3-(4-Bromo­phenyl­sulfin­yl)-5-chloro-2-methyl-1-benzofuran

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

doi:10.1107/S1600536812025846

organic compounds

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ISSN: 2056-9890

Volume 68| Part 7| July 2012| Page o2080

https://doi.org/10.1107/S1600536812025846

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3-(4-Bromophenylsulfinyl)-5-chloro-2-methyl-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 15 May 2012; accepted 7 June 2012; online 13 June 2012)

In the title compound, C₁₅H₁₀BrClO₂S, the 4-bromophenyl ring makes a dihedral angle of 86.85 (6)° with the mean plane [mean deviation = 0.009 (2) Å] of the benzofuran fragment. In the crystal, molecules are linked by slipped π–π interactions between the benzene and the furan rings of adjacent molecules [centroid–centroid distance = 3.884 (2), interplanar distance = 3.369 (2) and slippage = 1.945 (2) Å], and between the 4-bromophenyl rings of adjacent molecules [centroid–centroid distance = 3.882 (2), interplanar distance = 3.552 (2) and slippage = 1.566 (2) Å]. A Br⋯Br [3.6446 (4) Å] halogen interaction is also observed.

Related literature

For background information and the crystal structures of related compounds, see: Choi et al. (2008 , 2010 ).

Experimental

Crystal data

C₁₅H₁₀BrClO₂S
M_r = 369.65
Triclinic, $[P \overline 1]$
a = 6.4192 (1) Å
b = 9.9185 (2) Å
c = 11.7755 (2) Å
α = 100.681 (1)°
β = 92.113 (1)°
γ = 104.168 (1)°
V = 711.67 (2) Å³
Z = 2
Mo Kα radiation
μ = 3.22 mm⁻¹
T = 173 K
0.38 × 0.31 × 0.27 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.374, T_max = 0.475
13131 measured reflections
3529 independent reflections
3236 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.081
S = 1.12
3529 reflections
182 parameters
H-atom parameters constrained
Δρ_max = 0.55 e Å⁻³
Δρ_min = −0.76 e Å⁻³

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 datablock I. DOI: https://doi.org/10.1107/S1600536812025846/ds2198sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812025846/ds2198Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812025846/ds2198Isup3.cml

checkCIF report

Comment top

As a part of our ongoing study of 5-chloro-2-methyl-1-benzofuran derivatives containing 3-phenylsulfonyl (Choi et al., 2008) and 3-(4-fluorophenylsulfonyl) (Choi et al., 2010) substituents, 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 0.009 (2) Å from the least-squares plane defined by the nine constituent atoms. The dihedral angle between the 4-bromophenyl ring and the mean plane of the benzofuran fragment is 86.85 (6)°. In the crystal structure (Fig. 2), molecules are connected by slipped π···π interactions; the first one between the benzene and the furan rings of adjacent molecules, with a Cg1···Cg2ⁱ distance of 3.884 (2) Å and an interplanar distance of 3.369 (2) Å resulting in a slippage of 1.945 (2) Å (Cg1 and Cg2 are the centroids of the C2–C7 benzene ring and the C1/C2/C7/O1/C8 furan ring, respectively), and the second one between the 4-bromophenyl rings of adjacent molecules, with a Cg3···Cg3ⁱⁱ distance of 3.882 (2) Å and an interplanar distance of 3.552 (2) Å resulting in a slippage of 1.566 (2) Å (Cg3 is the centroid of the C10–C15 benzene ring). The crystal packing (Fig. 2) also exhibits a Br···Br contact at [3.6446 (4) Å].

Related literature top

For background information and the crystal structures of related compounds, see: Choi et al. (2008, 2010).

Experimental top

3-Chloroperoxybenzoic acid (77%, 202 mg, 0.9 mmol) was added in small portions to a stirred solution of 3-(4-bromophenylsulfanyl)-5-chloro-2-methyl-1-benzofuran (283 mg, 0.8 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 73%, m.p. 395–396 K; R_f = 0.44 (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.

