organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

5-Bromo-7-methyl-2-(4-methyl­phen­yl)-3-methyl­sulfinyl-1-benzo­furan

aDepartment of Chemistry, Dongeui University, San 24 Kaya-dong, Busanjin-gu, Busan 614-714, Republic of Korea, and bDepartment of Chemistry, Pukyong National University, 599-1 Daeyeon 3-dong, Nam-gu, Busan 608-737, Republic of Korea
*Correspondence e-mail: uklee@pknu.ac.kr

(Received 7 November 2012; accepted 14 November 2012; online 28 November 2012)

In the title compound, C17H15BrO2S, the 4-methyl­phenyl ring makes a dihedral angle of 14.46 (5)° with the mean plane [r.m.s. deviation = 0.005 (1) Å] of the benzofuran fragment. In the crystal, mol­ecules are linked by pairs of Br⋯O contacts [3.151 (2) Å] into centrosymmetric dimers.

Related literature

For background information and the crystal structures of related compounds, see: Choi et al. (2010[Choi, H. D., Seo, P. J., Son, B. W. & Lee, U. (2010). Acta Cryst. E66, o215.]); Seo et al. (2009[Seo, P. J., Choi, H. D., Son, B. W. & Lee, U. (2009). Acta Cryst. E65, o2302.]). For a review of halogen bonding, see: Politzer et al. (2007[Politzer, P., Lane, P., Concha, M. C., Ma, Y. & Murray, J. S. (2007). J. Mol. Model. 13, 305-311.]).

[Scheme 1]

Experimental

Crystal data
  • C17H15BrO2S

  • Mr = 363.26

  • Triclinic, [P \overline 1]

  • a = 7.6375 (2) Å

  • b = 9.5170 (2) Å

  • c = 11.2413 (2) Å

  • α = 75.513 (1)°

  • β = 84.848 (1)°

  • γ = 71.626 (1)°

  • V = 750.72 (3) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 2.88 mm−1

  • T = 173 K

  • 0.28 × 0.24 × 0.22 mm

Data collection
  • Bruker SMART APEXII CCD diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2009[Bruker (2009). APEX2, SADABS and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.504, Tmax = 0.568

  • 14012 measured reflections

  • 3716 independent reflections

  • 3331 reflections with I > 2σ(I)

  • Rint = 0.040

Refinement
  • R[F2 > 2σ(F2)] = 0.028

  • wR(F2) = 0.075

  • S = 1.05

  • 3716 reflections

  • 193 parameters

  • H-atom parameters constrained

  • Δρmax = 0.48 e Å−3

  • Δρmin = −0.56 e Å−3

Data collection: APEX2 (Bruker, 2009[Bruker (2009). APEX2, SADABS and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2009[Bruker (2009). APEX2, SADABS and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 (Farrugia, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.]) and DIAMOND (Brandenburg, 1998[Brandenburg, K. (1998). DIAMOND. Crystal Impact GbR, Bonn, Germany.]); software used to prepare material for publication: SHELXL97.

Supporting information


Comment top

As a part of our ongoing study of 5-bromo-7-methyl-3-methylsulfinyl-1-benzofuran derivatives containing 4-fluorophenyl (Choi et al., 2010) and methyl (Seo et al., 2009) substituents in 2-position, we report herein the crystal structure of the title compound.

In the title molecule (Fig. 1), the benzofuran unit is essentially planar, with a mean deviation of 0.005 (1) Å from the least-squares plane defined by the nine constituent atoms. The dihedral angle between the 4-methylphenyl ring and the mean plane of the benzofuran ring is 14.46 (5)°. In the crystal structure, molecules are linked via pairs of Br···O halogen-bondings between the bromine and the oxygen of the SO unit [Br1···O2i = 3.151 (2) Å, C4—Br1···O2i = 166.55 (6)°, symmetry code : (i) - x + 2, - y + 1, - z + 2] (Politzer et al., 2007) into centrosymmetric dimers.

Related literature top

For background information and the crystal structures of related compounds, see: Choi et al. (2010); Seo et al. (2009). For a review of halogen bonding, see: Politzer et al. (2007).

