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

Choi, H.D.; Seo, P.J.; Lee, U.

doi:10.1107/S1600536812045205

organic compounds

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ISSN: 2056-9890

Volume 68| Part 12| December 2012| Page o3292

doi:10.1107/S1600536812045205

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

Hong Dae Choi,^a Pil Ja Seo ^a and Uk Lee ^b ^*

^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 29 October 2012; accepted 1 November 2012; online 7 November 2012)

In the title compound, C₁₆H₁₃BrO₂S, the 4-methylphenyl ring makes a dihedral angle of 29.58 (7)° with the mean plane [r.m.s. deviation = 0.007 (2) Å] of the benzofuran fragment. In the crystal, the molecules are linked by pairs of C—H⋯O hydrogen bonds into centrosymmetric dimers.

Related literature

For background information and the crystal structures of related compounds, see: Choi et al. (2007 , 2010 ).

Experimental

Crystal data

C₁₆H₁₃BrO₂S
M_r = 349.23
Triclinic, $[P \overline 1]$
a = 8.0922 (2) Å
b = 8.1401 (2) Å
c = 11.4535 (3) Å
α = 92.074 (2)°
β = 94.740 (1)°
γ = 111.141 (1)°
V = 699.50 (3) Å³
Z = 2
Mo Kα radiation
μ = 3.09 mm⁻¹
T = 173 K
0.33 × 0.23 × 0.13 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.549, T_max = 0.746
12899 measured reflections
3460 independent reflections
3093 reflections with I > 2σ(I)
R_int = 0.044

Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.073
S = 1.05
3460 reflections
183 parameters
H-atom parameters constrained
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.64 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C14—H14⋯O2ⁱ	0.95	2.51	3.418 (3)	160
Symmetry code: (i) -x+1, -y, -z+1.

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812045205/ld2082sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812045205/ld2082Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812045205/ld2082Isup3.cml

checkCIF report

Comment top

As a part of our ongoing study of 5-bromo-3-methylsulfinyl-1-benzofuran derivatives containing phenyl (Choi et al., 2007) and 4-fluorophenyl (Choi et al., 2010) 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 0.007 (2) 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 fragment is 29.58 (7)°. In the crystal structure, molecules are connected by weak C—H···O hydrogen bonds (Table 1).

Related literature top

For background information and the crystal structures of related compounds, see: Choi et al. (2007, 2010).

Experimental top

3-Chloroperoxybenzoic acid (77%, 224 mg, 1.0 mmol) was added in small portions to a stirred solution of 5-bromo-2-(4-methylphenyl)-3-methylsulfanyl-1-benzofuran (300 mg, 0.9 mmol) in dichloromethane (30 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 78%, m.p. 467–468 K; R_f = 0.51 (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.

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, 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 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-2-(4-methylphenyl)-3-methylsulfinyl-1-benzofuran top

Crystal data top

C₁₆H₁₃BrO₂S	Z = 2
M_r = 349.23	F(000) = 352
Triclinic, P1	D_x = 1.658 Mg m⁻³
Hall symbol: -P 1	Melting point: 467.5 K
a = 8.0922 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.1401 (2) Å	Cell parameters from 6092 reflections
c = 11.4535 (3) Å	θ = 2.7–28.1°
α = 92.074 (2)°	µ = 3.09 mm⁻¹
β = 94.740 (1)°	T = 173 K
γ = 111.141 (1)°	Block, colourless
V = 699.50 (3) Å³	0.33 × 0.23 × 0.13 mm

Data collection top

Bruker SMART APEXII CCD diffractometer	3460 independent reflections
Radiation source: rotating anode	3093 reflections with I > 2σ(I)
Graphite multilayer monochromator	R_int = 0.044
Detector resolution: 10.0 pixels mm^-1	θ_max = 28.3°, θ_min = 2.7°
ϕ and ω scans	h = −10→10
Absorption correction: multi-scan (SADABS; Bruker, 2009)	k = −10→10
T_min = 0.549, T_max = 0.746	l = −15→15
12899 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)] = 0.029	Hydrogen site location: difference Fourier map
wR(F²) = 0.073	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0337P)² + 0.2757P] where P = (F_o² + 2F_c²)/3
3460 reflections	(Δ/σ)_max < 0.001
183 parameters	Δρ_max = 0.39 e Å⁻³
0 restraints	Δρ_min = −0.64 e Å⁻³

