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The title compound, C15H11BrO2S, was prepared by the oxidation of 5-bromo-2-methyl-3-phenyl­sulfanyl-1-benzofuran using 3-chloro­perbenzoic acid. The O atom and the phenyl group of the phenyl­sulfinyl substituent lie on opposite sides of the plane of the benzofuran fragment. The phenyl ring is almost perpendicular to the plane of the benzofuran fragment [84.61 (6)°] and is tilted slightly towards it. The crystal structure is stabilized by inter­molecular aromatic π–π inter­actions, with a centroid–centroid distance of 3.622 (3) Å for the furan and benzene rings, C—H...O hydrogen bonds and a Br...O (π-anti­bondng of S=O to π-non-bonding of Br) inter­action, with a distance of 3.204 (2) Å.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807028504/wk2060sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807028504/wk2060Isup2.hkl
Contains datablock I

CCDC reference: 654948

Key indicators

  • Single-crystal X-ray study
  • T = 173 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.030
  • wR factor = 0.085
  • Data-to-parameter ratio = 17.1

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT431_ALERT_2_C Short Inter HL..A Contact Br .. O2 .. 3.20 Ang.
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 1 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

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

The benzofuran unit is essentially planar, with a mean deviation of 0.008 Å from the least-squares plane defined by the nine constituent atoms. The phenyl ring (C9—C14) is almost perpendicular to the plane of the benzofuran (84.61 (6) degrees and is tilted slightly towards it. The molecular packing (Fig. 2) is stabilized by ππ stacking interactions between adjacent benzofuran units. The Cg1···Cg2 distance is 3.622 (3) Å (Cg1 and Cg2 are of the centroids of the O1/C8/C1/C2/C7 and C2—C7 rings; symmetry code as in Fig. 2). Further stability comes from weak C—H···O hydrogen bond in Table 1, and Br···O2i interaction at 3.204 (2) Å {Symmetry code; (i): x, 1/2 - y, 1/2 - z.}

Related literature top

For the crystal structures of isomers of the title compound, see: Choi et al. (2007a,b).

Experimental top

3-Chloroperbenzoic acid (77%, 291 mg, 1.30 mmol) was added in small portions to a stirred solution of 5-bromo-2-methyl-3-phenylsulfanyl-1-benzofuran (383 mg, 1.20 mmol) in dichloromethane (30 ml) at 273 K. After being stirred at room temperature for 2hrs, the mixture was washed with saturated sodium bicarbonate solution and the organic layer separated, dried over magnesium sulfate, filtered and concentrated in vacuum. The residue was purified by column chromatography (hexane-ethyl acetate, 1:1 v/v) to afford the title compound as a colorless solid [yield 89%, m.p. 413–414 K; Rf = 0.56 (hexane-ethyl acetate, 1:1 v/v)]. Single crystals suitable for X-ray diffraction were prepared by slow evaporation of a dilute solution of title compound (I) in benzene at room temperature.

Refinement top

All H atoms were geometrically located in ideal positions and refined using a riding model, with C—H = 0.93 Å for aromatic H atoms and C—H=0.96 Å for methyl H atoms, and with Uiso(H) = 1.2Ueq(C) for aromatic H atoms, and Uiso(H) = 1.5Ueq(C) for methyl H atoms. The highest peak in the difference map is 0.74 Å from Br and the largest hole is 0.75 Å from Br.

Structure description top

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

The benzofuran unit is essentially planar, with a mean deviation of 0.008 Å from the least-squares plane defined by the nine constituent atoms. The phenyl ring (C9—C14) is almost perpendicular to the plane of the benzofuran (84.61 (6) degrees and is tilted slightly towards it. The molecular packing (Fig. 2) is stabilized by ππ stacking interactions between adjacent benzofuran units. The Cg1···Cg2 distance is 3.622 (3) Å (Cg1 and Cg2 are of the centroids of the O1/C8/C1/C2/C7 and C2—C7 rings; symmetry code as in Fig. 2). Further stability comes from weak C—H···O hydrogen bond in Table 1, and Br···O2i interaction at 3.204 (2) Å {Symmetry code; (i): x, 1/2 - y, 1/2 - z.}

