5-Bromo-2-methyl-3-phenyl­sulfonyl-1-benzofuran

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

doi:10.1107/S1600536808008489

5-Bromo-2-methyl-3-phenylsulfonyl-1-benzofuran

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

The title compound, C₁₅H₁₁BrO₃S, was prepared by the oxidation of 5-bromo-2-methyl-3-phenylsulfanyl-1-benzofuran with 3-chloroperoxybenzoic acid. The phenyl ring makes a dihedral angle of 78.99 (8)° with the plane of the benzofuran fragment. The crystal structure is stabilized by C—H

π interactions between a benzene H atom of the benzofuran unit and the phenyl ring of the phenylsulfonyl substituent from a neighbouring molecule. In addition, the crystal structure exhibits intra- and intermolecular C—H

O interactions.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536808008489/cf2191sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536808008489/cf2191Isup2.hkl Contains datablock I

CCDC reference: 688893

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Key indicators

Single-crystal X-ray study
T = 173 K
Mean (C-C)= 0.004 Å
R factor = 0.033
wR factor = 0.087
Data-to-parameter ratio = 16.5

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No errors found in this datablock

Comment top

This work is related to earlier communications on the synthesis and structure of 5-bromo-2-methyl-1-benzofuran analogues, viz. 5-bromo-2-methyl-3-methylsulfinyl-1-benzofuran (Choi et al., 2007) and 5-bromo-2-methyl-3-phenylsulfinyl-1-benzofuran (Seo et al., 2007). Here we report the crystal structure of the title compound, 5-bromo-2-methyl-3-phenylsulfonyl-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 phenyl ring (C9–C14) makes a dihedral angle of 78.99 (8)° with the plane of the benzofuran fragment. The crystal packing (Fig. 2) is stabilized by intermolecular C—H···π interactions between a benzene H atom of the benzofuran unit and the phenyl ring of the phenylsulfonyl substituent from an adjacent molecule, with a C6—H6···Cgⁱ separation of 2.74 Å (Fig. 2; Cg is the centroid of the C9–C14 phenyl ring, symmetry code as in Fig. 2). Additionally, intra- and intermolecular C—H···O interactions in the structure are observed (Fig. 2).

Related literature top

For the crystal structures of similar 5-bromo-2-methyl-1-benzofuran derivatives, see: Choi et al. (2007); Seo et al. (2007).

Experimental top

3-Chloroperoxybenzoic acid (77%, 336 mg, 1.5 mmol) was added in small portions to a stirred solution of 5-bromo-2-methyl-3-phenylsulfonyl-1-benzofuran (223 mg, 0.7 mmol) in dichloromethane (30 ml) at 273 K. After being stirred for 4 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, 2:1 v/v) to afford the title compound as a colorless solid [yield 78%, m.p. 464–465 K; Rf = 0.59 (hexane-ethyl acetate, 2:1 v/v)]. Single crystals suitable for X-ray diffraction were prepared by evaporation of a solution of the title compound in chloroform at room temperature. Spectroscopic analysis: ¹H NMR (CDCl₃, 400 MHz) δ 2.80 (s, 3H), 7.29 (d, J = 8.44 Hz, 1H), 7.41 (dd, J = 8.44 Hz and J = 1.84 Hz, 1H), 7.51–7.56 (m, 2H), 7.58–7.61 (m, 1H), 7.98–8.02 (m, 2H), 8.05 (d, J = 2.20 Hz, 1H); EI—MS 352 [M+2], 350 [M⁺].

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

	Fig. 1. The molecular structure of the title compound, showing displacement ellipsoides drawn at the 50% probability level.
	Fig. 2. C—H···π and C—H···O interactions (dotted lines) in the title compound. Cg denotes the ring centroid. [Symmetry code: (i) -x + 2, -y + 1, -z; (ii) -x + 3/2, y - 1/2, -z + 1/2; (iii) -x + 3/2, y + 1/2, -z + 1/2.]

