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Acta Crystallogr Sect E Struct Rep Online. 2008 December 1; 64(Pt 12): o2250.
Published online 2008 November 8. doi:  10.1107/S160053680803506X
PMCID: PMC2959940

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

Abstract

In the title compound, C14H15BrO4S, the O atom and the methyl group of the methyl­sulfinyl substituent lie on opposite sides of the plane of the benzofuran fragment. The crystal structure is stabilized by C—H(...)π inter­actions between a methyl H atom and the benzene ring of a neighbouring mol­ecule, and by weak inter­molecular C—H(...)O hydrogen bonds.

Related literature

For the crystal structures of similar alkyl 2-(3-methyl­sulfinyl-1-benzofuran-2-yl)acetate derivatives, see: Choi et al. (2007 [triangle], 2008 [triangle]).

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Object name is e-64-o2250-scheme1.jpg

Experimental

Crystal data

  • C14H15BrO4S
  • M r = 359.23
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o2250-efi1.jpg
  • a = 7.947 (1) Å
  • b = 10.078 (1) Å
  • c = 10.868 (1) Å
  • α = 69.623 (2)°
  • β = 82.027 (2)°
  • γ = 67.409 (2)°
  • V = 753.33 (14) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 2.88 mm−1
  • T = 298 (2) K
  • 0.40 × 0.40 × 0.20 mm

Data collection

  • Bruker SMART CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1999 [triangle]) T min = 0.321, T max = 0.559
  • 3979 measured reflections
  • 2604 independent reflections
  • 2123 reflections with I > 2σ(I)
  • R int = 0.011

Refinement

  • R[F 2 > 2σ(F 2)] = 0.031
  • wR(F 2) = 0.085
  • S = 1.02
  • 2604 reflections
  • 181 parameters
  • H-atom parameters constrained
  • Δρmax = 0.46 e Å−3
  • Δρmin = −0.46 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 global, I. DOI: 10.1107/S160053680803506X/sg2276sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680803506X/sg2276Isup2.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 structure of alkyl 2-(3-methylsulfinyl-1-benzofuran-2-yl)acetate analogues, viz. ethyl 2-(5-bromo-3-methylsulfinyl-1-benzofuran-2-yl)acetate (Choi et al., 2007) and isopropyl 2-(5-methyl-3-methylsulfinyl-1-benzofuran-2-yl) acetate (Choi et al., 2008). Here we report the crystal structure of the title compound, isopropyl 2-(5-bromo-3-methylsulfinyl-1-benzofuran-2-yl) acetate (Fig. 1).

The benzofuran unit is essentially planar, with a mean deviation of 0.014 (2) Å from the least-squares plane defined by the nine constituent atoms. The molecular packing (Fig. 2) is stabilized by intermolecular C—H···π interactions between a methyl H atom of isoproyl group and the benzene ring of the benzofuran fragment, with a C13—H13C···Cgiii separation of 2.78 Å (Fig. 2 and Table 1; Cg is the centroid of the C2–C7 benzene ring, symmetry code as in Fig. 2). The molecular packing is further stabilized by two intermolecular C—H···O hydrogen bonds (Fig. 2 and Table 1)

Experimental

77% 3-chloroperoxybenzoic acid (370 mg, 1.65 mmol) was added in small portions to a stirred solution of isopropyl 2-(5-bromo-3-methylsulfanyl-1-benzofuran-2-yl)acetate (515 mg, 1.50 mmol) in dichloromethane (40 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 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 78%, m.p. 429–430 K; Rf = 0.74 (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 benzene at room temperature. Spectroscopic analysis: 1H NMR (CDCl3, 400 MHz) δ 1.26 (d, J = 6.24 Hz, 6H), 3.07 (s, 3H), 4.01 (s, 2H), 5.01–5.08 (m, 1H), 7.39 (d, J = 8.80 Hz, 1H), 7.48 (d, J = 8.76 Hz, 1H), 8.09 (s, 1H); EI—MS 360 [M+2], 358 [M+].