For the crystal structures of isomers of the title compound, see: Choi et al. (2007a,b).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 1998); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing displacement ellipsoides drawn at the 50% probability level.
[Figure 2] Fig. 2. ππ stacking interactions (dotted lines) in (I). Cg denotes the ring centroid. [Symmetry code: (i) 1 - x, 1 - y, -z.]
5-Bromo-2-methyl-3-phenylsulfinyl-1-benzofuran top
Crystal data top
C15H11BrO2SF(000) = 672
Mr = 335.21Dx = 1.633 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -p_2ybcCell parameters from 4433 reflections
a = 12.8097 (7) Åθ = 2.5–28.1°
b = 11.1838 (6) ŵ = 3.16 mm1
c = 9.9046 (5) ÅT = 173 K
β = 106.084 (1)°Block, colorless
V = 1363.40 (13) Å30.42 × 0.40 × 0.12 mm
Z = 4
Data collection top
Bruker SMART CCD
diffractometer
2964 independent reflections
Radiation source: fine-focus sealed tube2534 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.020
Detector resolution: 10.00 pixels mm-1θmax = 27.0°, θmin = 2.5°
φ and ω scansh = 1216
Absorption correction: multi-scan
(SADABS; Sheldrick, 1999)
k = 1413
Tmin = 0.275, Tmax = 0.692l = 1211
8012 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)] = 0.030Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.085H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0451P)2 + 0.7554P]
where P = (Fo2 + 2Fc2)/3
2964 reflections(Δ/σ)max < 0.001
173 parametersΔρmax = 0.66 e Å3
0 restraintsΔρmin = 0.89 e Å3
Crystal data top
C15H11BrO2SV = 1363.40 (13) Å3
Mr = 335.21Z = 4
Monoclinic, P21/cMo Kα radiation
a = 12.8097 (7) ŵ = 3.16 mm1
b = 11.1838 (6) ÅT = 173 K
c = 9.9046 (5) Å0.42 × 0.40 × 0.12 mm
β = 106.084 (1)°
Data collection top
Bruker SMART CCD
diffractometer
2964 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1999)
2534 reflections with I > 2σ(I)
Tmin = 0.275, Tmax = 0.692Rint = 0.020
8012 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0300 restraints
wR(F2) = 0.085H-atom parameters constrained
S = 1.05Δρmax = 0.66 e Å3
2964 reflectionsΔρmin = 0.89 e Å3
173 parameters
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
Br0.28113 (2)0.16625 (2)0.03045 (3)0.04675 (11)
S0.20038 (4)0.67420 (5)0.27287 (5)0.02839 (13)
O10.43606 (12)0.67227 (13)0.07797 (15)0.0301 (3)
O20.21425 (14)0.59407 (16)0.38714 (16)0.0400 (4)
C10.29805 (16)0.63812 (19)0.1152 (2)0.0257 (4)
C20.32238 (15)0.52620 (18)0.0398 (2)0.0245 (4)
C30.28368 (16)0.40820 (18)0.0591 (2)0.0275 (4)
H30.22700.38540.13930.033*
C40.33223 (19)0.32668 (18)0.0444 (2)0.0315 (5)
C50.41681 (19)0.3558 (2)0.1623 (2)0.0337 (5)
H50.44660.29630.23050.040*
C60.45763 (18)0.4713 (2)0.1802 (2)0.0317 (5)
H60.51650.49290.25830.038*