5-Bromo-2-methyl-3-phenylsulfonyl-1-benzofuran top

Crystal data top

C₁₅H₁₁BrO₃S	F(000) = 704
M_r = 351.21	D_x = 1.693 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P_2yn	Cell parameters from 3065 reflections
a = 7.337 (1) Å	θ = 2.5–27.7°
b = 11.345 (1) Å	µ = 3.14 mm⁻¹
c = 16.602 (2) Å	T = 173 K
β = 94.582 (3)°	Block, colorless
V = 1377.5 (3) Å³	0.30 × 0.20 × 0.20 mm
Z = 4

Data collection top

Bruker SMART CCD diffractometer	3009 independent reflections
Radiation source: fine-focus sealed tube	2349 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
Detector resolution: 10.0 pixels mm^-1	θ_max = 27.0°, θ_min = 2.5°
ϕ and ω scans	h = −9→9
Absorption correction: multi-scan (SADABS; Sheldrick, 1999)	k = −14→13
T_min = 0.463, T_max = 0.542	l = −14→21
8005 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.033	Hydrogen site location: difference Fourier map
wR(F²) = 0.086	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0401P)² + 0.6448P] where P = (F_o² + 2F_c²)/3
3009 reflections	(Δ/σ)_max < 0.001
182 parameters	Δρ_max = 0.55 e Å⁻³
0 restraints	Δρ_min = −0.44 e Å⁻³

Crystal data top

C₁₅H₁₁BrO₃S	V = 1377.5 (3) Å³
M_r = 351.21	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.337 (1) Å	µ = 3.14 mm⁻¹
b = 11.345 (1) Å	T = 173 K
c = 16.602 (2) Å	0.30 × 0.20 × 0.20 mm
β = 94.582 (3)°

Data collection top

Bruker SMART CCD diffractometer	3009 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1999)	2349 reflections with I > 2σ(I)
T_min = 0.463, T_max = 0.542	R_int = 0.033
8005 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.086	H-atom parameters constrained
S = 1.03	Δρ_max = 0.55 e Å⁻³
3009 reflections	Δρ_min = −0.44 e Å⁻³
182 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

	x	y	z	U_iso*/U_eq
Br	0.79772 (5)	0.88457 (2)	0.038216 (19)	0.03963 (12)
S	0.65781 (9)	0.40138 (5)	0.19581 (4)	0.02489 (16)
O1	0.7486 (3)	0.36914 (16)	−0.03375 (11)	0.0296 (4)
O2	0.5677 (3)	0.50746 (16)	0.21839 (12)	0.0327 (5)
O3	0.5740 (3)	0.28903 (15)	0.20838 (12)	0.0344 (5)
C1	0.6960 (4)	0.4145 (2)	0.09406 (16)	0.0242 (5)
C2	0.7309 (3)	0.5236 (2)	0.05267 (15)	0.0227 (5)
C3	0.7410 (4)	0.6429 (2)	0.07353 (16)	0.0255 (5)
H3	0.7209	0.6693	0.1264	0.031*
C4	0.7819 (4)	0.7208 (2)	0.01307 (17)	0.0287 (6)
C5	0.8107 (4)	0.6854 (2)	−0.06521 (16)	0.0305 (6)
H5	0.8372	0.7425	−0.1045	0.037*