Experimental top

3-Chloroperoxybenzoic acid (77%, 224 mg, 1.0 mmol) was added in small portions to a stirred solution of 5-bromo-7-methyl-2-(4-methylphenyl)-3-methylsulfanyl-1-benzofuran (312 mg, 0.9 mmol) in dichloromethane (40 mL) at 273 K. After being stirred at room temperature for 5h, the mixture was washed with saturated sodium bicarbonate solution and the organic layer was separated, dried over magnesium sulfate, filtered and concentrated at reduced pressure. The residue was purified by column chromatography (hexane/ethyl acetate, 1:1 v/v) to afford the title compound as a colorless solid [yield 68%, m.p. 462–463 K; Rf = 0.53 (hexane/ethyl acetate, 1:1 v/v)]. Single crystals suitable for X-ray diffraction were prepared by slow evaporation of a solution of the title compound in acetone at room temperature.

Refinement top

All H atoms were positioned geometrically and refined using a riding model, with C—H = 0.95 Å for aryl and 0.98 Å for methyl H atoms, and with Uiso(H) = 1.2Ueq(C) for aryl and 1.5Ueq(C) for methyl H atoms. The positions of methyl hydrogens were optimized rotationally.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 2012) 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 with the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are presented as small spheres of arbitrary radius.
5-Bromo-7-methyl-2-(4-methylphenyl)-3-methylsulfinyl-1-benzofuran top
Crystal data top
C17H15BrO2SZ = 2
Mr = 363.26F(000) = 368
Triclinic, P1Dx = 1.607 Mg m3
Hall symbol: -P 1Melting point = 462–463 K
a = 7.6375 (2) ÅMo Kα radiation, λ = 0.71073 Å
b = 9.5170 (2) ÅCell parameters from 6280 reflections
c = 11.2413 (2) Åθ = 2.6–28.3°
α = 75.513 (1)°µ = 2.88 mm1
β = 84.848 (1)°T = 173 K
γ = 71.626 (1)°Block, colourless
V = 750.72 (3) Å30.28 × 0.24 × 0.22 mm
Data collection top
Bruker SMART APEXII CCD
diffractometer
3716 independent reflections
Radiation source: rotating anode3331 reflections with I > 2σ(I)
Graphite multilayer monochromatorRint = 0.040
Detector resolution: 10.0 pixels mm-1θmax = 28.3°, θmin = 1.9°
ϕ and ω scansh = 1010
Absorption correction: multi-scan
(SADABS; Bruker, 2009)
k = 1212
Tmin = 0.504, Tmax = 0.568l = 1414
14012 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)] = 0.028Hydrogen site location: difference Fourier map
wR(F2) = 0.075H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.039P)2 + 0.174P]
where P = (Fo2 + 2Fc2)/3
3716 reflections(Δ/σ)max = 0.002
193 parametersΔρmax = 0.48 e Å3
0 restraintsΔρmin = 0.56 e Å3
Crystal data top
C17H15BrO2Sγ = 71.626 (1)°
Mr = 363.26V = 750.72 (3) Å3
Triclinic, P1Z = 2
a = 7.6375 (2) ÅMo Kα radiation
b = 9.5170 (2) ŵ = 2.88 mm1
c = 11.2413 (2) ÅT = 173 K
α = 75.513 (1)°0.28 × 0.24 × 0.22 mm
β = 84.848 (1)°
Data collection top
Bruker SMART APEXII CCD
diffractometer
3716 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2009)
3331 reflections with I > 2σ(I)
Tmin = 0.504, Tmax = 0.568Rint = 0.040
14012 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0280 restraints
wR(F2) = 0.075H-atom parameters constrained
S = 1.05Δρmax = 0.48 e Å3
3716 reflectionsΔρmin = 0.56 e Å3
193 parameters
Special details top

