2-(4-Bromo­phen­yl)-5-methyl-3-methyl­sulfinyl-1-benzofuran

The title compound, C₁₆H₁₃BrO₂S, was prepared by the oxidation of 2-(4-bromo­phen­yl)-5-methyl-3-methyl­sulfanyl-1-benzofuran using 3-chloro­perbenzoic acid. The O atom and the methyl group of the methyl­sulfinyl substituent lie on opposite sides of the plane of the benzofuran fragment. The 4-bromo­phenyl ring is rotated out of the benzofuran plane with a dihedral angle of 26.21 (5)°. The crystal structure contains aromatic π–π inter­actions, with a centroid–centroid distance of 3.857 (2) Å between furan rings of neighboring mol­ecules, and close CH₂—H...π contacts between the methyl­sulfinyl group and the aromatic system of the 4-bromo­phenyl ring.

Key indicators

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.020
• wR factor = 0.056
• Data-to-parameter ratio = 14.8

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S1. Comment

This work is related to preceding communications on the synthesis and structure of 5-methyl-3-methylsulfinyl-1-benzofuran analogues (Choi et al., 2007a,b). 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 0.010 Å from the least-squares plane defined by the nine constituent atoms. The dihedral angle in (I) between the planes of the benzofuran and the 4-bromophenyl rings is 26.21 (5)°. The molecular packing (Fig. 2) is stabilized by π···π stacking interactions between adjacent furan units and the Cg1···Cg1ⁱⁱ distance is 3.857 (2) Å. The molecular packing is further stabilized by CH₂—H···π interactions between the 3-methyl group and the 4-bromophenyl ring, with a C16—H16B···Cg2ⁱ separation of 3.50 Å. (Fig. 2 and hydrogen bonding table) (Cg1 and Cg2 are of the centroids of the O1/C8/C1/C2/C7 furan ring and the C9—C14 benzene ring, respectively; symmetry code as in Fig. 2).

Related literature

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

S2. Experimental

3-Chloroperbenzoic acid (77%, 247 mg, 1.10 mmol) was added in small portions to a stirred solution of 2-(4-bromophenyl)-5-methyl-3-methylsulfanyl-1-benzofuran (331 mg, 1.0 mmol) in dichloromethane (30 ml) at 273 K. After being stirred at room temperature for 2 h, 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, 1:1 v/v) to afford the title compound as a colorless solid [yield 82%, m.p. 454–455 K; R_f = 0.31 (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 tetrahydrofuran at room temperature.

S3. 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 C—H = 0.98 Å for methyl H atoms, and with U_iso(H) = 1.2Ueq(C) for aromatic H atoms, and U_iso(H) = 1.5Ueq(C) for methyl H atoms. The highest peak in the difference map is 1.16 Å from S and the largest hole is 0.58 Å from the S atom.

Computing details

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

	Fig. 1. The molecular structure of (I), showing displacement ellipsoides drawn at the 50% probability level.
	Fig. 2. π···π and CH2—H···π interactions (dotted lines) in (I). Cg denotes the ring centroids. [Symmetry code: (i) 1 - x, 1 - y, 1 - z; (ii) 2 - x, 1 - y, 1 - z; (iii) 1 + x, y, z.]

2-(4-Bromophenyl)-5-methyl-3-methylsulfinyl-1-benzofuran

Crystal data

C16H13BrO2S	Z = 2
Mr = 349.23	F(000) = 352
Triclinic, P1	Dx = 1.651 Mg m^−3
Hall symbol: -p 1	Melting point: 455 K
a = 7.9693 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.2016 (5) Å	Cell parameters from 4752 reflections
c = 12.1816 (8) Å	θ = 2.7–28.3°
α = 77.634 (1)°	µ = 3.07 mm^−1
β = 72.344 (1)°	T = 173 K
γ = 68.777 (1)°	Block, colorless
V = 702.34 (8) Å^3	0.40 × 0.40 × 0.10 mm

