B	0.9600
C1—C2	1.446 (2)	C12—H12C	0.9600
C2—C3	1.3984 (19)	C13—H13A	0.9600
C3—C4	1.373 (2)	C13—H13B	0.9600
C3—H3	0.9300	C13—H13C	0.9600
C4—C5	1.396 (2)
O4—S—C1	106.41 (7)	O1—C8—C9	116.26 (11)
O4—S—C13	106.04 (8)	C8—C9—C10	113.99 (12)
C1—S—C13	98.86 (8)	C8—C9—H9A	108.8
C8—O1—C7	106.33 (10)	C10—C9—H9A	108.8
C10—O2—C11	116.58 (13)	C8—C9—H9B	108.8
C6—C7—O1	125.26 (12)	C10—C9—H9B	108.8
C6—C7—C2	124.13 (13)	H9A—C9—H9B	107.6
O1—C7—C2	110.62 (12)	O3—C10—O2	123.99 (15)
C8—C1—C2	107.22 (12)	O3—C10—C9	126.12 (13)
C8—C1—S	122.68 (11)	O2—C10—C9	109.88 (12)
C2—C1—S	129.73 (10)	O2—C11—C12	107.55 (15)
C7—C2—C3	119.44 (13)	O2—C11—H11A	110.2
C7—C2—C1	104.72 (12)	C12—C11—H11A	110.2
C3—C2—C1	135.84 (13)	O2—C11—H11B	110.2
C4—C3—C2	115.78 (14)	C12—C11—H11B	110.2
C4—C3—H3	122.1	H11A—C11—H11B	108.5
C2—C3—H3	122.1	C11—C12—H12A	109.5
F—C4—C3	118.07 (14)	C11—C12—H12B	109.5
F—C4—C5	116.90 (15)	H12A—C12—H12B	109.5
C3—C4—C5	125.04 (14)	C11—C12—H12C	109.5
C6—C5—C4	119.12 (15)	H12A—C12—H12C	109.5
C6—C5—H5	120.4	H12B—C12—H12C	109.5
C4—C5—H5	120.4	S—C13—H13A	109.5
C7—C6—C5	116.48 (14)	S—C13—H13B	109.5
C7—C6—H6	121.8	H13A—C13—H13B	109.5
C5—C6—H6	121.8	S—C13—H13C	109.5
C1—C8—O1	111.11 (12)	H13A—C13—H13C	109.5
C1—C8—C9	132.64 (13)	H13B—C13—H13C	109.5
C8—O1—C7—C6	178.81 (15)	F—C4—C5—C6	−178.60 (15)
C8—O1—C7—C2	−1.02 (16)	C3—C4—C5—C6	1.5 (3)
O4—S—C1—C8	127.12 (13)	O1—C7—C6—C5	179.74 (15)
C13—S—C1—C8	−123.16 (14)	C2—C7—C6—C5	−0.4 (2)
O4—S—C1—C2	−45.00 (15)	C4—C5—C6—C7	−0.8 (2)
C13—S—C1—C2	64.72 (15)	C2—C1—C8—O1	−0.08 (17)
C6—C7—C2—C3	1.0 (2)	S—C1—C8—O1	−173.75 (10)
O1—C7—C2—C3	−179.12 (13)	C2—C1—C8—C9	179.69 (15)
C6—C7—C2—C1	−178.88 (14)	S—C1—C8—C9	6.0 (2)
O1—C7—C2—C1	0.96 (16)	C7—O1—C8—C1	0.67 (16)
C8—C1—C2—C7	−0.53 (16)	C7—O1—C8—C9	−179.15 (12)
S—C1—C2—C7	172.54 (12)	C1—C8—C9—C10	61.4 (2)
C8—C1—C2—C3	179.57 (17)	O1—C8—C9—C10	−118.84 (14)
S—C1—C2—C3	−7.4 (3)	C11—O2—C10—O3	0.1 (2)
C7—C2—C3—C4	−0.4 (2)	C11—O2—C10—C9	178.79 (15)
C1—C2—C3—C4	179.54 (16)	C8—C9—C10—O3	−13.8 (2)
C2—C3—C4—F	179.21 (14)	C8—C9—C10—O2	167.56 (12)
C2—C3—C4—C5	−0.9 (3)	C10—O2—C11—C12	164.80 (15)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O4i	0.93	2.42	3.3374 (19)	168
C5—H5···O3ii	0.93	2.67	3.482 (2)	147
C9—H9A···O4iii	0.97	2.21	3.177 (2)	172
C9—H9B···O1iv	0.97	2.59	3.542 (2)	169
C11—H11A···Cg2v	0.97	2.92	3.773 (2)	148
C12—H12C···Cg1v	0.97	2.81	3.502 (2)	129

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O4i	0.93	2.42	3.3374 (19)	168
C5—H5⋯O3ii	0.93	2.67	3.482 (2)	147
C9—H9A⋯O4iii	0.97	2.21	3.177 (2)	172
C9—H9B⋯O1iv	0.97	2.59	3.542 (2)	169
C11—H11A⋯Cg2v	0.97	2.92	3.773 (2)	148
C12—H12C⋯Cg1v	0.97	2.81	3.502 (2)	129

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .Cg1 and Cg2 are the centroids of the C1/C2/C7/O1/C8 furan ring and the C2–C7 benzene ring, respectively.