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Acta Crystallogr Sect E Struct Rep Online. 2008 September 1; 64(Pt 9): o1711.
Published online 2008 August 6. doi:  10.1107/S1600536808024689
PMCID: PMC2960547

Methyl 2-(5-methyl-3-methyl­sulfinyl-1-benzofuran-2-yl)acetate

Abstract

The title compound, C13H14O4S, was prepared by oxidation of methyl 2-(5-methyl-3-methyl­sulfanyl-1-benzofuran-2-yl)acetate with 3-chloro­peroxy­benzoic acid. The O atom and methyl group of the methyl­sulfinyl substituent lie on opposite sides of the plane of the benzofuran system. The crystal structure is stabilized by inter­molecular aromatic π–π inter­actions between the benzene rings of neighbouring mol­ecules, with a centroid–centroid separation of 3.841 (3) Å.

Related literature

For the crystal structures of similar ethyl 2-(3-methyl­sulfinyl-1-benzofuran-2-yl)acetate derivatives, see: Choi et al. (2007a [triangle],b [triangle]).

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Object name is e-64-o1711-scheme1.jpg

Experimental

Crystal data

  • C13H14O4S
  • M r = 266.30
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1711-efi1.jpg
  • a = 7.9331 (6) Å
  • b = 8.1097 (6) Å
  • c = 10.7017 (8) Å
  • α = 71.601 (1)°
  • β = 81.107 (1)°
  • γ = 84.303 (1)°
  • V = 644.51 (8) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.26 mm−1
  • T = 298 (2) K
  • 0.40 × 0.20 × 0.20 mm

Data collection

  • Bruker SMART CCD diffractometer
  • Absorption correction: none
  • 3414 measured reflections
  • 2237 independent reflections
  • 1788 reflections with I > 2σ(I)
  • R int = 0.052

Refinement

  • R[F 2 > 2σ(F 2)] = 0.045
  • wR(F 2) = 0.123
  • S = 1.03
  • 2237 reflections
  • 166 parameters
  • H-atom parameters constrained
  • Δρmax = 0.34 e Å−3
  • Δρmin = −0.35 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.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808024689/bh2186sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808024689/bh2186Isup2.hkl

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

supplementary crystallographic information

Comment

This work is related to our previous communications on the synthesis and structures of ethyl 2-(3-methylsulfinyl-1-benzofuran-2-yl)acetate analogues, viz. ethyl 2-(5-chloro-3-methylsulfinyl-1-benzofuran-2-yl)acetate (Choi et al., 2007a) and ethyl 2-(5-methyl-3-methylsulfinyl-1-benzofuran-2-yl)acetate (Choi et al., 2007b). Here we report the crystal structure of the title compound, methyl 2-(5-methyl-3-methylsulfinyl-1-benzofuran-2-yl)acetate (Fig. 1).

The benzofuran unit is essentially planar, with a mean deviation of 0.009 (2) Å from the least-squares plane defined by the nine constituent atoms. The packing structure is stabilized by aromatic π–π stacking interactions between adjacent benzene units, with a Cg···Cgi distance is 3.841 (3) Å (Fig. 2).

Experimental

77% 3-Chloroperoxybenzoic acid (359 mg, 1.6 mmol) was added in small portions to a stirred solution of methyl 2-(5-methyl-3-methylsulfanyl-1-benzofuran-2-yl)acetate (375 mg, 1.5 mmol) in dichloromethane (30 ml) at 273 K. After being stirred for 3 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 under vacuum. The residue was purified by column chromatography (ethyl acetate) to afford the title compound as a colorless solid [yield 79%, m.p. 380–381 K; Rf = 0.58 (ethyl acetate)]. Single crystals suitable for X-ray diffraction were prepared by evaporation of a solution of the title compound in ethyl acetate at room temperature. Spectroscopic analysis: 1H NMR (CDCl3, 400 MHz) δ 2.45 (s, 3H), 3.07 (s, 3H), 3.74 (s, 3H), 4.04 (s, 2H), 7.17 (dd, J = 8.44 Hz and J = 1.08 Hz, 1H), 7.38 (d, J = 8.40 Hz, 1H), 7.71 (s, 1H); EI–MS 266 [M+].

Refinement

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

Figures

Fig. 1.
The molecular structure of the title compound, showing displacement ellipsoids drawn at the 30% probability level.
Fig. 2.
Intermolecular π–π interactions (dotted lines) in the title compound. Cg denotes ring centroid. Symmetry code: (i) 1-x, 2-y, -z.