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) top
xyzUiso*/Ueq
Br11.01640 (2)0.25733 (2)1.044940 (18)0.03262 (8)
S10.65991 (7)0.79517 (5)0.61463 (5)0.03608 (13)
O10.80729 (16)0.39887 (14)0.52060 (12)0.0266 (3)
O20.7824 (3)0.80345 (17)0.70610 (17)0.0516 (4)
C10.7300 (2)0.60520 (19)0.60028 (18)0.0262 (4)
C20.8166 (2)0.47429 (19)0.69618 (17)0.0247 (3)
C30.8598 (2)0.44924 (19)0.81916 (18)0.0270 (4)
H30.83040.53000.86010.032*
C60.9504 (2)0.2018 (2)0.69871 (19)0.0278 (4)
C100.6566 (2)0.6248 (2)0.37333 (17)0.0258 (3)
C40.9481 (2)0.3001 (2)0.87834 (18)0.0265 (4)
C140.6396 (3)0.6087 (2)0.16459 (19)0.0339 (4)
H140.67600.55160.10340.041*
C50.9929 (2)0.1788 (2)0.82077 (18)0.0285 (4)
H51.05350.07870.86610.034*
C80.7269 (2)0.55446 (19)0.49709 (17)0.0251 (3)
C70.8620 (2)0.35210 (19)0.64087 (17)0.0244 (3)
C120.4659 (3)0.8359 (2)0.22513 (19)0.0322 (4)
H120.38370.93680.20610.039*
C130.5173 (2)0.7551 (2)0.13389 (19)0.0315 (4)
C110.5323 (3)0.7721 (2)0.34314 (19)0.0310 (4)
H110.49310.82860.40450.037*
C150.7097 (3)0.5440 (2)0.28117 (19)0.0306 (4)
H150.79430.44410.29900.037*
C160.4439 (3)0.8233 (3)0.0066 (2)0.0401 (5)
H16A0.35790.92550.00270.060*
H16B0.37940.75910.01490.060*
H16C0.54640.83000.05140.060*
C90.9909 (3)0.0770 (2)0.6320 (2)0.0389 (5)
H9A1.03090.02200.69080.058*
H9B1.08900.08620.57080.058*
H9C0.87930.08500.59070.058*
C170.4442 (3)0.7945 (3)0.6906 (2)0.0482 (6)
H17A0.46450.70940.76330.072*
H17B0.36130.78320.63440.072*
H17C0.38840.89060.71580.072*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.04139 (12)0.03114 (11)0.02435 (12)0.01163 (8)0.01237 (8)0.00023 (8)
S10.0551 (3)0.0203 (2)0.0333 (3)0.01144 (19)0.0163 (2)0.00163 (19)
O10.0316 (6)0.0258 (6)0.0205 (7)0.0063 (5)0.0039 (5)0.0037 (5)
O20.0753 (11)0.0340 (8)0.0538 (11)0.0211 (7)0.0298 (9)0.0090 (7)
C10.0327 (8)0.0213 (7)0.0247 (10)0.0096 (6)0.0067 (7)0.0014 (7)
C20.0276 (8)0.0232 (8)0.0234 (10)0.0095 (6)0.0055 (7)0.0016 (7)
C30.0328 (8)0.0251 (8)0.0247 (10)0.0104 (7)0.0067 (7)0.0042 (7)
C60.0272 (8)0.0256 (8)0.0288 (10)0.0046 (6)0.0037 (7)0.0062 (7)
C100.0283 (8)0.0292 (8)0.0202 (9)0.0124 (7)0.0042 (7)0.0004 (7)
C40.0289 (8)0.0295 (8)0.0211 (9)0.0106 (7)0.0076 (7)0.0013 (7)
C140.0405 (10)0.0418 (10)0.0217 (10)0.0152 (8)0.0013 (8)0.0078 (8)
C50.0294 (8)0.0248 (8)0.0283 (10)0.0066 (6)0.0069 (7)0.0008 (7)
C80.0261 (8)0.0243 (8)0.0243 (10)0.0089 (6)0.0033 (7)0.0018 (7)
C70.0260 (8)0.0261 (8)0.0209 (9)0.0081 (6)0.0034 (6)0.0038 (7)
C120.0337 (9)0.0334 (9)0.0261 (11)0.0093 (7)0.0065 (8)0.0000 (8)
C130.0312 (9)0.0429 (10)0.0215 (10)0.0172 (8)0.0055 (7)0.0001 (8)
C110.0362 (9)0.0313 (9)0.0238 (10)0.0088 (7)0.0048 (7)0.0037 (8)
C150.0331 (9)0.0319 (9)0.0256 (10)0.0098 (7)0.0019 (7)0.0042 (8)
C160.0398 (10)0.0549 (13)0.0250 (11)0.0181 (9)0.0075 (8)0.0009 (10)
C90.0461 (11)0.0272 (9)0.0374 (13)0.0001 (8)0.0038 (9)0.0103 (9)
C170.0543 (13)0.0416 (12)0.0459 (15)0.0019 (10)0.0051 (11)0.0202 (11)