Data collection

Bruker SMART CCD diffractometer	2707 independent reflections
Radiation source: fine-focus sealed tube	2576 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.014
Detector resolution: 10.00 pixels mm^-1	θmax = 26.0°, θmin = 1.8°
φ and ω scans	h = −9→9
Absorption correction: multi-scan (SADABS; Sheldrick, 1999)	k = −10→10
Tmin = 0.297, Tmax = 0.730	l = −15→15
5542 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.020	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.056	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.031P)^2 + 0.2818P] where P = (Fo^2 + 2Fc^2)/3
2707 reflections	(Δ/σ)max < 0.001
183 parameters	Δρmax = 0.27 e Å^−3
0 restraints	Δρmin = −0.33 e Å^−3

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 (Ų)

	x	y	z	Uiso*/Ueq
Br	0.67916 (2)	0.76665 (2)	−0.014702 (14)	0.02974 (7)
S	0.62961 (6)	0.79742 (5)	0.59939 (4)	0.02538 (10)
O1	0.84540 (16)	0.31832 (15)	0.49907 (10)	0.0242 (3)
O2	0.71676 (19)	0.82196 (18)	0.68449 (13)	0.0371 (3)
C1	0.7157 (2)	0.5700 (2)	0.58281 (15)	0.0228 (3)
C2	0.7688 (2)	0.4268 (2)	0.67133 (15)	0.0229 (3)
C3	0.7545 (2)	0.4103 (2)	0.79027 (15)	0.0261 (4)
H3	0.6988	0.5109	0.8312	0.031*
C4	0.8235 (2)	0.2437 (3)	0.84743 (15)	0.0278 (4)
C5	0.9052 (3)	0.0964 (2)	0.78581 (16)	0.0296 (4)
H5	0.9525	−0.0162	0.8262	0.036*
C6	0.9195 (2)	0.1090 (2)	0.66804 (16)	0.0277 (4)
H6	0.9742	0.0086	0.6270	0.033*
C7	0.8495 (2)	0.2764 (2)	0.61426 (15)	0.0237 (3)
C8	0.7634 (2)	0.4992 (2)	0.48187 (15)	0.0227 (3)
C9	0.7438 (2)	0.5682 (2)	0.36426 (14)	0.0221 (3)
C10	0.8668 (2)	0.4757 (2)	0.27141 (15)	0.0238 (3)
H10	0.9648	0.3717	0.2854	0.029*
C11	0.8462 (2)	0.5348 (2)	0.16032 (15)	0.0251 (4)
H11	0.9288	0.4711	0.0978	0.030*
C12	0.7041 (2)	0.6881 (2)	0.13980 (15)	0.0230 (3)
C13	0.5815 (2)	0.7830 (2)	0.22925 (16)	0.0259 (4)
H13	0.4858	0.8884	0.2142	0.031*
C14	0.6013 (2)	0.7212 (2)	0.34139 (16)	0.0262 (4)
