5-Bromo-2-methyl-3-(3-methyl­phenyl­sulfin­yl)-1-benzo­furan

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

doi:10.1107/S1600536814003365

organic compounds

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ISSN: 2056-9890

Volume 70| Part 3| March 2014| Page o320

doi:10.1107/S1600536814003365

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5-Bromo-2-methyl-3-(3-methylphenylsulfinyl)-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 13 February 2014; accepted 14 February 2014; online 19 February 2014)

In the title compound, C₁₆H₁₃BrO₂S, the dihedral angle between the mean plane [r.m.s. deviation = 0.012 (1) Å] of the benzofuran ring system and the 3-methylphenyl ring is 84.83 (4)°. In the crystal, molecules are linked via pairs of Br⋯O [3.240 (1) Å] contacts, forming inversion dimers. These dimers are linked by C—H⋯π interactions, forming a three-dimensional network.

CCDC reference: 986770

Related literature

For background information and the crystal structures of related compounds, see: Choi et al. (2010 , 2012a ,b ). For a review of halogen bonding, see: Politzer et al. (2007 ).

Experimental

Crystal data

C₁₆H₁₃BrO₂S
M_r = 349.23
Triclinic, $[P \overline 1]$
a = 8.4209 (1) Å
b = 8.9042 (1) Å
c = 10.8628 (1) Å
α = 106.956 (1)°
β = 90.441 (1)°
γ = 108.900 (1)°
V = 732.38 (1) Å³
Z = 2
Mo Kα radiation
μ = 2.95 mm⁻¹
T = 173 K
0.43 × 0.32 × 0.09 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.365, T_max = 0.746
13736 measured reflections
3667 independent reflections
3391 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.025
wR(F²) = 0.066
S = 1.09
3667 reflections
183 parameters
H-atom parameters constrained
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.54 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of rings C10–C15 (3-methylphenyl) and C2–C7 (benzene), respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9A⋯Cg1ⁱ	0.98	2.91	3.785 (2)	150
C12—H12⋯Cg2ⁱⁱ	0.95	2.79	3.674 (2)	154
Symmetry codes: (i) -x+1, -y+1, -z+2; (ii) x+1, y, z.

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 for Windows (Farrugia, 2012 ) and DIAMOND (Brandenburg, 1998 ); software used to prepare material for publication: SHELXL97.

Supporting information

CCDC reference: 986770

Crystal structure: contains datablock I. DOI: 10.1107/S1600536814003365/su2700sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814003365/su2700Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814003365/su2700Isup3.cml

checkCIF report

Comment top

As a part of our continuing study of 5-bromo-2-methyl-1-benzofuran derivatives containing 4-chlorophenylsulfinyl (Choi et al., 2010), 4-methylphenylsulfinyl (Choi et al., 2012a) and 3-fluorophenylsulfinyl (Choi et al., 2012b) substituents in the 3-position, we report herein on the crystal structure of the title compound.

In the title molecule, Fig. 1, the benzofuran unit is essentially planar, with a mean deviation of 0.012 (1) Å from the mean plane defined by the nine constituent atoms. It is inclined to the 3-methylphenyl ring by 84.83 (4)°.

In the crystal, Fig. 2, molecules are connected by pairs of Br···O halogen-bonds (Politzer et al., 2007), between the bromine atom and the O atom of the S═O unit [Br1···O2ⁱⁱⁱ = 3.240 (1) Å, C4—Br1···O2ⁱⁱⁱ = 175.63 (5)°; symmetry code: (iii) - x, - y + 1, - z + 1] forming inversion dimers. These dimers are linked by C—H···π interactions into supramolecular chains running along the a-axis. In addition, there are C—H···π interactions resulting in inversion related dimers (Table 1 and Fig. 2).

Related literature top

For background information and the crystal structures of related compounds, see: Choi et al. (2010, 2012a,b). 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-2-methyl-3-(3-methylphenylsulfanyl)-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, 2:1 v/v) to afford the title compound as a colorless solid [Yield 78%, M.p. 413–414 K; R_f = 0.49 (hexane-ethyl acetate, 2:1 v/v)]. Single crystals suitable for X-ray diffraction were prepared by slow evaporation of a solution of the title compound in ethyl acetate 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 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 1998); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title molecule, with atom labelling. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A view along the b axis of the crystal packing of the title compound, showing the C—H···π and Br···O interactions as dotted lines [see Table 1 for details; H atoms not involved in hydrogen-bonding have been omitted for clarity; symmetry codes : (i) - x + 1, - y + 1, - z + 2; (ii) x + 1, y, z; (iii) - x, - y + 1, - z + 1; (iv) x - 1, y, z].

