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Acta Crystallogr Sect E Struct Rep Online. 2009 October 1; 65(Pt 10): o2488.
Published online 2009 September 19. doi:  10.1107/S1600536809037003
PMCID: PMC2970216

Isopropyl 2-(5-fluoro-3-methyl­sulfinyl-1-benzofuran-2-yl)acetate

Abstract

In the title compound, C14H15FO4S, the O atom and the methyl group of the methyl­sulfinyl substituent are located on opposite sides of the plane of the benzofuran fragment which is essentially planar with a mean deviation of 0.008 (1) Å from its least-squares plane. The crystal structure stabilized by three different inter­molecular non-classical C—H(...)O hydrogen bonds. The crystal structure also exhibits aromatic π–π inter­actions between the benzene rings of adjacent benzofuran ring systems [centroid–centroid distance = 3.688 (2) Å]

Related literature

For the crystal structures of similar alkyl 2-(5-fluoro-3-methyl­sulfinyl-1-benzofuran-2-yl) acetate derivatives, see: Choi et al. (2009a [triangle],b [triangle]). For the pharmacological activity of benzofuran compounds, see: Howlett et al. (1999 [triangle]); Twyman & Allsop (1999 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o2488-scheme1.jpg

Experimental

Crystal data

  • C14H15FO4S
  • M r = 298.32
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2488-efi4.jpg
  • a = 11.6332 (6) Å
  • b = 14.9522 (7) Å
  • c = 8.2333 (4) Å
  • β = 102.277 (1)°
  • V = 1399.36 (12) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.25 mm−1
  • T = 173 K
  • 0.25 × 0.20 × 0.16 mm

Data collection

  • Bruker SMART CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 2000 [triangle]) T min = 0.940, T max = 0.961
  • 12229 measured reflections
  • 3173 independent reflections
  • 2476 reflections with I > 2σ(I)
  • R int = 0.043

Refinement

  • R[F 2 > 2σ(F 2)] = 0.036
  • wR(F 2) = 0.098
  • S = 1.09
  • 3173 reflections
  • 182 parameters
  • H-atom parameters constrained
  • Δρmax = 0.39 e Å−3
  • Δρmin = −0.39 e Å−3

Data collection: SMART (Bruker, 2001 [triangle]); cell refinement: SAINT (Bruker, 2001 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 (Farrugia, 1997 [triangle]) and DIAMOND (Brandenburg, 1998 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I. DOI: 10.1107/S1600536809037003/bq2158sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809037003/bq2158Isup2.hkl

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

supplementary crystallographic information

Comment

Molecules involving benzofuran skeleton have attracted particular interest in view of their biological and pharmacological properties (Howlett et al., 1999; Twyman & Allsop, 1999). As a part of our ongoing studies of the effect of side chain substituents on the solid state structures of alkyl 2-(5-fluoro-3-methylsulfinyl-1-benzofuran-2-yl) acetate analogues (Choi et al., 2009a,b), we report the crystal structure of the title compound (Fig. 1).

The benzofuran unit is essentially planar, with a mean deviation of 0.008 (1) Å from the least-squares plane defined by the nine constituent atoms. The crystal packing (Fig. 2) is stabilized by three intermolecular non-classical C—H···O hydrogen bonds; the first between an H atom of the benzofuran ring and the oxygen of the C═O unit, with a C5–H5···O3i, the second between an H atom of the benzofuran ring and the oxygen of the isopropoxy group, with a C6—H6···O2ii, the third between a methylene H atom and the oxygen of the S═O unit, with a C9—H9B···O4iii, respectively (Table 1). The crystal packing (Fig. 2) is further stabilized by aromatic π···π interactions between the benzene rings of neighboring molecules, with a Cg···Cgi distance of 3.688 (2) Å (Cg is the centroid of the C2–C7 benzene ring).

Experimental

77% 3-chloroperoxybenzoic acid (247 mg, 1.1 mmol) was added in small portions to a stirred solution of isopropyl 2-(5-fluoro-3-methylsulfanyl-1-benzofuran-2-yl) acetate (282 mg, 1.0 mmol) in dichloromethane (30 ml) at 273 K. After being stirred for 4 h at room temperature, the mixture was washed with saturated sodium bicarbonate solution and the organic layer was separated, dried over magnesium sulfate, filtered and concentrated in vacuum. The residue was purified by column chromatography (hexane–ethyl acetate, 1:2 v/v) to afford the title compound as a colorless solid [yield 83%, m.p. 391–392 K; Rf = 0.67 (hexane–ethyl acetate, 1;2 v/v )]. Single crystals suitable for X-ray diffraction were prepared by evaporation of a solution of the title compound in acetone at room temperature. Spectroscopic analysis: EI-MS 298 [M+].