Crystal data top

C₁₆H₁₃BrO₂S	γ = 111.141 (1)°
M_r = 349.23	V = 699.50 (3) Å³
Triclinic, P1	Z = 2
a = 8.0922 (2) Å	Mo Kα radiation
b = 8.1401 (2) Å	µ = 3.09 mm⁻¹
c = 11.4535 (3) Å	T = 173 K
α = 92.074 (2)°	0.33 × 0.23 × 0.13 mm
β = 94.740 (1)°

Data collection top

Bruker SMART APEXII CCD diffractometer	3460 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	3093 reflections with I > 2σ(I)
T_min = 0.549, T_max = 0.746	R_int = 0.044
12899 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	0 restraints
wR(F²) = 0.073	H-atom parameters constrained
S = 1.05	Δρ_max = 0.39 e Å⁻³
3460 reflections	Δρ_min = −0.64 e Å⁻³
183 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

	x	y	z	U_iso*/U_eq
Br1	0.21210 (3)	−0.07754 (3)	−0.011426 (16)	0.02948 (8)
S1	0.79265 (6)	0.31621 (6)	0.39466 (4)	0.02465 (11)
O1	0.30712 (17)	0.14982 (19)	0.49856 (11)	0.0248 (3)
O2	0.8172 (2)	0.1916 (2)	0.30537 (15)	0.0374 (4)
C1	0.5622 (2)	0.2385 (3)	0.41230 (16)	0.0224 (4)
C2	0.4203 (2)	0.1408 (3)	0.32362 (16)	0.0221 (4)
C3	0.4062 (2)	0.0933 (3)	0.20404 (16)	0.0240 (4)
H3	0.5074	0.1278	0.1611	0.029*
C4	0.2384 (3)	−0.0061 (3)	0.15103 (17)	0.0247 (4)
C5	0.0857 (3)	−0.0589 (3)	0.21114 (18)	0.0272 (4)
H5	−0.0268	−0.1276	0.1705	0.033*
C6	0.0989 (3)	−0.0110 (3)	0.32963 (17)	0.0266 (4)
H6	−0.0025	−0.0444	0.3725	0.032*
C7	0.2666 (2)	0.0878 (3)	0.38217 (16)	0.0228 (4)
C8	0.4889 (2)	0.2400 (3)	0.51483 (17)	0.0225 (4)
C9	0.5589 (2)	0.3174 (3)	0.63344 (16)	0.0224 (4)
C10	0.7074 (3)	0.4730 (3)	0.65431 (18)	0.0269 (4)
H10	0.7650	0.5303	0.5900	0.032*
C16	0.8052 (3)	0.5093 (3)	0.3208 (2)	0.0349 (5)
H16A	0.9238	0.5629	0.2941	0.052*
H16B	0.7841	0.5940	0.3749	0.052*
H16C	0.7148	0.4769	0.2530	0.052*
C11	0.7721 (3)	0.5453 (3)	0.76747 (18)	0.0282 (4)
H11	0.8746	0.6507	0.7802	0.034*
C12	0.6884 (3)	0.4647 (3)	0.86292 (17)	0.0256 (4)