C70.40803 (16)0.55317 (19)0.0783 (2)0.0268 (4)
C80.36849 (17)0.72134 (19)0.0416 (2)0.0275 (4)
C90.08227 (16)0.62234 (19)0.2262 (2)0.0270 (4)
C100.02089 (18)0.5314 (2)0.3034 (2)0.0351 (5)
H100.04390.49240.37540.042*
C110.0750 (2)0.4979 (3)0.2743 (3)0.0456 (6)
H110.11820.43570.32700.055*
C120.10762 (19)0.5542 (3)0.1696 (3)0.0462 (6)
H120.17340.53080.15040.055*
C130.0453 (2)0.6448 (3)0.0920 (3)0.0443 (6)
H130.06800.68260.01910.053*
C140.05024 (19)0.6807 (2)0.1201 (2)0.0359 (5)
H140.09280.74370.06820.043*
C150.3859 (2)0.84977 (19)0.0639 (3)0.0354 (5)
H15A0.34550.87230.15970.053*
H15B0.46360.86460.05030.053*
H15C0.36030.89740.00360.053*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br0.04578 (17)0.02535 (14)0.0674 (2)0.00332 (9)0.01274 (13)0.00219 (10)
S0.0311 (3)0.0303 (3)0.0241 (2)0.0034 (2)0.0083 (2)0.00379 (19)
O10.0279 (8)0.0317 (8)0.0296 (7)0.0025 (6)0.0062 (6)0.0040 (6)
O20.0448 (9)0.0505 (10)0.0284 (8)0.0034 (8)0.0161 (7)0.0036 (7)
C10.0240 (9)0.0288 (10)0.0257 (10)0.0017 (8)0.0091 (8)0.0021 (8)
C20.0217 (9)0.0289 (10)0.0243 (9)0.0035 (8)0.0086 (7)0.0001 (8)
C30.0244 (10)0.0287 (10)0.0297 (10)0.0015 (8)0.0078 (8)0.0021 (8)
C40.0317 (11)0.0258 (10)0.0391 (12)0.0048 (8)0.0131 (9)0.0014 (8)
C50.0357 (12)0.0335 (11)0.0315 (11)0.0122 (9)0.0086 (9)0.0041 (9)
C60.0299 (11)0.0385 (12)0.0251 (10)0.0070 (9)0.0049 (8)0.0021 (8)
C70.0245 (10)0.0297 (10)0.0274 (10)0.0006 (8)0.0091 (8)0.0041 (8)
C80.0262 (10)0.0315 (10)0.0278 (10)0.0012 (8)0.0126 (8)0.0004 (8)
C90.0251 (10)0.0306 (10)0.0235 (9)0.0069 (8)0.0039 (7)0.0033 (8)
C100.0325 (11)0.0388 (12)0.0324 (11)0.0030 (9)0.0064 (9)0.0075 (9)
C110.0321 (12)0.0494 (14)0.0525 (15)0.0054 (11)0.0068 (11)0.0071 (12)
C120.0269 (11)0.0633 (17)0.0490 (14)0.0002 (11)0.0115 (10)0.0019 (13)
C130.0363 (13)0.0616 (16)0.0379 (13)0.0083 (12)0.0149 (10)0.0040 (12)
C140.0333 (12)0.0424 (13)0.0305 (11)0.0034 (9)0.0065 (9)0.0061 (9)
C150.0391 (12)0.0295 (11)0.0416 (12)0.0029 (9)0.0179 (10)0.0002 (9)
Geometric parameters (Å, º) top
Br—C41.902 (2)C6—H60.9500
Br—O2i3.204 (2)C8—C151.480 (3)
S—O21.492 (2)C9—C101.380 (3)
S—C11.756 (2)C9—C141.391 (3)
S—C91.796 (2)C10—C111.389 (3)
O1—C81.373 (3)C10—H100.9500
O1—C71.380 (2)C11—C121.373 (4)
C1—C81.359 (3)C11—H110.9500
C1—C21.447 (3)C12—C131.384 (4)
C2—C71.397 (3)C12—H120.9500
C2—C31.404 (3)C13—C141.387 (4)
C3—C41.385 (3)C13—H130.9500
C3—H30.9500C14—H140.9500
C4—C51.393 (3)C15—H15A0.9800
C5—C61.387 (3)C15—H15B0.9800
C5—H50.9500C15—H15C0.9800
C6—C71.380 (3)
O2—S—C1109.34 (10)C1—C8—C15133.6 (2)
O2—S—C9106.69 (10)O1—C8—C15115.56 (19)
C1—S—C998.07 (9)C10—C9—C14121.5 (2)
C8—O1—C7106.61 (16)C10—C9—S119.09 (16)
C8—C1—C2107.41 (17)C14—C9—S119.24 (17)