Refinement

All H atoms were geometrically positioned and refined using a riding model, with C—H = 0.93 Å for the aryl, 0.97 Å for the methine, 0.98 Å for the methylene, and 0.96 Å for the methyl H atoms. Uiso(H) = 1.2Ueq(C) for the aryl, methine, and methylene H atoms, and 1.5Ueq(C) for the methyl H atoms.

Figures

Fig. 1.
The molecular structure of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
Fig. 2.
The C—H···O and π···π interactions (dotted lines) in the title compound. Cg denotes the benzene ring centroid. [Symmetry codes: (i) - x + 1, - y + 1, - z + 1; (ii) - x + 1, - y + ...

Crystal data

C14H15FO4SF(000) = 624
Mr = 298.32Dx = 1.416 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 5216 reflections
a = 11.6332 (6) Åθ = 2.3–27.4°
b = 14.9522 (7) ŵ = 0.25 mm1
c = 8.2333 (4) ÅT = 173 K
β = 102.277 (1)°Block, colorless
V = 1399.36 (12) Å30.25 × 0.20 × 0.16 mm
Z = 4

Data collection

Bruker SMART CCD diffractometer3173 independent reflections
Radiation source: fine-focus sealed tube2476 reflections with I > 2σ(I)
graphiteRint = 0.043
Detector resolution: 10.0 pixels mm-1θmax = 27.5°, θmin = 1.8°
[var phi] and ω scansh = −14→15
Absorption correction: multi-scan (SADABS; Sheldrick, 2000)k = −19→19
Tmin = 0.940, Tmax = 0.961l = −10→10
12229 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.036Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.098H-atom parameters constrained
S = 1.09w = 1/[σ2(Fo2) + (0.0423P)2 + 0.5417P] where P = (Fo2 + 2Fc2)/3
3173 reflections(Δ/σ)max = 0.001
182 parametersΔρmax = 0.39 e Å3
0 restraintsΔρmin = −0.39 e Å3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
S0.16889 (4)0.32823 (3)0.59899 (5)0.02546 (13)
F0.53377 (11)0.32123 (8)0.19202 (14)0.0427 (3)
O10.47612 (10)0.43326 (8)0.79555 (14)0.0242 (3)
O20.19830 (10)0.54133 (8)1.03615 (14)0.0264 (3)
O30.17889 (11)0.53806 (9)0.75830 (15)0.0329 (3)
O40.17181 (12)0.23235 (9)0.54858 (18)0.0393 (3)
C10.31410 (14)0.36896 (11)0.6411 (2)0.0222 (3)
C20.40529 (14)0.36553 (11)0.5455 (2)0.0222 (3)
C30.41420 (16)0.33514 (12)0.3875 (2)0.0264 (4)
H30.35160.30780.31550.032*
C40.52168 (16)0.34834 (12)0.3458 (2)0.0289 (4)
C50.61801 (16)0.38849 (12)0.4473 (2)0.0284 (4)