C6	0.8010 (4)	0.5675 (3)	−0.08587 (16)	0.0308 (6)
H6	0.8198	0.5412	−0.1389	0.037*
C7	0.7626 (3)	0.4899 (2)	−0.02563 (16)	0.0245 (5)
C8	0.7097 (4)	0.3254 (2)	0.03977 (16)	0.0271 (6)
C9	0.8786 (4)	0.3998 (2)	0.24546 (16)	0.0259 (6)
C10	0.9716 (4)	0.2932 (2)	0.25599 (16)	0.0321 (6)
H10	0.9160	0.2218	0.2368	0.039*
C11	1.1457 (5)	0.2921 (3)	0.29469 (19)	0.0446 (8)
H11	1.2105	0.2200	0.3024	0.054*
C12	1.2249 (5)	0.3974 (3)	0.32221 (19)	0.0506 (9)
H12	1.3445	0.3969	0.3488	0.061*
C13	1.1314 (5)	0.5031 (3)	0.31132 (19)	0.0467 (8)
H13	1.1870	0.5745	0.3304	0.056*
C14	0.9580 (4)	0.5048 (2)	0.27289 (17)	0.0333 (6)
H14	0.8935	0.5771	0.2652	0.040*
C15	0.6972 (4)	0.1947 (2)	0.04402 (19)	0.0374 (7)
H15A	0.8193	0.1605	0.0419	0.056*
H15B	0.6169	0.1657	−0.0017	0.056*
H15C	0.6471	0.1719	0.0947	0.056*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br	0.0526 (2)	0.02501 (16)	0.0412 (2)	−0.00489 (13)	0.00320 (14)	0.00437 (12)
S	0.0301 (4)	0.0189 (3)	0.0269 (3)	−0.0004 (2)	0.0096 (3)	0.0010 (2)
O1	0.0328 (11)	0.0301 (10)	0.0263 (10)	0.0005 (8)	0.0042 (8)	−0.0057 (8)
O2	0.0393 (12)	0.0266 (9)	0.0341 (11)	0.0064 (8)	0.0149 (9)	−0.0020 (8)
O3	0.0392 (12)	0.0259 (10)	0.0398 (12)	−0.0066 (8)	0.0140 (9)	0.0038 (8)
C1	0.0256 (14)	0.0230 (12)	0.0246 (13)	0.0000 (10)	0.0059 (11)	−0.0002 (10)
C2	0.0191 (13)	0.0259 (12)	0.0235 (13)	0.0019 (10)	0.0038 (10)	0.0020 (10)
C3	0.0302 (14)	0.0242 (12)	0.0224 (13)	0.0021 (10)	0.0046 (11)	−0.0006 (10)
C4	0.0273 (15)	0.0262 (13)	0.0325 (15)	−0.0024 (11)	0.0019 (12)	0.0024 (11)
C5	0.0288 (15)	0.0371 (15)	0.0258 (14)	0.0000 (12)	0.0039 (11)	0.0081 (12)
C6	0.0296 (15)	0.0427 (15)	0.0202 (14)	0.0016 (12)	0.0033 (11)	−0.0001 (12)
C7	0.0224 (13)	0.0252 (12)	0.0258 (14)	0.0019 (10)	0.0007 (11)	−0.0038 (10)
C8	0.0243 (14)	0.0275 (13)	0.0298 (15)	−0.0014 (11)	0.0032 (11)	−0.0022 (11)
C9	0.0337 (15)	0.0256 (13)	0.0196 (13)	−0.0007 (10)	0.0096 (11)	0.0012 (10)
C10	0.0420 (18)	0.0317 (14)	0.0239 (14)	0.0033 (12)	0.0101 (12)	0.0077 (11)
C11	0.043 (2)	0.059 (2)	0.0330 (17)	0.0144 (16)	0.0095 (14)	0.0149 (15)
C12	0.0376 (19)	0.087 (3)	0.0264 (17)	−0.0062 (18)	0.0010 (14)	0.0063 (17)
C13	0.053 (2)	0.059 (2)	0.0276 (16)	−0.0175 (17)	0.0033 (14)	−0.0068 (15)
C14	0.0444 (18)	0.0305 (14)	0.0258 (14)	−0.0048 (12)	0.0087 (13)	−0.0023 (11)
C15	0.0437 (19)	0.0249 (14)	0.0443 (18)	−0.0021 (12)	0.0074 (14)	−0.0072 (12)