5-Bromo-2-methyl-3-(3-methylphenylsulfinyl)-1-benzofuran top

Crystal data top

C₁₆H₁₃BrO₂S	Z = 2
M_r = 349.23	F(000) = 352
Triclinic, P1	D_x = 1.584 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.4209 (1) Å	Cell parameters from 8553 reflections
b = 8.9042 (1) Å	θ = 2.5–28.4°
c = 10.8628 (1) Å	µ = 2.95 mm⁻¹
α = 106.956 (1)°	T = 173 K
β = 90.441 (1)°	Block, colourless
γ = 108.900 (1)°	0.43 × 0.32 × 0.09 mm
V = 732.38 (1) Å³

Data collection top

Bruker SMART APEXII CCD diffractometer	3667 independent reflections
Radiation source: rotating anode	3391 reflections with I > 2σ(I)
Graphite multilayer monochromator	R_int = 0.034
Detector resolution: 10.0 pixels mm^-1	θ_max = 28.4°, θ_min = 2.0°
φ and ω scans	h = −11→11
Absorption correction: multi-scan (SADABS; Bruker, 2009)	k = −11→11
T_min = 0.365, T_max = 0.746	l = −14→14
13736 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)] = 0.025	Hydrogen site location: difference Fourier map
wR(F²) = 0.066	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0306P)² + 0.2396P] where P = (F_o² + 2F_c²)/3
3667 reflections	(Δ/σ)_max = 0.001
183 parameters	Δρ_max = 0.36 e Å⁻³
0 restraints	Δρ_min = −0.54 e Å⁻³

Crystal data top

C₁₆H₁₃BrO₂S	γ = 108.900 (1)°
M_r = 349.23	V = 732.38 (1) Å³
Triclinic, P1	Z = 2
a = 8.4209 (1) Å	Mo Kα radiation
b = 8.9042 (1) Å	µ = 2.95 mm⁻¹
c = 10.8628 (1) Å	T = 173 K
α = 106.956 (1)°	0.43 × 0.32 × 0.09 mm
β = 90.441 (1)°