H50.68800.39500.41110.034*
C60.60937 (14)0.41885 (12)0.6032 (2)0.0257 (4)
H60.67220.44640.67440.031*
C70.50247 (14)0.40604 (11)0.6470 (2)0.0224 (3)
C80.36106 (14)0.40933 (11)0.7872 (2)0.0229 (4)
C90.31082 (15)0.43478 (12)0.9330 (2)0.0252 (4)
H9A0.37430.45241.02390.030*
H9B0.27250.38310.96890.030*
C100.22306 (14)0.51050 (12)0.8949 (2)0.0234 (4)
C110.11677 (16)0.61749 (12)1.0234 (2)0.0298 (4)
H110.05550.61210.92180.036*
C120.06204 (17)0.61224 (13)1.1728 (2)0.0340 (4)
H12A0.01910.55721.16990.051*
H12B0.00940.66181.17180.051*
H12C0.12260.61431.27210.051*
C130.1857 (2)0.70278 (14)1.0176 (3)0.0504 (6)
H13A0.21830.70280.91990.076*
H13B0.24820.70641.11460.076*
H13C0.13440.75331.01470.076*
C140.11297 (18)0.39058 (15)0.4135 (2)0.0397 (5)
H14A0.15290.37250.32820.060*
H14B0.12580.45320.43560.060*
H14C0.03020.37940.37730.060*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S0.0205 (2)0.0281 (2)0.0274 (2)−0.00173 (17)0.00402 (16)−0.00285 (18)
F0.0481 (7)0.0526 (8)0.0320 (6)−0.0002 (6)0.0189 (5)−0.0125 (5)
O10.0211 (6)0.0286 (6)0.0221 (6)−0.0011 (5)0.0031 (5)−0.0028 (5)
O20.0283 (6)0.0295 (7)0.0213 (6)0.0066 (5)0.0046 (5)−0.0010 (5)
O30.0323 (7)0.0439 (8)0.0226 (6)0.0096 (6)0.0062 (5)0.0042 (6)
O40.0339 (7)0.0291 (7)0.0529 (9)−0.0065 (6)0.0048 (6)−0.0116 (6)
C10.0203 (8)0.0202 (8)0.0253 (8)0.0012 (6)0.0030 (6)0.0000 (7)
C20.0222 (8)0.0196 (8)0.0241 (8)0.0022 (6)0.0033 (6)0.0002 (7)
C30.0281 (9)0.0243 (9)0.0258 (8)0.0002 (7)0.0037 (7)−0.0046 (7)
C40.0359 (10)0.0275 (9)0.0254 (9)0.0052 (8)0.0113 (8)−0.0022 (7)
C50.0256 (9)0.0279 (9)0.0339 (9)0.0044 (7)0.0108 (7)0.0028 (8)
C60.0200 (8)0.0263 (9)0.0298 (9)0.0015 (7)0.0029 (7)0.0005 (7)
C70.0241 (8)0.0213 (8)0.0217 (8)0.0028 (7)0.0042 (6)0.0000 (6)
C80.0198 (8)0.0233 (8)0.0251 (8)0.0009 (6)0.0037 (6)0.0026 (7)
C90.0263 (9)0.0283 (9)0.0205 (8)0.0009 (7)0.0037 (7)0.0005 (7)
C100.0215 (8)0.0274 (9)0.0214 (8)−0.0046 (7)0.0052 (6)−0.0015 (7)
C110.0299 (9)0.0320 (10)0.0269 (9)0.0098 (8)0.0049 (7)0.0021 (8)
C120.0301 (9)0.0382 (11)0.0359 (10)0.0079 (8)0.0119 (8)0.0019 (9)
C130.0648 (15)0.0322 (11)0.0636 (15)0.0043 (10)0.0345 (13)0.0087 (11)
C140.0302 (10)0.0517 (13)0.0329 (10)0.0040 (9)−0.0030 (8)0.0067 (9)