Geometric parameters (Å, º) top

Br—C4	1.906 (3)	C6—H6	0.950
S—O2	1.4372 (18)	C8—C15	1.487 (4)
S—O3	1.4377 (18)	C9—C14	1.387 (4)
S—C1	1.740 (3)	C9—C10	1.393 (4)
S—C9	1.758 (3)	C10—C11	1.383 (4)
O1—C8	1.369 (3)	C10—H10	0.950
O1—C7	1.380 (3)	C11—C12	1.389 (5)
C1—C8	1.363 (4)	C11—H11	0.950
C1—C2	1.448 (3)	C12—C13	1.387 (5)
C2—C7	1.392 (3)	C12—H12	0.950
C2—C3	1.398 (3)	C13—C14	1.377 (4)
C3—C4	1.388 (4)	C13—H13	0.950
C3—H3	0.950	C14—H14	0.950
C4—C5	1.392 (4)	C15—H15A	0.980
C5—C6	1.381 (4)	C15—H15B	0.980
C5—H5	0.950	C15—H15C	0.980
C6—C7	1.378 (4)

O2—S—O3	119.57 (12)	C1—C8—O1	110.7 (2)
O2—S—C1	107.14 (12)	C1—C8—C15	134.4 (3)
O3—S—C1	108.70 (12)	O1—C8—C15	114.9 (2)
O2—S—C9	108.19 (12)	C14—C9—C10	121.1 (3)
O3—S—C9	108.15 (12)	C14—C9—S	119.5 (2)
C1—S—C9	104.02 (12)	C10—C9—S	119.5 (2)
C8—O1—C7	106.97 (19)	C11—C10—C9	119.4 (3)
C8—C1—C2	107.1 (2)	C11—C10—H10	120.3
C8—C1—S	127.2 (2)	C9—C10—H10	120.3
C2—C1—S	125.57 (19)	C10—C11—C12	119.5 (3)
C7—C2—C3	119.2 (2)	C10—C11—H11	120.3
C7—C2—C1	104.9 (2)	C12—C11—H11	120.3
C3—C2—C1	135.9 (2)	C13—C12—C11	120.7 (3)
C4—C3—C2	116.6 (2)	C13—C12—H12	119.6
C4—C3—H3	121.7	C11—C12—H12	119.6
C2—C3—H3	121.7	C14—C13—C12	120.1 (3)
C3—C4—C5	123.3 (2)	C14—C13—H13	119.9
C3—C4—Br	118.4 (2)	C12—C13—H13	119.9
C5—C4—Br	118.32 (19)	C13—C14—C9	119.2 (3)
C6—C5—C4	120.1 (2)	C13—C14—H14	120.4
C6—C5—H5	119.9	C9—C14—H14	120.4
C4—C5—H5	119.9	C8—C15—H15A	109.5
C7—C6—C5	116.6 (2)	C8—C15—H15B	109.5
C7—C6—H6	121.7	H15A—C15—H15B	109.5
C5—C6—H6	121.7	C8—C15—H15C	109.5
C6—C7—O1	125.5 (2)	H15A—C15—H15C	109.5
C6—C7—C2	124.2 (2)	H15B—C15—H15C	109.5
O1—C7—C2	110.3 (2)

O2—S—C1—C8	−152.5 (2)	C3—C2—C7—O1	179.2 (2)
O3—S—C1—C8	−22.0 (3)	C1—C2—C7—O1	0.1 (3)
C9—S—C1—C8	93.1 (3)	C2—C1—C8—O1	−0.8 (3)
O2—S—C1—C2	31.8 (3)	S—C1—C8—O1	−177.14 (19)
O3—S—C1—C2	162.3 (2)	C2—C1—C8—C15	177.1 (3)
C9—S—C1—C2	−82.7 (2)	S—C1—C8—C15	0.8 (5)
C8—C1—C2—C7	0.4 (3)	C7—O1—C8—C1	0.8 (3)
S—C1—C2—C7	176.8 (2)	C7—O1—C8—C15	−177.5 (2)
C8—C1—C2—C3	−178.5 (3)	O2—S—C9—C14	−21.6 (2)
S—C1—C2—C3	−2.0 (5)	O3—S—C9—C14	−152.5 (2)
C7—C2—C3—C4	0.3 (4)	C1—S—C9—C14	92.0 (2)
C1—C2—C3—C4	179.1 (3)	O2—S—C9—C10	158.9 (2)
C2—C3—C4—C5	0.5 (4)	O3—S—C9—C10	28.0 (2)
C2—C3—C4—Br	−179.92 (19)	C1—S—C9—C10	−87.4 (2)
C3—C4—C5—C6	−0.6 (4)	C14—C9—C10—C11	0.2 (4)
Br—C4—C5—C6	179.8 (2)	S—C9—C10—C11	179.7 (2)
C4—C5—C6—C7	−0.2 (4)	C9—C10—C11—C12	−0.2 (4)
C5—C6—C7—O1	−179.4 (2)	C10—C11—C12—C13	0.1 (5)
C5—C6—C7—C2	1.1 (4)	C11—C12—C13—C14	0.0 (5)
C8—O1—C7—C6	179.8 (3)	C12—C13—C14—C9	0.1 (4)
C8—O1—C7—C2	−0.6 (3)	C10—C9—C14—C13	−0.2 (4)
C3—C2—C7—C6	−1.2 (4)	S—C9—C14—C13	−179.6 (2)
C1—C2—C7—C6	179.7 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···Cgⁱ	0.95	2.74	3.561 (3)	145
C10—H10···O2ⁱⁱ	0.95	2.54	3.285 (3)	135
C14—H14···O3ⁱⁱⁱ	0.95	2.45	3.249 (3)	141
C15—H15C···O3	0.98	2.40	3.131 (4)	131

Symmetry codes: (i) −x+2, −y+1, −z; (ii) −x+3/2, y−1/2, −z+1/2; (iii) −x+3/2, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₅H₁₁BrO₃S
M_r	351.21
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	173
a, b, c (Å)	7.337 (1), 11.345 (1), 16.602 (2)
β (°)	94.582 (3)
V (Å³)	1377.5 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.14
Crystal size (mm)	0.30 × 0.20 × 0.20

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1999)
T_min, T_max	0.463, 0.542
No. of measured, independent and observed [I > 2σ(I)] reflections	8005, 3009, 2349
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.086, 1.03
No. of reflections	3009
No. of parameters	182
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.55, −0.44

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 1998).