H14	0.5165	0.7840	0.4037	0.031*
C15	0.8122 (3)	0.2222 (3)	0.97538 (17)	0.0355 (4)
H15A	0.9345	0.2053	0.9864	0.053*
H15B	0.7729	0.1194	1.0137	0.053*
H15C	0.7219	0.3279	1.0092	0.053*
C16	0.3960 (3)	0.8089 (3)	0.67703 (19)	0.0355 (4)
H16A	0.3976	0.7243	0.7473	0.053*
H16B	0.3358	0.7806	0.6277	0.053*
H16C	0.3268	0.9282	0.6985	0.053*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br	0.03109 (11)	0.02932 (11)	0.02304 (11)	−0.00261 (8)	−0.00838 (7)	−0.00132 (7)
S	0.0259 (2)	0.0197 (2)	0.0294 (2)	−0.00610 (17)	−0.00501 (17)	−0.00528 (16)
O1	0.0280 (6)	0.0201 (6)	0.0225 (6)	−0.0053 (5)	−0.0061 (5)	−0.0028 (5)
O2	0.0359 (7)	0.0311 (7)	0.0504 (9)	−0.0064 (6)	−0.0166 (6)	−0.0162 (6)
C1	0.0236 (8)	0.0201 (8)	0.0242 (8)	−0.0060 (6)	−0.0061 (7)	−0.0032 (6)
C2	0.0230 (8)	0.0224 (8)	0.0247 (9)	−0.0088 (7)	−0.0060 (7)	−0.0026 (7)
C3	0.0283 (9)	0.0278 (9)	0.0250 (9)	−0.0109 (7)	−0.0072 (7)	−0.0045 (7)
C4	0.0283 (9)	0.0346 (10)	0.0240 (9)	−0.0142 (7)	−0.0093 (7)	0.0009 (7)
C5	0.0287 (9)	0.0270 (9)	0.0319 (10)	−0.0090 (7)	−0.0108 (8)	0.0042 (7)
C6	0.0281 (9)	0.0236 (9)	0.0300 (9)	−0.0064 (7)	−0.0070 (7)	−0.0035 (7)
C7	0.0236 (8)	0.0262 (9)	0.0219 (8)	−0.0088 (7)	−0.0052 (7)	−0.0032 (7)
C8	0.0214 (8)	0.0200 (8)	0.0251 (9)	−0.0055 (6)	−0.0051 (7)	−0.0023 (6)
C9	0.0226 (8)	0.0227 (8)	0.0221 (8)	−0.0092 (7)	−0.0043 (6)	−0.0032 (6)
C10	0.0204 (8)	0.0206 (8)	0.0265 (9)	−0.0039 (6)	−0.0035 (7)	−0.0027 (7)
C11	0.0231 (8)	0.0245 (9)	0.0226 (8)	−0.0052 (7)	−0.0001 (7)	−0.0048 (7)
C12	0.0232 (8)	0.0239 (8)	0.0223 (8)	−0.0085 (7)	−0.0060 (6)	−0.0009 (6)
C13	0.0218 (8)	0.0246 (9)	0.0288 (9)	−0.0023 (7)	−0.0077 (7)	−0.0050 (7)
C14	0.0232 (8)	0.0265 (9)	0.0262 (9)	−0.0041 (7)	−0.0037 (7)	−0.0079 (7)
C15	0.0424 (11)	0.0398 (11)	0.0275 (10)	−0.0151 (9)	−0.0149 (8)	0.0020 (8)
C16	0.0260 (9)	0.0343 (10)	0.0437 (11)	−0.0071 (8)	−0.0022 (8)	−0.0133 (9)