Structure description top

For background information and the crystal structures of related compounds, see: Choi et al. (2008, 2010).

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.
	Fig. 2. A view of the π···π and Br···Br interactions (dotted lines) in the crystal structure of the title compound. H atoms were omitted for clarity. [Symmetry codes: (i) - x, - y, - z + 1; (ii) - x + 1, - y + 1, - z + 2; (iii) - x + 2, - y + 2, - z + 2.]

3-(4-Bromophenylsulfinyl)-5-chloro-2-methyl-1-benzofuran top

Crystal data top

C₁₅H₁₀BrClO₂S	Z = 2
M_r = 369.65	F(000) = 368
Triclinic, P1	D_x = 1.725 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.4192 (1) Å	Cell parameters from 7922 reflections
b = 9.9185 (2) Å	θ = 2.5–28.3°
c = 11.7755 (2) Å	µ = 3.22 mm⁻¹
α = 100.681 (1)°	T = 173 K
β = 92.113 (1)°	Block, colourless
γ = 104.168 (1)°	0.38 × 0.31 × 0.27 mm
V = 711.67 (2) Å³

Data collection top

Bruker SMART APEXII CCD diffractometer	3529 independent reflections
Radiation source: rotating anode	3236 reflections with I > 2σ(I)
Graphite multilayer monochromator	R_int = 0.034
Detector resolution: 10.0 pixels mm^-1	θ_max = 28.3°, θ_min = 1.8°
φ and ω scans	h = −8→8
Absorption correction: multi-scan (SADABS; Bruker, 2009)	k = −13→13
T_min = 0.374, T_max = 0.475	l = −15→15
13131 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)] = 0.031	Hydrogen site location: difference Fourier map
wR(F²) = 0.081	H-atom parameters constrained
S = 1.12	w = 1/[σ²(F_o²) + (0.0418P)² + 0.3308P] where P = (F_o² + 2F_c²)/3
3529 reflections	(Δ/σ)_max = 0.001
182 parameters	Δρ_max = 0.55 e Å⁻³
0 restraints	Δρ_min = −0.76 e Å⁻³

Crystal data top

C₁₅H₁₀BrClO₂S	γ = 104.168 (1)°
M_r = 369.65	V = 711.67 (2) Å³
Triclinic, P1	Z = 2
a = 6.4192 (1) Å	Mo Kα radiation
b = 9.9185 (2) Å	µ = 3.22 mm⁻¹
c = 11.7755 (2) Å	T = 173 K
α = 100.681 (1)°	0.38 × 0.31 × 0.27 mm
β = 92.113 (1)°