Refinement

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

Figures

Fig. 1.
The molecular structure of the title compound, showing displacement ellipsoids drawn at the 30% probability level.
Fig. 2.
C—H···π and C—H···O interactions (dotted lines) in the title compound. Cg denotes ring centroid. [Symmetry code: (i) x, y + 1, z; (ii) -x, -y + 1, -z + 2; (iii) x, y - 1, z.]

Crystal data

C14H15BrO4SZ = 2
Mr = 359.23F000 = 364
Triclinic, P1Dx = 1.584 Mg m3
Hall symbol: -P_1Melting point = 429–430 K
a = 7.947 (1) ÅMo Kα radiation λ = 0.71073 Å
b = 10.078 (1) ÅCell parameters from 2313 reflections
c = 10.868 (1) Åθ = 2.8–28.2º
α = 69.623 (2)ºµ = 2.88 mm1
β = 82.027 (2)ºT = 298 (2) K
γ = 67.409 (2)ºBlock, colorless
V = 753.33 (14) Å30.40 × 0.40 × 0.20 mm

Data collection

Bruker SMART CCD diffractometer2604 independent reflections
Radiation source: fine-focus sealed tube2123 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.011
Detector resolution: 10.0 pixels mm-1θmax = 25.0º
T = 298(2) Kθmin = 2.3º
[var phi] and ω scansh = −9→5
Absorption correction: multi-scan(SADABS; Sheldrick, 1999)k = −11→11
Tmin = 0.321, Tmax = 0.559l = −12→12
3979 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.031H-atom parameters constrained
wR(F2) = 0.085  w = 1/[σ2(Fo2) + (0.042P)2 + 0.4644P] where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max < 0.001
2604 reflectionsΔρmax = 0.46 e Å3
181 parametersΔρmin = −0.46 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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 > σ(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
Br0.70616 (5)0.79293 (4)0.62791 (4)0.07083 (16)
S0.25401 (10)0.39786 (9)0.96079 (7)0.0469 (2)
O10.1648 (2)0.5361 (2)0.58148 (17)0.0407 (4)
O20.2529 (3)0.5174 (3)1.0122 (2)0.0624 (6)
O3−0.0241 (3)0.1540 (2)0.7747 (2)0.0532 (5)
O40.2603 (3)0.1418 (3)0.7888 (3)0.0651 (6)
C10.2522 (4)0.4734 (3)0.7885 (3)0.0377 (6)
C20.3526 (3)0.5637 (3)0.7033 (3)0.0367 (6)
C30.4811 (4)0.6187 (3)0.7202 (3)0.0422 (6)
H30.52640.59560.80260.051*
C40.5377 (4)0.7090 (3)0.6087 (3)0.0457 (7)
C50.4752 (4)0.7448 (3)0.4839 (3)0.0487 (7)
H50.51840.80630.41190.058*
C60.3495 (4)0.6897 (3)0.4662 (3)0.0441 (7)