Crystal data

C13H14O4SZ = 2
Mr = 266.30F000 = 280
Triclinic, P1Dx = 1.372 Mg m3
Hall symbol: -P 1Melting point = 380–381 K
a = 7.9331 (6) ÅMo Kα radiation λ = 0.71073 Å
b = 8.1097 (6) ÅCell parameters from 1817 reflections
c = 10.7017 (8) Åθ = 2.6–27.3º
α = 71.601 (1)ºµ = 0.26 mm1
β = 81.107 (1)ºT = 298 (2) K
γ = 84.303 (1)ºBlock, colorless
V = 644.51 (8) Å30.40 × 0.20 × 0.20 mm

Data collection

Bruker SMART CCD diffractometer2237 independent reflections
Radiation source: fine-focus sealed tube1788 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.052
Detector resolution: 10.0 pixels mm-1θmax = 25.0º
T = 298(2) Kθmin = 2.0º
[var phi] and ω scansh = −9→9
Absorption correction: nonek = −9→9
3414 measured reflectionsl = −9→12

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.045H-atom parameters constrained
wR(F2) = 0.123  w = 1/[σ2(Fo2) + (0.0647P)2 + 0.1924P] where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max < 0.001
2237 reflectionsΔρmax = 0.34 e Å3
166 parametersΔρmin = −0.35 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

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

xyzUiso*/Ueq
S0.22227 (8)0.36975 (8)0.45695 (6)0.0430 (2)
O10.16435 (19)0.5432 (2)0.07927 (16)0.0392 (4)
O2−0.1560 (3)0.0853 (3)0.3071 (3)0.0850 (8)
O30.1251 (2)0.0969 (2)0.2923 (2)0.0565 (5)
O40.2489 (3)0.5059 (3)0.51807 (19)0.0597 (5)
C10.2418 (3)0.4676 (3)0.2838 (2)0.0348 (5)
C20.3713 (3)0.5757 (3)0.1944 (2)0.0342 (5)
C30.5246 (3)0.6396 (3)0.2059 (3)0.0410 (6)
H30.56470.61110.28770.049*
C40.6143 (3)0.7457 (3)0.0930 (3)0.0445 (6)
C50.5523 (3)0.7870 (3)−0.0291 (3)0.0486 (7)
H50.61470.8592−0.10380.058*
C60.4028 (3)0.7256 (3)−0.0442 (3)0.0460 (6)
H60.36280.7534−0.12600.055*
C70.3168 (3)0.6199 (3)0.0709 (2)0.0366 (5)
C80.1227 (3)0.4533 (3)0.2103 (2)0.0352 (5)
C9−0.0416 (3)0.3635 (3)0.2452 (3)0.0404 (6)
H9A−0.10490.40710.16970.048*
H9B−0.10810.39750.31810.048*
C10−0.0307 (3)0.1679 (3)0.2841 (3)0.0447 (6)
C110.1449 (4)−0.0918 (4)0.3298 (4)0.0801 (11)
H11A0.0761−0.14090.41320.120*
H11B0.2627−0.12800.33820.120*
H11C0.1090−0.13120.26290.120*
C120.7804 (3)0.8174 (4)0.1000 (3)0.0616 (8)
H12A0.81190.76770.18780.092*
H12B0.76610.94160.07970.092*
H12C0.86850.78840.03690.092*
C130.4142 (4)0.2333 (4)0.4661 (3)0.0573 (7)
H13A0.51120.30420.43960.086*
H13B0.41760.16350.40800.086*
H13C0.41670.15880.55560.086*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S0.0403 (4)0.0487 (4)0.0362 (4)−0.0034 (3)−0.0055 (3)−0.0072 (3)
O10.0378 (9)0.0428 (9)0.0376 (9)−0.0039 (7)−0.0099 (7)−0.0104 (7)
O20.0557 (13)0.0589 (13)0.135 (2)−0.0209 (11)−0.0173 (13)−0.0150 (14)
O30.0415 (10)0.0357 (9)0.0832 (14)−0.0039 (8)0.0035 (9)−0.0100 (9)
O40.0708 (13)0.0711 (13)0.0456 (11)0.0066 (10)−0.0141 (10)−0.0297 (10)
C10.0363 (12)0.0338 (12)0.0349 (12)−0.0017 (9)−0.0056 (10)−0.0110 (10)
C20.0354 (12)0.0307 (11)0.0377 (13)0.0006 (9)−0.0047 (10)−0.0128 (10)
C30.0376 (13)0.0413 (13)0.0482 (15)−0.0020 (10)−0.0082 (11)−0.0182 (12)
C40.0369 (13)0.0363 (13)0.0611 (17)−0.0010 (10)−0.0039 (12)−0.0175 (12)
C50.0433 (14)0.0415 (14)0.0517 (16)−0.0044 (11)0.0054 (12)−0.0060 (12)
C60.0492 (15)0.0442 (14)0.0397 (14)−0.0006 (12)−0.0058 (12)−0.0065 (11)
C70.0337 (12)0.0341 (12)0.0435 (14)0.0006 (9)−0.0065 (10)−0.0139 (10)
C80.0354 (12)0.0317 (11)0.0381 (13)−0.0004 (9)−0.0038 (10)−0.0110 (10)
C90.0317 (12)0.0448 (14)0.0466 (15)−0.0027 (10)−0.0082 (11)−0.0152 (11)
C100.0423 (14)0.0478 (15)0.0453 (15)−0.0094 (11)−0.0040 (11)−0.0148 (12)
C110.070 (2)0.0385 (16)0.115 (3)−0.0043 (15)0.006 (2)−0.0086 (17)
C120.0427 (15)0.0532 (16)0.088 (2)−0.0115 (12)−0.0069 (15)−0.0182 (16)
C130.0571 (17)0.0524 (16)0.0596 (18)0.0078 (13)−0.0169 (14)−0.0116 (14)