Geometric parameters (Å, º) top
Br1—C41.8987 (19)C14—C151.377 (3)
Br1—O2i3.1514 (17)C14—C131.389 (3)
S1—O21.4825 (16)C14—H140.9500
S1—C11.7611 (17)C5—H50.9500
S1—C171.787 (3)C12—C111.382 (3)
O1—C71.372 (2)C12—C131.389 (3)
O1—C81.378 (2)C12—H120.9500
C1—C81.368 (3)C13—C161.494 (3)
C1—C21.445 (2)C11—H110.9500
C2—C71.388 (2)C15—H150.9500
C2—C31.395 (3)C16—H16A0.9800
C3—C41.385 (2)C16—H16B0.9800
C3—H30.9500C16—H16C0.9800
C6—C51.386 (3)C9—H9A0.9800
C6—C71.389 (2)C9—H9B0.9800
C6—C91.497 (3)C9—H9C0.9800
C10—C151.398 (3)C17—H17A0.9800
C10—C111.401 (3)C17—H17B0.9800
C10—C81.454 (3)C17—H17C0.9800
C4—C51.398 (3)
C4—Br1—O2i166.55 (6)O1—C7—C6123.97 (16)
O2—S1—C1106.92 (9)C2—C7—C6124.96 (18)
O2—S1—C17106.93 (12)C11—C12—C13121.09 (18)
C1—S1—C1797.14 (10)C11—C12—H12119.5
C7—O1—C8106.78 (13)C13—C12—H12119.5
C8—C1—C2107.54 (15)C12—C13—C14117.90 (18)
C8—C1—S1127.55 (14)C12—C13—C16121.17 (18)
C2—C1—S1124.74 (14)C14—C13—C16120.94 (19)
C7—C2—C3119.56 (16)C12—C11—C10120.76 (19)
C7—C2—C1104.61 (16)C12—C11—H11119.6
C3—C2—C1135.82 (17)C10—C11—H11119.6
C4—C3—C2116.29 (16)C14—C15—C10120.27 (18)
C4—C3—H3121.9C14—C15—H15119.9
C2—C3—H3121.9C10—C15—H15119.9
C5—C6—C7114.80 (16)C13—C16—H16A109.5
C5—C6—C9124.04 (17)C13—C16—H16B109.5
C7—C6—C9121.14 (18)H16A—C16—H16B109.5
C15—C10—C11118.12 (18)C13—C16—H16C109.5
C15—C10—C8120.06 (16)H16A—C16—H16C109.5
C11—C10—C8121.81 (17)H16B—C16—H16C109.5
C3—C4—C5123.18 (18)C6—C9—H9A109.5
C3—C4—Br1118.81 (14)C6—C9—H9B109.5
C5—C4—Br1118.00 (13)H9A—C9—H9B109.5
C15—C14—C13121.86 (19)C6—C9—H9C109.5
C15—C14—H14119.1H9A—C9—H9C109.5
C13—C14—H14119.1H9B—C9—H9C109.5
C6—C5—C4121.20 (16)S1—C17—H17A109.5
C6—C5—H5119.4S1—C17—H17B109.5
C4—C5—H5119.4H17A—C17—H17B109.5
C1—C8—O1109.99 (15)S1—C17—H17C109.5
C1—C8—C10135.25 (16)H17A—C17—H17C109.5
O1—C8—C10114.74 (15)H17B—C17—H17C109.5
O1—C7—C2111.07 (15)
O2—S1—C1—C8146.49 (17)C15—C10—C8—C1166.89 (19)
C17—S1—C1—C8103.34 (18)C11—C10—C8—C114.6 (3)
O2—S1—C1—C228.10 (19)C15—C10—C8—O114.8 (2)
C17—S1—C1—C282.07 (17)C11—C10—C8—O1163.75 (15)
C8—C1—C2—C70.78 (19)C8—O1—C7—C20.72 (18)
S1—C1—C2—C7174.73 (13)C8—O1—C7—C6179.55 (16)
C8—C1—C2—C3179.73 (19)C3—C2—C7—O1179.48 (14)
S1—C1—C2—C34.8 (3)C1—C2—C7—O10.92 (19)
C7—C2—C3—C40.3 (2)C3—C2—C7—C60.2 (3)
C1—C2—C3—C4179.18 (19)C1—C2—C7—C6179.35 (16)
C2—C3—C4—C50.2 (3)C5—C6—C7—O1179.58 (15)
C2—C3—C4—Br1178.66 (12)C9—C6—C7—O10.8 (3)
O2i—Br1—C4—C392.2 (3)C5—C6—C7—C20.1 (3)
O2i—Br1—C4—C586.6 (3)C9—C6—C7—C2178.91 (18)
C7—C6—C5—C40.0 (3)C11—C12—C13—C140.9 (3)
C9—C6—C5—C4178.76 (18)C11—C12—C13—C16179.26 (18)
C3—C4—C5—C60.0 (3)C15—C14—C13—C120.2 (3)
Br1—C4—C5—C6178.79 (13)C15—C14—C13—C16179.66 (18)
C2—C1—C8—O10.37 (19)C13—C12—C11—C101.4 (3)
S1—C1—C8—O1174.97 (13)C15—C10—C11—C120.8 (3)
C2—C1—C8—C10178.02 (18)C8—C10—C11—C12179.30 (16)
S1—C1—C8—C106.6 (3)C13—C14—C15—C100.8 (3)
C7—O1—C8—C10.20 (18)C11—C10—C15—C140.3 (3)
C7—O1—C8—C10178.95 (14)C8—C10—C15—C14178.27 (16)
Symmetry code: (i) x+2, y+1, z+2.