Data collection top

Bruker SMART APEXII CCD diffractometer	3667 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	3391 reflections with I > 2σ(I)
T_min = 0.365, T_max = 0.746	R_int = 0.034
13736 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.025	0 restraints
wR(F²) = 0.066	H-atom parameters constrained
S = 1.09	Δρ_max = 0.36 e Å⁻³
3667 reflections	Δρ_min = −0.54 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	0.04187 (2)	0.75979 (2)	0.479648 (15)	0.03138 (7)
S1	0.24413 (5)	0.49344 (5)	0.90916 (4)	0.02597 (9)
O1	0.23301 (15)	0.94970 (14)	1.04896 (11)	0.0283 (2)
O2	0.08675 (15)	0.36872 (15)	0.82700 (13)	0.0339 (3)
C1	0.23351 (19)	0.69433 (19)	0.93705 (15)	0.0230 (3)
C2	0.18550 (18)	0.76541 (18)	0.84534 (14)	0.0209 (3)
C3	0.14284 (19)	0.71368 (19)	0.71172 (15)	0.0224 (3)
H3	0.1423	0.6081	0.6579	0.027*
C4	0.10115 (19)	0.82404 (19)	0.66114 (15)	0.0235 (3)
C5	0.0980 (2)	0.9788 (2)	0.73792 (17)	0.0271 (3)
H5	0.0661	1.0488	0.6989	0.033*
C6	0.1413 (2)	1.03082 (19)	0.87084 (17)	0.0273 (3)
H6	0.1405	1.1358	0.9249	0.033*
C7	0.18532 (19)	0.92194 (19)	0.92009 (15)	0.0234 (3)
C8	0.2602 (2)	0.8082 (2)	1.05582 (16)	0.0266 (3)
C9	0.3152 (3)	0.8114 (3)	1.18646 (17)	0.0384 (4)
H9A	0.3161	0.7005	1.1833	0.058*
H9B	0.2369	0.8424	1.2469	0.058*
H9C	0.4291	0.8934	1.2159	0.058*
C10	0.40882 (18)	0.50755 (19)	0.80452 (15)	0.0234 (3)
C11	0.5604 (2)	0.6403 (2)	0.84122 (18)	0.0317 (3)
H11	0.5760	0.7300	0.9187	0.038*
C12	0.6883 (2)	0.6386 (2)	0.7623 (2)	0.0384 (4)
H12	0.7932	0.7281	0.7859	0.046*
C13	0.6648 (2)	0.5077 (2)	0.64917 (19)	0.0345 (4)
H13	0.7539	0.5090	0.5959	0.041*
C14	0.5133 (2)	0.3745 (2)	0.61235 (17)	0.0289 (3)
C15	0.3854 (2)	0.3760 (2)	0.69235 (16)	0.0266 (3)
H15	0.2810	0.2857	0.6697	0.032*
C16	0.4876 (3)	0.2305 (3)	0.4904 (2)	0.0424 (4)
H16A	0.5240	0.2737	0.4181	0.064*
H16B	0.3678	0.1614	0.4714	0.064*
H16C	0.5545	0.1629	0.5023	0.064*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.03812 (10)	0.03427 (10)	0.02629 (9)	0.01357 (7)	0.00008 (6)	0.01480 (7)
S1	0.02985 (19)	0.02419 (19)	0.0310 (2)	0.01154 (15)	0.00610 (15)	0.01633 (16)
O1	0.0335 (6)	0.0250 (6)	0.0242 (6)	0.0104 (5)	0.0017 (4)	0.0042 (5)
O2	0.0277 (6)	0.0229 (6)	0.0491 (8)	0.0053 (5)	0.0083 (5)	0.0119 (5)
C1	0.0248 (7)	0.0231 (7)	0.0238 (7)	0.0085 (6)	0.0040 (5)	0.0107 (6)
C2	0.0214 (6)	0.0196 (7)	0.0245 (7)	0.0077 (5)	0.0052 (5)	0.0099 (6)
C3	0.0259 (7)	0.0199 (7)	0.0233 (7)	0.0092 (5)	0.0032 (5)	0.0079 (6)
C4	0.0225 (7)	0.0249 (7)	0.0256 (7)	0.0075 (6)	0.0022 (5)	0.0121 (6)
C5	0.0260 (7)	0.0227 (7)	0.0373 (9)	0.0088 (6)	0.0034 (6)	0.0156 (7)
C6	0.0292 (8)	0.0184 (7)	0.0345 (8)	0.0093 (6)	0.0036 (6)	0.0070 (6)
C7	0.0241 (7)	0.0212 (7)	0.0237 (7)	0.0069 (5)	0.0031 (5)	0.0063 (6)
C8	0.0259 (7)	0.0286 (8)	0.0264 (8)	0.0080 (6)	0.0039 (6)	0.0113 (6)
C9	0.0439 (10)	0.0467 (11)	0.0243 (8)	0.0141 (8)	−0.0007 (7)	0.0124 (8)
C10	0.0219 (7)	0.0236 (7)	0.0296 (8)	0.0100 (6)	0.0012 (6)	0.0131 (6)
C11	0.0277 (8)	0.0259 (8)	0.0368 (9)	0.0069 (6)	0.0001 (7)	0.0057 (7)
C12	0.0253 (8)	0.0308 (9)	0.0524 (12)	0.0037 (7)	0.0050 (7)	0.0097 (8)
C13	0.0293 (8)	0.0335 (9)	0.0450 (10)	0.0131 (7)	0.0123 (7)	0.0157 (8)
C14	0.0315 (8)	0.0285 (8)	0.0316 (8)	0.0152 (6)	0.0026 (6)	0.0111 (7)
C15	0.0245 (7)	0.0225 (7)	0.0338 (8)	0.0081 (6)	−0.0015 (6)	0.0103 (6)
C16	0.0451 (10)	0.0391 (10)	0.0401 (10)	0.0190 (8)	0.0048 (8)	0.0027 (8)

Geometric parameters (Å, º) top

Br1—C4	1.8988 (16)	C8—C9	1.479 (2)
Br1—O2ⁱ	3.2399 (14)	C9—H9A	0.9800
S1—O2	1.4954 (13)	C9—H9B	0.9800
S1—C1	1.7571 (16)	C9—H9C	0.9800
S1—C10	1.7960 (16)	C10—C15	1.382 (2)
O1—C8	1.373 (2)	C10—C11	1.387 (2)
O1—C7	1.3810 (19)	C11—C12	1.382 (3)
C1—C8	1.352 (2)	C11—H11	0.9500
C1—C2	1.444 (2)	C12—C13	1.386 (3)
C2—C3	1.394 (2)	C12—H12	0.9500
C2—C7	1.394 (2)	C13—C14	1.389 (2)
C3—C4	1.388 (2)	C13—H13	0.9500
C3—H3	0.9500	C14—C15	1.390 (2)
C4—C5	1.396 (2)	C14—C16	1.507 (3)
C5—C6	1.387 (2)	C15—H15	0.9500
C5—H5	0.9500	C16—H16A	0.9800
C6—C7	1.377 (2)	C16—H16B	0.9800
C6—H6	0.9500	C16—H16C	0.9800