Geometric parameters (Å, °)

S—O41.495 (2)C5—H50.9300
S—C11.759 (2)C6—C71.381 (3)
S—C131.788 (3)C6—H60.9300
O1—C81.366 (3)C8—C91.495 (3)
O1—C71.392 (3)C9—C101.505 (3)
O2—C101.204 (3)C9—H9A0.9700
O3—C101.315 (3)C9—H9B0.9700
O3—C111.453 (3)C11—H11A0.9600
C1—C81.354 (3)C11—H11B0.9600
C1—C21.444 (3)C11—H11C0.9600
C2—C71.382 (3)C12—H12A0.9600
C2—C31.405 (3)C12—H12B0.9600
C3—C41.381 (4)C12—H12C0.9600
C3—H30.9300C13—H13A0.9600
C4—C51.397 (4)C13—H13B0.9600
C4—C121.513 (3)C13—H13C0.9600
C5—C61.382 (4)
O4—S—C1107.63 (11)O1—C8—C9116.0 (2)
O4—S—C13105.85 (13)C8—C9—C10117.4 (2)
C1—S—C1398.82 (13)C8—C9—H9A108.0
C8—O1—C7106.00 (17)C10—C9—H9A108.0
C10—O3—C11117.3 (2)C8—C9—H9B108.0
C8—C1—C2107.3 (2)C10—C9—H9B108.0
C8—C1—S122.09 (18)H9A—C9—H9B107.2
C2—C1—S130.59 (18)O2—C10—O3123.6 (2)
C7—C2—C3119.0 (2)O2—C10—C9121.9 (2)
C7—C2—C1104.91 (19)O3—C10—C9114.4 (2)
C3—C2—C1136.1 (2)O3—C11—H11A109.5
C4—C3—C2118.5 (2)O3—C11—H11B109.5
C4—C3—H3120.8H11A—C11—H11B109.5
C2—C3—H3120.8O3—C11—H11C109.5
C3—C4—C5120.0 (2)H11A—C11—H11C109.5
C3—C4—C12120.5 (3)H11B—C11—H11C109.5
C5—C4—C12119.4 (2)C4—C12—H12A109.5
C6—C5—C4123.0 (2)C4—C12—H12B109.5
C6—C5—H5118.5H12A—C12—H12B109.5
C4—C5—H5118.5C4—C12—H12C109.5
C7—C6—C5115.3 (2)H12A—C12—H12C109.5
C7—C6—H6122.4H12B—C12—H12C109.5
C5—C6—H6122.4S—C13—H13A109.5
C6—C7—C2124.2 (2)S—C13—H13B109.5
C6—C7—O1125.2 (2)H13A—C13—H13B109.5
C2—C7—O1110.58 (19)S—C13—H13C109.5
C1—C8—O1111.21 (19)H13A—C13—H13C109.5
C1—C8—C9132.8 (2)H13B—C13—H13C109.5
O4—S—C1—C8−129.6 (2)C1—C2—C7—C6179.0 (2)
C13—S—C1—C8120.6 (2)C3—C2—C7—O1179.36 (19)
O4—S—C1—C248.5 (2)C1—C2—C7—O1−1.1 (2)
C13—S—C1—C2−61.4 (2)C8—O1—C7—C6−178.8 (2)
C8—C1—C2—C70.5 (2)C8—O1—C7—C21.2 (2)
S—C1—C2—C7−177.78 (18)C2—C1—C8—O10.3 (3)
C8—C1—C2—C3180.0 (3)S—C1—C8—O1178.70 (15)
S—C1—C2—C31.7 (4)C2—C1—C8—C9−178.3 (2)
C7—C2—C3—C40.5 (3)S—C1—C8—C90.1 (4)
C1—C2—C3—C4−178.9 (2)C7—O1—C8—C1−0.9 (2)
C2—C3—C4—C5−0.1 (4)C7—O1—C8—C9177.97 (19)
C2—C3—C4—C12−179.8 (2)C1—C8—C9—C10−72.1 (3)
C3—C4—C5—C6−0.3 (4)O1—C8—C9—C10109.3 (2)
C12—C4—C5—C6179.4 (2)C11—O3—C10—O20.7 (4)
C4—C5—C6—C70.3 (4)C11—O3—C10—C9179.8 (3)
C5—C6—C7—C20.2 (4)C8—C9—C10—O2−176.1 (3)
C5—C6—C7—O1−179.8 (2)C8—C9—C10—O34.8 (3)
C3—C2—C7—C6−0.6 (3)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BH2186).

References

  • Brandenburg, K. (1998). DIAMOND Crystal Impact GbR, Bonn, Germany.
  • Bruker (2001). SAINT and SMART Bruker AXS Inc., Madison, Wisconsin, USA.
  • Choi, H. D., Seo, P. J., Son, B. W. & Lee, U. (2007a). Acta Cryst. E63, o3832.
  • Choi, H. D., Seo, P. J., Son, B. W. & Lee, U. (2007b). Acta Cryst. E63, o3839.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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