H60.30650.71160.38340.053*
C70.2906 (4)0.6004 (3)0.5777 (3)0.0377 (6)
C80.1423 (4)0.4614 (3)0.7115 (3)0.0389 (6)
C90.4813 (5)0.2606 (4)0.9795 (3)0.0648 (9)
H9A0.50680.20671.07110.097*
H9B0.56600.31130.94260.097*
H9C0.49300.19030.93500.097*
C100.0116 (4)0.3821 (3)0.7411 (3)0.0437 (7)
H10A−0.06960.42390.66710.052*
H10B−0.06170.40140.81650.052*
C110.1016 (4)0.2131 (3)0.7692 (3)0.0416 (6)
C120.0375 (5)−0.0102 (4)0.7976 (4)0.0630 (9)
H120.1468−0.06520.85240.076*
C130.0742 (7)−0.0350 (4)0.6682 (5)0.0978 (16)
H13A0.16490.00550.62200.117*
H13B−0.03610.01530.61800.117*
H13C0.1175−0.14180.68100.117*
C14−0.1201 (8)−0.0562 (5)0.8665 (4)0.1008 (16)
H14A−0.2254−0.00170.81100.121*
H14B−0.1470−0.03290.94710.121*
H14C−0.0881−0.16330.88510.121*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br0.0636 (2)0.0633 (2)0.0936 (3)−0.04221 (19)−0.00607 (19)−0.0111 (2)
S0.0499 (4)0.0555 (5)0.0372 (4)−0.0265 (4)−0.0032 (3)−0.0078 (3)
O10.0454 (11)0.0435 (11)0.0376 (10)−0.0190 (9)−0.0054 (8)−0.0131 (9)
O20.0709 (15)0.0739 (16)0.0505 (13)−0.0259 (12)−0.0048 (11)−0.0285 (12)
O30.0584 (13)0.0409 (11)0.0657 (14)−0.0251 (10)−0.0142 (10)−0.0103 (10)
O40.0492 (14)0.0484 (13)0.0931 (18)−0.0181 (11)−0.0084 (12)−0.0138 (12)
C10.0402 (15)0.0386 (15)0.0379 (15)−0.0181 (12)−0.0022 (12)−0.0113 (12)
C20.0382 (14)0.0316 (14)0.0398 (15)−0.0117 (11)−0.0041 (11)−0.0105 (11)
C30.0416 (15)0.0407 (15)0.0462 (16)−0.0164 (13)−0.0063 (12)−0.0123 (13)
C40.0419 (16)0.0372 (15)0.0593 (19)−0.0181 (13)0.0002 (13)−0.0131 (14)
C50.0498 (17)0.0399 (16)0.0483 (17)−0.0164 (14)0.0071 (14)−0.0075 (13)
C60.0486 (17)0.0403 (16)0.0373 (15)−0.0116 (13)−0.0008 (12)−0.0103 (12)
C70.0403 (15)0.0327 (14)0.0400 (15)−0.0114 (12)−0.0035 (12)−0.0125 (12)
C80.0414 (15)0.0372 (14)0.0405 (15)−0.0154 (12)−0.0024 (12)−0.0132 (12)
C90.067 (2)0.060 (2)0.058 (2)−0.0173 (18)−0.0160 (17)−0.0083 (17)
C100.0425 (16)0.0459 (16)0.0488 (16)−0.0203 (13)−0.0051 (13)−0.0159 (13)
C110.0480 (18)0.0459 (16)0.0364 (15)−0.0246 (14)−0.0020 (12)−0.0106 (12)
C120.078 (2)0.0388 (17)0.073 (2)−0.0261 (17)−0.0265 (19)−0.0036 (16)
C130.119 (4)0.051 (2)0.111 (4)−0.024 (2)0.042 (3)−0.036 (2)
C140.159 (5)0.084 (3)0.086 (3)−0.086 (3)0.024 (3)−0.022 (2)