Geometric parameters (Å, º)

Br—C12	1.900 (2)	C8—C9	1.457 (2)
S—O2	1.492 (1)	C9—C14	1.398 (2)
S—C1	1.773 (2)	C9—C10	1.404 (2)
S—C16	1.793 (2)	C10—C11	1.375 (2)
O1—C7	1.379 (2)	C10—H10	0.9500
O1—C8	1.385 (2)	C11—C12	1.390 (2)
C1—C8	1.362 (2)	C11—H11	0.9500
C1—C2	1.447 (2)	C12—C13	1.384 (2)
C2—C7	1.393 (2)	C13—C14	1.387 (3)
C2—C3	1.399 (2)	C13—H13	0.9500
C3—C4	1.391 (3)	C14—H14	0.9500
C3—H3	0.9500	C15—H15A	0.9800
C4—C5	1.403 (3)	C15—H15B	0.9800
C4—C15	1.509 (2)	C15—H15C	0.9800
C5—C6	1.388 (3)	C16—H16A	0.9800
C5—H5	0.9500	C16—H16B	0.9800
C6—C7	1.381 (2)	C16—H16C	0.9800
C6—H6	0.9500
O2—S—C1	107.10 (8)	C14—C9—C8	121.74 (15)
O2—S—C16	105.85 (9)	C10—C9—C8	119.43 (15)
C1—S—C16	97.86 (9)	C11—C10—C9	120.35 (15)
C7—O1—C8	106.59 (13)	C11—C10—H10	119.8
C8—C1—C2	107.47 (15)	C9—C10—H10	119.8
C8—C1—S	126.27 (13)	C10—C11—C12	119.72 (15)
C2—C1—S	125.88 (13)	C10—C11—H11	120.1
C7—C2—C3	119.17 (16)	C12—C11—H11	120.1
C7—C2—C1	104.94 (15)	C13—C12—C11	121.34 (16)
C3—C2—C1	135.89 (16)	C13—C12—Br	119.91 (13)
C4—C3—C2	118.69 (16)	C11—C12—Br	118.76 (13)
C4—C3—H3	120.7	C12—C13—C14	118.67 (16)
C2—C3—H3	120.7	C12—C13—H13	120.7
C3—C4—C5	119.98 (16)	C14—C13—H13	120.7
C3—C4—C15	119.86 (17)	C13—C14—C9	121.12 (16)
C5—C4—C15	120.16 (17)	C13—C14—H14	119.4
C6—C5—C4	122.46 (17)	C9—C14—H14	119.4
C6—C5—H5	118.8	C4—C15—H15A	109.5
C4—C5—H5	118.8	C4—C15—H15B	109.5
C7—C6—C5	115.92 (16)	H15A—C15—H15B	109.5
C7—C6—H6	122.0	C4—C15—H15C	109.5
C5—C6—H6	122.0	H15A—C15—H15C	109.5
O1—C7—C6	125.55 (15)	H15B—C15—H15C	109.5
O1—C7—C2	110.66 (15)	S—C16—H16A	109.5
C6—C7—C2	123.78 (16)	S—C16—H16B	109.5
C1—C8—O1	110.33 (15)	H16A—C16—H16B	109.5
C1—C8—C9	135.14 (16)	S—C16—H16C	109.5
O1—C8—C9	114.51 (14)	H16A—C16—H16C	109.5
C14—C9—C10	118.78 (16)	H16B—C16—H16C	109.5
O2—S—C1—C8	−140.78 (16)	C1—C2—C7—C6	−179.89 (16)
C16—S—C1—C8	109.89 (17)	C2—C1—C8—O1	−0.28 (19)
O2—S—C1—C2	31.28 (17)	S—C1—C8—O1	172.99 (12)
C16—S—C1—C2	−78.04 (16)	C2—C1—C8—C9	177.77 (18)
C8—C1—C2—C7	0.86 (18)	S—C1—C8—C9	−9.0 (3)
S—C1—C2—C7	−172.44 (13)	C7—O1—C8—C1	−0.43 (18)
C8—C1—C2—C3	−178.08 (19)	C7—O1—C8—C9	−178.91 (14)
S—C1—C2—C3	8.6 (3)	C1—C8—C9—C14	−26.6 (3)
C7—C2—C3—C4	0.7 (2)	O1—C8—C9—C14	151.41 (16)
C1—C2—C3—C4	179.51 (18)	C1—C8—C9—C10	155.75 (19)
C2—C3—C4—C5	−0.1 (3)	O1—C8—C9—C10	−26.3 (2)
C2—C3—C4—C15	179.24 (16)	C14—C9—C10—C11	−0.3 (3)
C3—C4—C5—C6	−0.5 (3)	C8—C9—C10—C11	177.44 (15)
C15—C4—C5—C6	−179.85 (17)	C9—C10—C11—C12	0.8 (3)
C4—C5—C6—C7	0.5 (3)	C10—C11—C12—C13	−0.2 (3)
C8—O1—C7—C6	179.72 (17)	C10—C11—C12—Br	179.97 (13)
C8—O1—C7—C2	1.00 (18)	C11—C12—C13—C14	−0.7 (3)
C5—C6—C7—O1	−178.41 (16)	Br—C12—C13—C14	179.05 (13)
C5—C6—C7—C2	0.1 (3)	C12—C13—C14—C9	1.2 (3)
C3—C2—C7—O1	178.01 (14)	C10—C9—C14—C13	−0.7 (3)
C1—C2—C7—O1	−1.15 (18)	C8—C9—C14—C13	−178.39 (16)
C3—C2—C7—C6	−0.7 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C16—H16B···Cg2^i	0.98	3.50	3.896 (2)	107

Symmetry code: (i) −x+1, −y+1, −z+1.