C13	0.5395 (3)	0.3109 (3)	0.84128 (17)	0.0254 (4)
H13	0.4812	0.2548	0.9057	0.030*
C14	0.4735 (3)	0.2369 (3)	0.72894 (17)	0.0237 (4)
H14	0.3706	0.1319	0.7165	0.028*
C15	0.7567 (3)	0.5428 (3)	0.98612 (19)	0.0354 (5)
H15A	0.8662	0.5222	1.0103	0.053*
H15B	0.6667	0.4872	1.0392	0.053*
H15C	0.7819	0.6701	0.9893	0.053*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.02978 (12)	0.03373 (13)	0.02214 (11)	0.00932 (9)	−0.00028 (7)	−0.00267 (8)
S1	0.0187 (2)	0.0260 (3)	0.0285 (2)	0.00706 (18)	0.00329 (17)	0.00160 (19)
O1	0.0202 (6)	0.0304 (7)	0.0221 (7)	0.0074 (6)	0.0031 (5)	−0.0015 (5)
O2	0.0289 (8)	0.0321 (8)	0.0520 (10)	0.0109 (7)	0.0139 (7)	−0.0059 (7)
C1	0.0207 (9)	0.0242 (9)	0.0228 (9)	0.0088 (7)	0.0020 (7)	−0.0002 (7)
C2	0.0194 (8)	0.0222 (9)	0.0254 (9)	0.0083 (7)	0.0026 (7)	0.0008 (7)
C3	0.0230 (9)	0.0269 (10)	0.0232 (9)	0.0103 (8)	0.0040 (7)	0.0000 (7)
C4	0.0271 (10)	0.0246 (10)	0.0232 (9)	0.0106 (8)	0.0015 (7)	0.0007 (7)
C5	0.0221 (9)	0.0287 (10)	0.0279 (10)	0.0071 (8)	−0.0020 (7)	−0.0002 (8)
C6	0.0206 (9)	0.0315 (11)	0.0270 (10)	0.0083 (8)	0.0042 (7)	0.0029 (8)
C7	0.0239 (9)	0.0251 (10)	0.0208 (9)	0.0106 (8)	0.0024 (7)	0.0008 (7)
C8	0.0201 (8)	0.0220 (9)	0.0250 (9)	0.0071 (7)	0.0025 (7)	0.0009 (7)
C9	0.0226 (9)	0.0241 (9)	0.0220 (9)	0.0103 (7)	0.0026 (7)	−0.0004 (7)
C10	0.0281 (10)	0.0235 (10)	0.0260 (10)	0.0049 (8)	0.0071 (7)	0.0020 (8)
C16	0.0376 (12)	0.0293 (11)	0.0397 (12)	0.0120 (9)	0.0114 (9)	0.0102 (9)
C11	0.0273 (10)	0.0235 (10)	0.0306 (10)	0.0052 (8)	0.0060 (8)	−0.0013 (8)
C12	0.0273 (10)	0.0267 (10)	0.0237 (9)	0.0114 (8)	0.0020 (7)	−0.0025 (8)
C13	0.0271 (10)	0.0259 (10)	0.0232 (9)	0.0091 (8)	0.0056 (7)	0.0032 (8)
C14	0.0225 (9)	0.0224 (9)	0.0256 (9)	0.0076 (7)	0.0023 (7)	0.0022 (7)
C15	0.0364 (12)	0.0373 (12)	0.0277 (11)	0.0088 (10)	0.0019 (9)	−0.0070 (9)

