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Acta Cryst. (2008). E64, o2250    [ doi:10.1107/S160053680803506X ]

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

H. D. Choi, P. J. Seo, B. W. Son and U. Lee

Abstract top

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...[pi] interactions between a methyl H atom and the benzene ring of a neighbouring molecule, and by weak intermolecular C-H...O hydrogen bonds.

Comment top

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)

Related literature top

For the crystal structures of similar alkyl 2-(3-methylsulfinyl-1-benzofuran-2-yl)acetate derivatives, see: Choi et al. (2007, 2008). Cg is the centroid of the C2–C7 benzene ring

Experimental top

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 top

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.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); 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 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, showing displacement ellipsoids drawn at the 30% probability level.
[Figure 2] 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.]
Isopropyl 2-(5-bromo-3-methylsulfinyl-1-benzofuran-2-yl)acetate top
Crystal data top
C14H15BrO4SZ = 2
Mr = 359.23F(000) = 364
Triclinic, P1Dx = 1.584 Mg m−3
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 = 2.8–28.2°
α = 69.623 (2)°µ = 2.88 mm−1
β = 82.027 (2)°T = 298 K
γ = 67.409 (2)°Block, colorless
V = 753.33 (14) Å30.40 × 0.40 × 0.20 mm
Data collection top
Bruker SMART CCD
diffractometer		2604 independent reflections
Radiation source: fine-focus sealed tube2123 reflections with I > 2σ(I)
graphiteRint = 0.011
Detector resolution: 10.0 pixels mm-1θmax = 25.0°, θmin = 2.3°
φ 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 top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.031Hydrogen site location: difference Fourier map
wR(F2) = 0.085H-atom parameters constrained
S = 1.02 w = 1/[σ2(Fo2) + (0.042P)2 + 0.4644P]
where P = (Fo2 + 2Fc2)/3
2604 reflections(Δ/σ)max < 0.001
181 parametersΔρmax = 0.46 e Å−3
0 restraintsΔρmin = −0.46 e Å−3
Crystal data top
C14H15BrO4Sγ = 67.409 (2)°
Mr = 359.23V = 753.33 (14) Å3
Triclinic, P1Z = 2
a = 7.947 (1) ÅMo Kα radiation
b = 10.078 (1) ŵ = 2.88 mm−1
c = 10.868 (1) ÅT = 298 K
α = 69.623 (2)°0.40 × 0.40 × 0.20 mm
β = 82.027 (2)°
Data collection top
Bruker SMART CCD
diffractometer		2604 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1999)		2123 reflections with I > 2σ(I)
Tmin = 0.321, Tmax = 0.559Rint = 0.011
3979 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.031H-atom parameters constrained
wR(F2) = 0.085Δρmax = 0.46 e Å−3
S = 1.02Δρmin = −0.46 e Å−3
2604 reflectionsAbsolute structure: ?
181 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

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) top
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) top
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, °) top
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, °) top
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.
Table 1
Hydrogen-bond geometry (Å, °) top
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.
references
References top

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.

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.