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Acta Crystallogr Sect E Struct Rep Online. 2008 January 1; 64(Pt 1): o148.
Published online 2007 December 6. doi:  10.1107/S1600536807063052
PMCID: PMC2915216

2-(4-Bromo­phen­yl)-5,7-dimethyl-3-methyl­sulfanyl-1-benzofuran

Abstract

The title compound, C17H15BrOS, was prepared by the Lewis acid-catalysed reaction of 2,4-dimethyl­phenol with 4′-bromo-2-chloro-2-(methyl­sulfan­yl)acetophenone. The 4-bromo­phenyl ring is rotated slightly out of the benzofuran plane, making a dihedral angle of 8.4 (1)°. The crystal structure is stabilized by a CH2—H(...)π inter­action between the 5-methyl group and the benzene ring of the benzofuran system.

Related literature

For the crystal structures of similar 2-(4-bromo­phen­yl)-1-benzofuran compounds, see: Choi et al. (2007a [triangle],b [triangle]).

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Object name is e-64-0o148-scheme1.jpg

Experimental

Crystal data

  • C17H15BrOS
  • M r = 347.26
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o148-efi1.jpg
  • a = 5.2332 (1) Å
  • b = 10.6602 (2) Å
  • c = 13.6374 (2) Å
  • β = 98.092 (1)°
  • V = 753.21 (2) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 2.86 mm−1
  • T = 296 (2) K
  • 0.30 × 0.24 × 0.08 mm

Data collection

  • Bruker SMART CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 2000 [triangle]) T min = 0.481, T max = 0.804
  • 7779 measured reflections
  • 3448 independent reflections
  • 2957 reflections with I > 2σ(I)
  • R int = 0.020

Refinement

  • R[F 2 > 2σ(F 2)] = 0.026
  • wR(F 2) = 0.066
  • S = 0.87
  • 3448 reflections
  • 182 parameters
  • 1 restraint
  • H-atom parameters constrained
  • Δρmax = 0.20 e Å−3
  • Δρmin = −0.20 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 1477 Friedel pairs
  • Flack parameter: 0.011 (7)

Data collection: SMART (Bruker, 2001 [triangle]); cell refinement: SAINT (Bruker, 2001 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 [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, global. DOI: 10.1107/S1600536807063052/om2192sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807063052/om2192Isup2.hkl

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

supplementary crystallographic information

Comment

As part of our continuing studies on the synthesis and structures of 2-(4-bromophenyl)-1-benzofuran derivatives, the crystal structures of 2-(4-bromophenyl)-5-methyl-3-methylsulfinyl-1-benzofuran (Choi et al., 2007a) and 2-(4-bromophenyl)-5,7-dimethyl-3-methylsulfinyl-1-benzofuran (Choi et al., 2007b) have been described to the literature. Herein we report the molecular and crystal structure of the title compound, 2-(4-bromophenyl)-5,7-dimethyl-3-methylsulfanyl-1-benzofuran (Fig. 1).

The benzofuran unit is essentially planar, with a mean deviation of 0.007 Å from the least-squares plane defined by the nine constituent atoms. The dihedral angle in the title compound formed by the plane of the benzofuran unit and the plane of the 4-bromophenyl ring is 8.4 (1)°. The molecular packing (Fig. 2) is stabilized by a CH2—H···π interaction between 5-methyl group and the benzene ring of benzofuran system, with a C15—H15A···Cgi separation of 2.97 Å (Table 1; Cg is a centroid of the C2—C7 benzene ring, symmetry code as in Fig. 2).

Experimental

Zinc chloride (546 mg, 4.0 mmol) was added at room temperature to a stirred solution of 2,4-dimethylphenol (489 mg, 4.0 mmol) and 4'-bromo-2-chloro-2-(methylsulfanyl)acetophenone (1.12 g, 4.0 mmol) in dichloromethane (30 ml) and stirred for 40 min. The mixture was quenched with water and the organic layer was separated, dried over magnesium sulfate, filtered and concentrated in vacuum. The residue was purified by column chromatography (CCl4) to afford the title compound as a colorless solid [yield 52%, m.p. 385–386 K; Rf = 0.81 (CCl4)]. Single crystals suitable for X-ray diffraction were prepared by slow evaporation of a dilute solution of the title compound in chloroform at room temperature.