C4—Br1—O2ⁱ	175.63 (5)	C8—C9—H9B	109.5
O2—S1—C1	108.56 (7)	H9A—C9—H9B	109.5
O2—S1—C10	106.16 (7)	C8—C9—H9C	109.5
C1—S1—C10	98.49 (7)	H9A—C9—H9C	109.5
C8—O1—C7	106.43 (12)	H9B—C9—H9C	109.5
C8—C1—C2	107.45 (14)	C15—C10—C11	121.21 (15)
C8—C1—S1	123.80 (12)	C15—C10—S1	118.01 (12)
C2—C1—S1	128.62 (12)	C11—C10—S1	120.56 (13)
C3—C2—C7	119.50 (13)	C12—C11—C10	118.38 (17)
C3—C2—C1	135.70 (14)	C12—C11—H11	120.8
C7—C2—C1	104.80 (13)	C10—C11—H11	120.8
C4—C3—C2	116.72 (14)	C11—C12—C13	120.62 (16)
C4—C3—H3	121.6	C11—C12—H12	119.7
C2—C3—H3	121.6	C13—C12—H12	119.7
C3—C4—C5	122.96 (15)	C12—C13—C14	121.11 (17)
C3—C4—Br1	118.47 (12)	C12—C13—H13	119.4
C5—C4—Br1	118.57 (11)	C14—C13—H13	119.4
C6—C5—C4	120.40 (14)	C13—C14—C15	118.14 (16)
C6—C5—H5	119.8	C13—C14—C16	121.43 (17)
C4—C5—H5	119.8	C15—C14—C16	120.43 (16)
C7—C6—C5	116.32 (14)	C10—C15—C14	120.54 (15)
C7—C6—H6	121.8	C10—C15—H15	119.7
C5—C6—H6	121.8	C14—C15—H15	119.7
C6—C7—O1	125.57 (14)	C14—C16—H16A	109.5
C6—C7—C2	124.08 (15)	C14—C16—H16B	109.5
O1—C7—C2	110.35 (13)	H16A—C16—H16B	109.5
C1—C8—O1	110.95 (14)	C14—C16—H16C	109.5
C1—C8—C9	133.31 (16)	H16A—C16—H16C	109.5
O1—C8—C9	115.71 (15)	H16B—C16—H16C	109.5
C8—C9—H9A	109.5

O2—S1—C1—C8	129.11 (14)	C1—C2—C7—O1	1.19 (16)
C10—S1—C1—C8	−120.59 (14)	C2—C1—C8—O1	0.05 (18)
O2—S1—C1—C2	−46.22 (16)	S1—C1—C8—O1	−176.13 (11)
C10—S1—C1—C2	64.09 (15)	C2—C1—C8—C9	−178.18 (18)
C8—C1—C2—C3	179.77 (17)	S1—C1—C8—C9	5.6 (3)
S1—C1—C2—C3	−4.3 (3)	C7—O1—C8—C1	0.68 (17)
C8—C1—C2—C7	−0.75 (17)	C7—O1—C8—C9	179.25 (14)
S1—C1—C2—C7	175.18 (12)	O2—S1—C10—C15	−21.27 (13)
C7—C2—C3—C4	−0.4 (2)	C1—S1—C10—C15	−133.50 (12)
C1—C2—C3—C4	179.07 (16)	O2—S1—C10—C11	164.08 (13)
C2—C3—C4—C5	−1.1 (2)	C1—S1—C10—C11	51.85 (14)
C2—C3—C4—Br1	−179.96 (11)	C15—C10—C11—C12	0.3 (3)
C3—C4—C5—C6	1.5 (2)	S1—C10—C11—C12	174.82 (14)
Br1—C4—C5—C6	−179.67 (12)	C10—C11—C12—C13	0.2 (3)
C4—C5—C6—C7	−0.3 (2)	C11—C12—C13—C14	−0.4 (3)
C5—C6—C7—O1	179.71 (14)	C12—C13—C14—C15	−0.1 (3)
C5—C6—C7—C2	−1.2 (2)	C12—C13—C14—C16	−179.16 (18)
C8—O1—C7—C6	178.02 (15)	C11—C10—C15—C14	−0.8 (2)
C8—O1—C7—C2	−1.18 (17)	S1—C10—C15—C14	−175.41 (12)
C3—C2—C7—C6	1.6 (2)	C13—C14—C15—C10	0.6 (2)
C1—C2—C7—C6	−178.02 (15)	C16—C14—C15—C10	179.75 (15)
C3—C2—C7—O1	−179.22 (13)

Symmetry code: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of rings C10–C15 (3-methylphenyl) and C2–C7 (benzene), respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9A···Cg1ⁱⁱ	0.98	2.91	3.785 (2)	150
C12—H12···Cg2ⁱⁱⁱ	0.95	2.79	3.674 (2)	154

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

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of rings C10–C15 (3-methylphenyl) and C2–C7 (benzene), respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9A···Cg1ⁱ	0.98	2.91	3.785 (2)	150
C12—H12···Cg2ⁱⁱ	0.95	2.79	3.674 (2)	154

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

References

Brandenburg, K. (1998). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
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Volume 70| Part 3| March 2014| Page o320

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