Geometric parameters (Å, °)

S—O41.4949 (14)C6—C71.380 (2)
S—C11.7595 (17)C6—H60.9300
S—C141.7894 (19)C8—C91.491 (2)
F—C41.365 (2)C9—C101.512 (2)
O1—C81.3731 (19)C9—H9A0.9700
O1—C71.384 (2)C9—H9B0.9700
O2—C101.338 (2)C11—C121.502 (2)
O2—C111.472 (2)C11—C131.513 (3)
O3—C101.205 (2)C11—H110.9800
C1—C81.353 (2)C12—H12A0.9600
C1—C21.450 (2)C12—H12B0.9600
C2—C71.394 (2)C12—H12C0.9600
C2—C31.402 (2)C13—H13A0.9600
C3—C41.380 (2)C13—H13B0.9600
C3—H30.9300C13—H13C0.9600
C4—C51.384 (3)C14—H14A0.9600
C5—C61.385 (3)C14—H14B0.9600
C5—H50.9300C14—H14C0.9600
O4—S—C1108.00 (8)C10—C9—H9A109.0
O4—S—C14106.75 (10)C8—C9—H9B109.0
C1—S—C1498.47 (9)C10—C9—H9B109.0
C8—O1—C7106.03 (12)H9A—C9—H9B107.8
C10—O2—C11117.35 (13)O3—C10—O2124.43 (16)
C8—C1—C2107.15 (14)O3—C10—C9125.76 (15)
C8—C1—S121.23 (13)O2—C10—C9109.79 (14)
C2—C1—S131.57 (13)O2—C11—C12106.27 (14)
C7—C2—C3119.14 (15)O2—C11—C13108.45 (16)
C7—C2—C1104.64 (14)C12—C11—C13112.95 (17)
C3—C2—C1136.21 (16)O2—C11—H11109.7
C4—C3—C2115.75 (16)C12—C11—H11109.7
C4—C3—H3122.1C13—C11—H11109.7
C2—C3—H3122.1C11—C12—H12A109.5
F—C4—C3117.80 (16)C11—C12—H12B109.5
F—C4—C5117.32 (16)H12A—C12—H12B109.5
C3—C4—C5124.87 (16)C11—C12—H12C109.5
C4—C5—C6119.52 (16)H12A—C12—H12C109.5
C4—C5—H5120.2H12B—C12—H12C109.5
C6—C5—H5120.2C11—C13—H13A109.5
C7—C6—C5116.35 (16)C11—C13—H13B109.5
C7—C6—H6121.8H13A—C13—H13B109.5
C5—C6—H6121.8C11—C13—H13C109.5
C6—C7—O1124.87 (15)H13A—C13—H13C109.5
C6—C7—C2124.37 (16)H13B—C13—H13C109.5
O1—C7—C2110.75 (14)S—C14—H14A109.5
C1—C8—O1111.43 (14)S—C14—H14B109.5
C1—C8—C9132.54 (16)H14A—C14—H14B109.5
O1—C8—C9115.98 (14)S—C14—H14C109.5
C8—C9—C10112.79 (14)H14A—C14—H14C109.5
C8—C9—H9A109.0H14B—C14—H14C109.5
O4—S—C1—C8−126.67 (15)C3—C2—C7—C60.0 (3)
C14—S—C1—C8122.54 (15)C1—C2—C7—C6−178.66 (16)
O4—S—C1—C250.55 (18)C3—C2—C7—O1178.64 (14)
C14—S—C1—C2−60.23 (18)C1—C2—C7—O10.01 (18)
C8—C1—C2—C7−0.17 (18)C2—C1—C8—O10.27 (19)
S—C1—C2—C7−177.69 (14)S—C1—C8—O1178.10 (11)
C8—C1—C2—C3−178.44 (19)C2—C1—C8—C9177.57 (17)
S—C1—C2—C34.0 (3)S—C1—C8—C9−4.6 (3)
C7—C2—C3—C40.1 (2)C7—O1—C8—C1−0.26 (18)
C1—C2—C3—C4178.20 (18)C7—O1—C8—C9−178.05 (14)
C2—C3—C4—F−178.87 (15)C1—C8—C9—C10−69.4 (2)
C2—C3—C4—C50.0 (3)O1—C8—C9—C10107.82 (16)
F—C4—C5—C6178.67 (16)C11—O2—C10—O3−3.7 (2)
C3—C4—C5—C6−0.2 (3)C11—O2—C10—C9178.11 (14)
C4—C5—C6—C70.3 (3)C8—C9—C10—O313.5 (2)
C5—C6—C7—O1−178.66 (15)C8—C9—C10—O2−168.35 (14)
C5—C6—C7—C2−0.2 (3)C10—O2—C11—C12154.84 (15)
C8—O1—C7—C6178.81 (16)C10—O2—C11—C13−83.45 (19)
C8—O1—C7—C20.15 (18)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C5—H5···O3i0.932.503.370 (2)155
C6—H6···O2ii0.932.543.369 (2)149
C9—H9B···O4iii0.972.263.228 (2)176

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y+1, −z+2; (iii) x, −y+1/2, z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BQ2158).

References

  • Brandenburg, K. (1998). DIAMOND Crystal Impact GbR, Bonn, Germany.
  • Bruker (2001). SAINT and SMART Bruker AXS Inc., Madison, Wisconsin, USA.
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  • Choi, H. D., Seo, P. J., Son, B. W. & Lee, U. (2009b). Acta Cryst. E65, o2096. [PMC free article] [PubMed]
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Howlett, D. R., Perry, A. E., Godfrey, F., Swatton, J. E., Jennings, K. H., Spitzfaden, C., Wadsworth, H., Wood, S. J. & Markwell, R. E. (1999). Biochem. J 340, 283–289. [PubMed]
  • Sheldrick, G. M. (2000). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Twyman, L. J. & Allsop, D. (1999). Tetrahedron Lett 40, 9383–9384.

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