Refinement

All H atoms were geometrically located in ideal positions and refined using a riding model, with C—H = 0.95 Å for aromatic H atoms and 0.98 Å for methyl H atoms, and with Uiso(H) = 1.2Ueq(C) for aromatic 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 50% probability level.
Fig. 2.
C—H···π interaction (dotted lines) in the title compound. Cg denotes ring centroid. [Symmetry code: (i) x - 1, y, z; (ii) x + 1, y, z.]

Crystal data

C17H15BrOSF000 = 352
Mr = 347.26Dx = 1.531 Mg m3
Monoclinic, P21Melting point = 385–386 K
Hall symbol: p 2ybMo Kα radiation λ = 0.71073 Å
a = 5.2332 (1) ÅCell parameters from 3988 reflections
b = 10.6602 (2) Åθ = 3.0–27.1º
c = 13.6374 (2) ŵ = 2.86 mm1
β = 98.092 (1)ºT = 296 (2) K
V = 753.21 (2) Å3Block, silver
Z = 20.30 × 0.24 × 0.08 mm

Data collection

Bruker SMART CCD diffractometer3448 independent reflections
Radiation source: fine-focus sealed tube2957 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.020
Detector resolution: 10.0 pixels mm-1θmax = 28.4º
T = 296(2) Kθmin = 1.5º
[var phi] and ω scansh = −6→6
Absorption correction: multi-scan(SADABS; Sheldrick, 2000)k = −14→14
Tmin = 0.481, Tmax = 0.804l = −17→18
7779 measured reflections

Refinement

Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.026  w = 1/[σ2(Fo2) + (0.0308P)2] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.066(Δ/σ)max = 0.001
S = 0.87Δρmax = 0.20 e Å3
3448 reflectionsΔρmin = −0.20 e Å3
182 parametersExtinction correction: none
1 restraintAbsolute structure: Flack (1983), 1477 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.011 (7)
Secondary atom site location: difference Fourier map