Experimental details

Crystal data
Chemical formulaC17H15BrO2S
Mr363.26
Crystal system, space groupTriclinic, P1
Temperature (K)173
a, b, c (Å)7.6375 (2), 9.5170 (2), 11.2413 (2)
α, β, γ (°)75.513 (1), 84.848 (1), 71.626 (1)
V3)750.72 (3)
Z2
Radiation typeMo Kα
µ (mm1)2.88
Crystal size (mm)0.28 × 0.24 × 0.22
Data collection
DiffractometerBruker SMART APEXII CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2009)
Tmin, Tmax0.504, 0.568
No. of measured, independent and
observed [I > 2σ(I)] reflections
14012, 3716, 3331
Rint0.040
(sin θ/λ)max1)0.666
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.028, 0.075, 1.05
No. of reflections3716
No. of parameters193
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.48, 0.56

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 2012) and DIAMOND (Brandenburg, 1998).

 

Acknowledgements

This work was supported by the Blue-Bio Industry Regional Innovation Center (RIC08-06-07) at Dongeui University as an RIC program under the Ministry of Knowledge Economy and Busan City.

References

First citationBrandenburg, K. (1998). DIAMOND. Crystal Impact GbR, Bonn, Germany.
First citationBruker (2009). APEX2, SADABS and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
First citationChoi, H. D., Seo, P. J., Son, B. W. & Lee, U. (2010). Acta Cryst. E66, o215.  Web of Science CSD CrossRef IUCr Journals
First citationFarrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854.  Web of Science CrossRef CAS IUCr Journals
First citationPolitzer, P., Lane, P., Concha, M. C., Ma, Y. & Murray, J. S. (2007). J. Mol. Model. 13, 305–311.  Web of Science CrossRef PubMed CAS
First citationSeo, P. J., Choi, H. D., Son, B. W. & Lee, U. (2009). Acta Cryst. E65, o2302.  Web of Science CSD CrossRef IUCr Journals
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals

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