Geometric parameters (Å, °)

Br—C41.904 (3)C6—C71.380 (4)
S—O21.492 (2)C6—H60.9300
S—C11.759 (3)C8—C101.479 (4)
S—C91.790 (4)C9—H9A0.9600
O1—C81.374 (3)C9—H9B0.9600
O1—C71.375 (3)C9—H9C0.9600
O3—C111.331 (3)C10—C111.506 (4)
O3—C121.471 (4)C10—H10A0.9700
O4—C111.193 (3)C10—H10B0.9700
C1—C81.352 (4)C12—C131.483 (5)
C1—C21.445 (4)C12—C141.513 (6)
C2—C71.392 (4)C12—H120.9800
C2—C31.394 (4)C13—H13A0.9600
C3—C41.376 (4)C13—H13B0.9600
C3—H30.9300C13—H13C0.9600
C4—C51.387 (4)C14—H14A0.9600
C5—C61.378 (4)C14—H14B0.9600
C5—H50.9300C14—H14C0.9600
O2—S—C1107.21 (13)H9A—C9—H9B109.5
O2—S—C9106.82 (16)S—C9—H9C109.5
C1—S—C998.00 (15)H9A—C9—H9C109.5
C8—O1—C7106.32 (19)H9B—C9—H9C109.5
C11—O3—C12118.0 (2)C8—C10—C11113.5 (2)
C8—C1—C2107.3 (2)C8—C10—H10A108.9
C8—C1—S123.7 (2)C11—C10—H10A108.9
C2—C1—S129.0 (2)C8—C10—H10B108.9
C7—C2—C3119.5 (2)C11—C10—H10B108.9
C7—C2—C1104.7 (2)H10A—C10—H10B107.7
C3—C2—C1135.9 (2)O4—C11—O3125.0 (3)
C4—C3—C2116.6 (3)O4—C11—C10125.3 (3)
C4—C3—H3121.7O3—C11—C10109.6 (2)
C2—C3—H3121.7O3—C12—C13108.1 (3)
C3—C4—C5123.6 (3)O3—C12—C14105.3 (3)
C3—C4—Br118.0 (2)C13—C12—C14110.8 (3)
C5—C4—Br118.4 (2)O3—C12—H12110.8
C6—C5—C4120.2 (3)C13—C12—H12110.8
C6—C5—H5119.9C14—C12—H12110.8
C4—C5—H5119.9C12—C13—H13A109.5
C5—C6—C7116.6 (3)C12—C13—H13B109.5
C5—C6—H6121.7H13A—C13—H13B109.5
C7—C6—H6121.7C12—C13—H13C109.5
O1—C7—C6125.7 (2)H13A—C13—H13C109.5
O1—C7—C2110.7 (2)H13B—C13—H13C109.5
C6—C7—C2123.6 (3)C12—C14—H14A109.5
C1—C8—O1111.0 (2)C12—C14—H14B109.5
C1—C8—C10132.5 (3)H14A—C14—H14B109.5
O1—C8—C10116.5 (2)C12—C14—H14C109.5
S—C9—H9A109.5H14A—C14—H14C109.5
S—C9—H9B109.5H14B—C14—H14C109.5
O2—S—C1—C8−134.2 (2)C3—C2—C7—O1−179.9 (2)
C9—S—C1—C8115.3 (3)C1—C2—C7—O1−1.4 (3)
O2—S—C1—C241.9 (3)C3—C2—C7—C60.1 (4)
C9—S—C1—C2−68.5 (3)C1—C2—C7—C6178.5 (3)
C8—C1—C2—C70.5 (3)C2—C1—C8—O10.7 (3)
S—C1—C2—C7−176.2 (2)S—C1—C8—O1177.55 (18)
C8—C1—C2—C3178.5 (3)C2—C1—C8—C10178.8 (3)
S—C1—C2—C31.8 (5)S—C1—C8—C10−4.3 (5)
C7—C2—C3—C40.6 (4)C7—O1—C8—C1−1.5 (3)
C1—C2—C3—C4−177.2 (3)C7—O1—C8—C10180.0 (2)
C2—C3—C4—C5−0.7 (4)C1—C8—C10—C11−76.4 (4)
C2—C3—C4—Br177.7 (2)O1—C8—C10—C11101.6 (3)
C3—C4—C5—C60.1 (5)C12—O3—C11—O4−4.5 (4)
Br—C4—C5—C6−178.3 (2)C12—O3—C11—C10178.3 (3)
C4—C5—C6—C70.6 (4)C8—C10—C11—O412.3 (4)
C8—O1—C7—C6−178.1 (3)C8—C10—C11—O3−170.5 (2)
C8—O1—C7—C21.8 (3)C11—O3—C12—C13−89.9 (4)
C5—C6—C7—O1179.3 (3)C11—O3—C12—C14151.6 (3)
C5—C6—C7—C2−0.7 (4)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C3—H3···O2i0.932.503.392 (4)160
C10—H10B···O2ii0.972.403.365 (4)173
C13—H13C···Cgiii0.962.783.526 (4)136

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SG2276).

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. (2007). Acta Cryst. E63, o3850.
  • Choi, H. D., Seo, P. J., Son, B. W. & Lee, U. (2008). Acta Cryst. E64, o2079. [PMC free article] [PubMed]
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Sheldrick, G. M. (1999). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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