Geometric parameters (Å, º) top

Br1—C4	1.9007 (19)	C9—C10	1.392 (3)
S1—O2	1.4896 (15)	C9—C14	1.398 (3)
S1—C1	1.7720 (19)	C10—C11	1.382 (3)
S1—C16	1.786 (2)	C10—H10	0.9500
O1—C7	1.378 (2)	C16—H16A	0.9800
O1—C8	1.379 (2)	C16—H16B	0.9800
C1—C8	1.360 (3)	C16—H16C	0.9800
C1—C2	1.440 (3)	C11—C12	1.392 (3)
C2—C3	1.394 (3)	C11—H11	0.9500
C2—C7	1.398 (3)	C12—C13	1.386 (3)
C3—C4	1.380 (3)	C12—C15	1.501 (3)
C3—H3	0.9500	C13—C14	1.379 (3)
C4—C5	1.401 (3)	C13—H13	0.9500
C5—C6	1.383 (3)	C14—H14	0.9500
C5—H5	0.9500	C15—H15A	0.9800
C6—C7	1.376 (3)	C15—H15B	0.9800
C6—H6	0.9500	C15—H15C	0.9800
C8—C9	1.455 (3)

O2—S1—C1	106.50 (9)	C10—C9—C8	121.49 (18)
O2—S1—C16	106.04 (11)	C14—C9—C8	119.64 (18)
C1—S1—C16	97.95 (10)	C11—C10—C9	120.83 (19)
C7—O1—C8	106.54 (14)	C11—C10—H10	119.6
C8—C1—C2	107.55 (16)	C9—C10—H10	119.6
C8—C1—S1	126.28 (15)	S1—C16—H16A	109.5
C2—C1—S1	125.68 (14)	S1—C16—H16B	109.5
C3—C2—C7	119.12 (17)	H16A—C16—H16B	109.5
C3—C2—C1	135.99 (17)	S1—C16—H16C	109.5
C7—C2—C1	104.89 (16)	H16A—C16—H16C	109.5
C4—C3—C2	116.83 (17)	H16B—C16—H16C	109.5
C4—C3—H3	121.6	C10—C11—C12	120.50 (19)
C2—C3—H3	121.6	C10—C11—H11	119.7
C3—C4—C5	123.34 (18)	C12—C11—H11	119.7
C3—C4—Br1	118.59 (14)	C13—C12—C11	118.29 (18)
C5—C4—Br1	118.07 (15)	C13—C12—C15	120.79 (19)
C6—C5—C4	120.02 (18)	C11—C12—C15	120.92 (19)
C6—C5—H5	120.0	C14—C13—C12	121.94 (18)
C4—C5—H5	120.0	C14—C13—H13	119.0
C7—C6—C5	116.45 (18)	C12—C13—H13	119.0
C7—C6—H6	121.8	C13—C14—C9	119.58 (18)
C5—C6—H6	121.8	C13—C14—H14	120.2
C6—C7—O1	125.30 (17)	C9—C14—H14	120.2
C6—C7—C2	124.25 (18)	C12—C15—H15A	109.5
O1—C7—C2	110.45 (16)	C12—C15—H15B	109.5
C1—C8—O1	110.55 (16)	H15A—C15—H15B	109.5
C1—C8—C9	134.34 (18)	C12—C15—H15C	109.5
O1—C8—C9	115.09 (16)	H15A—C15—H15C	109.5
C10—C9—C14	118.85 (18)	H15B—C15—H15C	109.5

O2—S1—C1—C8	142.04 (18)	C1—C2—C7—O1	1.0 (2)
C16—S1—C1—C8	−108.55 (19)	C2—C1—C8—O1	−0.3 (2)
O2—S1—C1—C2	−28.91 (19)	S1—C1—C8—O1	−172.59 (14)
C16—S1—C1—C2	80.51 (18)	C2—C1—C8—C9	−178.7 (2)
C8—C1—C2—C3	179.5 (2)	S1—C1—C8—C9	9.0 (3)
S1—C1—C2—C3	−8.1 (3)	C7—O1—C8—C1	0.9 (2)
C8—C1—C2—C7	−0.4 (2)	C7—O1—C8—C9	179.68 (16)
S1—C1—C2—C7	171.91 (14)	C1—C8—C9—C10	29.9 (3)
C7—C2—C3—C4	−0.6 (3)	O1—C8—C9—C10	−148.46 (18)
C1—C2—C3—C4	179.4 (2)	C1—C8—C9—C14	−151.6 (2)
C2—C3—C4—C5	0.3 (3)	O1—C8—C9—C14	30.0 (2)
C2—C3—C4—Br1	−179.08 (14)	C14—C9—C10—C11	1.4 (3)
C3—C4—C5—C6	0.2 (3)	C8—C9—C10—C11	179.83 (18)
Br1—C4—C5—C6	179.55 (15)	C9—C10—C11—C12	−0.8 (3)
C4—C5—C6—C7	−0.3 (3)	C10—C11—C12—C13	0.1 (3)
C5—C6—C7—O1	179.33 (18)	C10—C11—C12—C15	−179.5 (2)
C5—C6—C7—C2	0.0 (3)	C11—C12—C13—C14	0.0 (3)
C8—O1—C7—C6	179.35 (19)	C15—C12—C13—C14	179.68 (19)
C8—O1—C7—C2	−1.2 (2)	C12—C13—C14—C9	0.5 (3)
C3—C2—C7—C6	0.5 (3)	C10—C9—C14—C13	−1.2 (3)
C1—C2—C7—C6	−179.53 (19)	C8—C9—C14—C13	−179.68 (17)
C3—C2—C7—O1	−178.94 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14···O2ⁱ	0.95	2.51	3.418 (3)	160

Symmetry code: (i) −x+1, −y, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₆H₁₃BrO₂S
M_r	349.23
Crystal system, space group	Triclinic, P1
Temperature (K)	173
a, b, c (Å)	8.0922 (2), 8.1401 (2), 11.4535 (3)
α, β, γ (°)	92.074 (2), 94.740 (1), 111.141 (1)
V (Å³)	699.50 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	3.09
Crystal size (mm)	0.33 × 0.23 × 0.13

Data collection
Diffractometer	Bruker SMART APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.549, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	12899, 3460, 3093
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.073, 1.05
No. of reflections	3460
No. of parameters	183
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.64

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 1998).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14···O2ⁱ	0.95	2.51	3.418 (3)	159.6

Symmetry code: (i) −x+1, −y, −z+1.

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

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