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
Br0.53020 (5)0.73216 (4)−0.179068 (16)0.06373 (10)
S−0.30384 (12)0.86959 (6)0.21002 (5)0.05180 (16)
O0.0436 (3)0.53588 (14)0.23230 (12)0.0412 (4)
C1−0.1770 (4)0.7187 (3)0.23497 (15)0.0404 (5)
C2−0.2370 (5)0.6414 (2)0.31587 (17)0.0407 (5)
C3−0.3917 (5)0.6547 (2)0.39043 (19)0.0470 (6)
H3−0.48890.72710.39460.056*
C4−0.3984 (5)0.5590 (2)0.45776 (18)0.0455 (5)
C5−0.2494 (5)0.4511 (2)0.44955 (17)0.0450 (5)
H5−0.25590.38780.49600.054*
C6−0.0931 (4)0.4327 (2)0.37673 (17)0.0410 (5)
C7−0.0959 (4)0.5314 (2)0.31082 (17)0.0398 (5)
C8−0.0091 (4)0.6519 (2)0.18701 (16)0.0404 (5)
C90.1192 (5)0.6724 (2)0.10053 (18)0.0404 (5)
C100.3069 (5)0.5879 (2)0.07758 (18)0.0468 (5)
H100.34910.51870.11820.056*
C110.4310 (5)0.6059 (2)−0.00479 (19)0.0510 (6)
H110.55680.5498−0.01900.061*
C120.3659 (5)0.7077 (2)−0.06535 (17)0.0465 (6)
C130.1811 (5)0.7927 (3)−0.04460 (19)0.0527 (6)
H130.13950.8613−0.08590.063*
C140.0585 (5)0.7753 (2)0.03788 (19)0.0491 (6)
H14−0.06550.83260.05180.059*
C15−0.5633 (5)0.5692 (3)0.5390 (2)0.0598 (7)
H15A−0.74030.58050.51050.072*
H15B−0.50810.63980.58030.072*
H15C−0.54710.49400.57800.072*
C160.0696 (5)0.3184 (2)0.3687 (2)0.0533 (6)
H16A0.01780.27850.30600.080*
H16B0.04730.26110.42120.080*
H16C0.24780.34240.37390.080*
C17−0.0310 (6)0.9643 (3)0.2543 (3)0.0748 (10)
H17A−0.07561.05120.24480.112*
H17B0.10870.94440.21830.112*
H17C0.02070.94830.32350.112*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br0.06774 (17)0.0829 (2)0.04418 (13)−0.01530 (17)0.02044 (10)0.00117 (15)
S0.0504 (4)0.0453 (3)0.0605 (4)0.0108 (3)0.0106 (3)0.0058 (3)
O0.0507 (9)0.0368 (9)0.0387 (9)0.0033 (7)0.0148 (7)0.0012 (6)
C10.0428 (11)0.0384 (12)0.0404 (10)0.0022 (11)0.0073 (8)−0.0004 (11)
C20.0446 (12)0.0388 (12)0.0397 (12)−0.0037 (10)0.0093 (9)−0.0049 (9)
C30.0501 (13)0.0448 (13)0.0483 (14)0.0014 (11)0.0144 (11)−0.0066 (11)
C40.0486 (12)0.0477 (14)0.0419 (13)−0.0117 (10)0.0125 (10)−0.0094 (10)
C50.0538 (14)0.0469 (13)0.0354 (11)−0.0120 (11)0.0099 (10)0.0023 (10)
C60.0457 (13)0.0378 (12)0.0395 (12)−0.0050 (10)0.0061 (10)−0.0001 (10)
C70.0441 (12)0.0418 (13)0.0347 (11)−0.0027 (11)0.0097 (9)−0.0039 (9)
C80.0456 (13)0.0394 (12)0.0361 (12)−0.0026 (10)0.0059 (10)0.0017 (9)
C90.0425 (12)0.0419 (12)0.0367 (12)−0.0040 (10)0.0055 (9)−0.0017 (9)
C100.0548 (14)0.0434 (13)0.0438 (13)0.0038 (11)0.0120 (10)0.0031 (11)
C110.0533 (15)0.0524 (15)0.0497 (14)0.0072 (12)0.0151 (11)−0.0009 (12)
C120.0470 (12)0.0553 (17)0.0375 (11)−0.0146 (12)0.0071 (9)−0.0032 (11)
C130.0625 (16)0.0527 (14)0.0427 (14)−0.0017 (13)0.0068 (12)0.0084 (11)
C140.0528 (14)0.0491 (15)0.0461 (14)0.0040 (11)0.0089 (11)0.0037 (10)
C150.0655 (17)0.0646 (17)0.0546 (16)−0.0084 (14)0.0272 (12)−0.0055 (13)
C160.0633 (17)0.0434 (14)0.0561 (16)0.0042 (12)0.0183 (13)0.0068 (11)
C170.069 (2)0.0472 (17)0.104 (3)−0.0002 (14)0.0003 (18)−0.0102 (17)

Geometric parameters (Å, °)