C8—C1—S121.56 (16)C9—C10—C11119.0 (2)
C2—C1—S131.03 (16)C9—C10—H10120.5
C7—C2—C3118.86 (19)C11—C10—H10120.5
C7—C2—C1104.62 (18)C12—C11—C10120.3 (2)
C3—C2—C1136.51 (18)C12—C11—H11119.8
C4—C3—C2116.67 (19)C10—C11—H11119.8
C4—C3—H3121.7C11—C12—C13120.4 (2)
C2—C3—H3121.7C11—C12—H12119.8
C3—C4—C5123.5 (2)C13—C12—H12119.8
C3—C4—Br119.49 (17)C12—C13—C14120.4 (2)
C5—C4—Br116.97 (17)C12—C13—H13119.8
C6—C5—C4120.2 (2)C14—C13—H13119.8
C6—C5—H5119.9C13—C14—C9118.5 (2)
C4—C5—H5119.9C13—C14—H14120.8
C7—C6—C5116.33 (19)C9—C14—H14120.8
C7—C6—H6121.8C8—C15—H15A109.5
C5—C6—H6121.8C8—C15—H15B109.5
O1—C7—C6125.09 (19)H15A—C15—H15B109.5
O1—C7—C2110.53 (18)C8—C15—H15C109.5
C6—C7—C2124.4 (2)H15A—C15—H15C109.5
C1—C8—O1110.82 (18)H15B—C15—H15C109.5
O2—S—C1—C8123.53 (18)C3—C2—C7—C60.7 (3)
C9—S—C1—C8125.54 (18)C1—C2—C7—C6179.76 (19)
O2—S—C1—C255.9 (2)C2—C1—C8—O11.0 (2)
C9—S—C1—C255.0 (2)S—C1—C8—O1179.47 (14)
C8—C1—C2—C70.7 (2)C2—C1—C8—C15179.1 (2)
S—C1—C2—C7179.84 (16)S—C1—C8—C150.4 (3)
C8—C1—C2—C3178.1 (2)C7—O1—C8—C10.9 (2)
S—C1—C2—C31.4 (4)C7—O1—C8—C15179.20 (18)
C7—C2—C3—C41.8 (3)O2—S—C9—C105.4 (2)
C1—C2—C3—C4179.6 (2)C1—S—C9—C10118.41 (18)
C2—C3—C4—C51.2 (3)O2—S—C9—C14179.50 (17)
C2—C3—C4—Br177.61 (15)C1—S—C9—C1466.44 (19)
C3—C4—C5—C60.6 (4)C14—C9—C10—C110.1 (3)
Br—C4—C5—C6179.43 (17)S—C9—C10—C11174.97 (19)
C4—C5—C6—C71.7 (3)C9—C10—C11—C120.3 (4)
C8—O1—C7—C6179.18 (19)C10—C11—C12—C130.1 (4)
C8—O1—C7—C20.4 (2)C11—C12—C13—C140.7 (4)
C5—C6—C7—O1179.39 (19)C12—C13—C14—C91.0 (4)
C5—C6—C7—C21.0 (3)C10—C9—C14—C130.6 (3)
C3—C2—C7—O1178.89 (17)S—C9—C14—C13175.62 (18)
C1—C2—C7—O10.1 (2)
Symmetry code: (i) x, y+1/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C5—H5···O1ii0.952.493.420 (3)166
Symmetry code: (ii) x+1, y1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC15H11BrO2S
Mr335.21
Crystal system, space groupMonoclinic, P21/c
Temperature (K)173
a, b, c (Å)12.8097 (7), 11.1838 (6), 9.9046 (5)
β (°) 106.084 (1)
V3)1363.40 (13)
Z4
Radiation typeMo Kα
µ (mm1)3.16
Crystal size (mm)0.42 × 0.40 × 0.12
Data collection
DiffractometerBruker SMART CCD
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1999)
Tmin, Tmax0.275, 0.692
No. of measured, independent and
observed [I > 2σ(I)] reflections
8012, 2964, 2534
Rint0.020
(sin θ/λ)max1)0.639
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.030, 0.085, 1.05
No. of reflections2964
No. of parameters173
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.66, 0.89

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 1998), SHELXL97.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C5—H5···O1i0.952.493.420 (3)166.1
Symmetry code: (i) x+1, y1/2, z+1/2.
 

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