Br—C121.894 (2)C9—C141.399 (3)
S—C11.755 (3)C10—C111.387 (4)
S—C171.783 (3)C10—H100.9300
O—C71.379 (3)C11—C121.377 (4)
O—C81.393 (3)C11—H110.9300
C1—C81.367 (3)C12—C131.383 (4)
C1—C21.447 (3)C13—C141.384 (4)
C2—C31.393 (3)C13—H130.9300
C2—C71.393 (3)C14—H140.9300
C3—C41.377 (4)C15—H15A0.9600
C3—H30.9300C15—H15B0.9600
C4—C51.402 (3)C15—H15C0.9600
C4—C151.501 (3)C16—H16A0.9600
C5—C61.387 (4)C16—H16B0.9600
C5—H50.9300C16—H16C0.9600
C6—C71.382 (3)C17—H17A0.9600
C6—C161.499 (3)C17—H17B0.9600
C8—C91.453 (3)C17—H17C0.9600
C9—C101.401 (3)
C1—S—C17100.98 (13)C9—C10—H10119.5
C7—O—C8106.38 (17)C12—C11—C10119.3 (2)
C8—C1—C2106.9 (2)C12—C11—H11120.3
C8—C1—S129.47 (19)C10—C11—H11120.3
C2—C1—S123.58 (18)C11—C12—C13121.0 (2)
C3—C2—C7119.2 (2)C11—C12—Br119.82 (19)
C3—C2—C1135.2 (2)C13—C12—Br119.21 (19)
C7—C2—C1105.6 (2)C12—C13—C14119.7 (2)
C4—C3—C2118.9 (2)C12—C13—H13120.1
C4—C3—H3120.6C14—C13—H13120.1
C2—C3—H3120.6C13—C14—C9120.7 (2)
C3—C4—C5119.2 (2)C13—C14—H14119.7
C3—C4—C15120.6 (2)C9—C14—H14119.7
C5—C4—C15120.2 (2)C4—C15—H15A109.5
C6—C5—C4124.4 (2)C4—C15—H15B109.5
C6—C5—H5117.8H15A—C15—H15B109.5
C4—C5—H5117.8C4—C15—H15C109.5
C7—C6—C5113.8 (2)H15A—C15—H15C109.5
C7—C6—C16121.7 (2)H15B—C15—H15C109.5
C5—C6—C16124.5 (2)C6—C16—H16A109.5
O—C7—C6125.0 (2)C6—C16—H16B109.5
O—C7—C2110.56 (19)H16A—C16—H16B109.5
C6—C7—C2124.5 (2)C6—C16—H16C109.5
C1—C8—O110.5 (2)H16A—C16—H16C109.5
C1—C8—C9135.3 (2)H16B—C16—H16C109.5
O—C8—C9114.1 (2)S—C17—H17A109.5
C10—C9—C14118.3 (2)S—C17—H17B109.5
C10—C9—C8120.2 (2)H17A—C17—H17B109.5
C14—C9—C8121.5 (2)S—C17—H17C109.5
C11—C10—C9121.0 (2)H17A—C17—H17C109.5
C11—C10—H10119.5H17B—C17—H17C109.5
C17—S—C1—C8−74.5 (3)C3—C2—C7—C6−1.3 (3)
C17—S—C1—C2104.8 (2)C1—C2—C7—C6178.4 (2)
C8—C1—C2—C3−180.0 (2)C2—C1—C8—O−0.1 (2)
S—C1—C2—C30.6 (4)S—C1—C8—O179.26 (16)
C8—C1—C2—C70.4 (2)C2—C1—C8—C9178.2 (2)
S—C1—C2—C7−179.06 (16)S—C1—C8—C9−2.4 (4)
C7—C2—C3—C40.7 (3)C7—O—C8—C1−0.2 (2)
C1—C2—C3—C4−178.9 (2)C7—O—C8—C9−178.89 (17)
C2—C3—C4—C50.1 (3)C1—C8—C9—C10172.7 (3)
C2—C3—C4—C15−179.7 (2)O—C8—C9—C10−9.0 (3)
C3—C4—C5—C6−0.4 (4)C1—C8—C9—C14−7.9 (4)
C15—C4—C5—C6179.4 (2)O—C8—C9—C14170.44 (19)
C4—C5—C6—C7−0.2 (3)C14—C9—C10—C110.4 (3)
C4—C5—C6—C16179.0 (2)C8—C9—C10—C11179.8 (2)
C8—O—C7—C6−178.4 (2)C9—C10—C11—C12−0.7 (4)
C8—O—C7—C20.4 (2)C10—C11—C12—C130.7 (4)
C5—C6—C7—O179.7 (2)C10—C11—C12—Br−179.15 (18)
C16—C6—C7—O0.5 (3)C11—C12—C13—C14−0.3 (4)
C5—C6—C7—C21.0 (3)Br—C12—C13—C14179.56 (18)
C16—C6—C7—C2−178.2 (2)C12—C13—C14—C9−0.1 (4)
C3—C2—C7—O179.8 (2)C10—C9—C14—C130.1 (3)
C1—C2—C7—O−0.5 (2)C8—C9—C14—C13−179.4 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C15—H15A···Cgi0.962.973.891 (3)161

Symmetry codes: (i) x−1, y, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: OM2192).

References

  • Brandenburg, K. (1998). DIAMOND. Version 2.1. Crystal Impact GbR, Bonn, Germany.
  • Bruker (2001). SMART (Version 5.625) and SAINT (Version 6.28a). Bruker AXS Inc., Madison, Wisconsin, USA.
  • Choi, H. D., Seo, P. J., Son, B. W. & Lee, U. (2007a). Acta Cryst. E63, o3295.
  • Choi, H. D., Seo, P. J., Son, B. W. & Lee, U. (2007b). Acta Cryst. E63, o4282.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Flack, H. D. (1983). Acta Cryst. A39, 876–881.
  • Sheldrick, G. M. (1997). SHELXS97 and SHELXL97 University of Göttingen, Germany.
  • Sheldrick, G. M. (2000). SADABS Version 2.03. University of Göttingen, Germany.

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