Data collection top

Bruker SMART APEXII CCD diffractometer	3529 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	3236 reflections with I > 2σ(I)
T_min = 0.374, T_max = 0.475	R_int = 0.034
13131 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.081	H-atom parameters constrained
S = 1.12	Δρ_max = 0.55 e Å⁻³
3529 reflections	Δρ_min = −0.76 e Å⁻³
182 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	0.73945 (4)	0.92053 (2)	0.917091 (18)	0.03412 (8)
Cl1	−0.34796 (9)	0.39254 (7)	0.44410 (7)	0.05267 (19)
S1	0.18432 (8)	0.27154 (5)	0.84285 (4)	0.02666 (11)
O1	0.3068 (2)	0.10245 (15)	0.53223 (12)	0.0280 (3)
O2	−0.0436 (3)	0.27377 (19)	0.86385 (15)	0.0408 (4)
C1	0.1970 (3)	0.21347 (19)	0.69398 (16)	0.0221 (3)
C2	0.0811 (3)	0.23994 (19)	0.59651 (16)	0.0218 (3)
C3	−0.0758 (3)	0.3123 (2)	0.58146 (19)	0.0273 (4)
H3	−0.1307	0.3616	0.6456	0.033*
C4	−0.1474 (3)	0.3084 (2)	0.4682 (2)	0.0329 (5)
C5	−0.0676 (4)	0.2384 (3)	0.3725 (2)	0.0381 (5)
H5	−0.1203	0.2402	0.2965	0.046*
C6	0.0869 (4)	0.1664 (3)	0.38686 (19)	0.0353 (5)
H6	0.1427	0.1179	0.3225	0.042*
C7	0.1560 (3)	0.1686 (2)	0.49963 (17)	0.0254 (4)
C8	0.3276 (3)	0.1306 (2)	0.65100 (18)	0.0253 (4)
C9	0.4833 (4)	0.0697 (2)	0.7071 (2)	0.0357 (5)
H9A	0.6304	0.1255	0.7026	0.054*
H9B	0.4668	−0.0287	0.6672	0.054*
H9C	0.4555	0.0720	0.7886	0.054*
C10	0.3331 (3)	0.4532 (2)	0.85442 (15)	0.0222 (3)
C11	0.2396 (3)	0.5607 (2)	0.89910 (18)	0.0283 (4)
H11	0.0936	0.5387	0.9172	0.034*
C12	0.3588 (3)	0.7010 (2)	0.91761 (18)	0.0296 (4)
H12	0.2961	0.7758	0.9486	0.036*
C13	0.5709 (3)	0.7301 (2)	0.89001 (16)	0.0247 (4)
C14	0.6662 (3)	0.6227 (2)	0.84636 (19)	0.0294 (4)
H14	0.8119	0.6448	0.8279	0.035*
C15	0.5474 (3)	0.4829 (2)	0.82977 (19)	0.0292 (4)
H15	0.6119	0.4080	0.8018	0.035*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.04322 (14)	0.02544 (12)	0.02911 (12)	0.00304 (9)	0.00126 (9)	0.00208 (8)
Cl1	0.0273 (3)	0.0545 (4)	0.0839 (5)	0.0083 (2)	−0.0072 (3)	0.0384 (4)
S1	0.0281 (2)	0.0293 (2)	0.0188 (2)	0.00123 (18)	0.00349 (17)	0.00343 (18)
O1	0.0258 (7)	0.0302 (7)	0.0268 (7)	0.0092 (6)	0.0044 (5)	−0.0010 (6)
O2	0.0277 (8)	0.0484 (9)	0.0358 (8)	−0.0032 (7)	0.0136 (6)	−0.0022 (7)
C1	0.0210 (8)	0.0223 (8)	0.0210 (8)	0.0032 (7)	0.0012 (7)	0.0024 (7)
C2	0.0194 (8)	0.0224 (8)	0.0214 (8)	0.0020 (7)	0.0022 (7)	0.0032 (7)
C3	0.0207 (9)	0.0270 (9)	0.0344 (10)	0.0038 (7)	0.0034 (7)	0.0090 (8)
C4	0.0203 (9)	0.0330 (10)	0.0460 (12)	0.0002 (8)	−0.0024 (8)	0.0195 (9)
C5	0.0302 (11)	0.0500 (13)	0.0286 (10)	−0.0052 (9)	−0.0063 (8)	0.0165 (10)
C6	0.0338 (11)	0.0448 (12)	0.0215 (9)	0.0014 (9)	0.0033 (8)	0.0035 (9)
C7	0.0208 (8)	0.0290 (9)	0.0233 (9)	0.0024 (7)	0.0026 (7)	0.0025 (7)
C8	0.0220 (9)	0.0233 (8)	0.0283 (9)	0.0030 (7)	0.0014 (7)	0.0032 (7)
C9	0.0286 (10)	0.0325 (11)	0.0471 (13)	0.0110 (8)	−0.0020 (9)	0.0075 (10)
C10	0.0216 (8)	0.0264 (9)	0.0160 (8)	0.0043 (7)	0.0001 (6)	0.0002 (7)
C11	0.0218 (9)	0.0363 (10)	0.0279 (10)	0.0105 (8)	0.0053 (7)	0.0042 (8)
C12	0.0308 (10)	0.0311 (10)	0.0290 (10)	0.0150 (8)	0.0053 (8)	0.0014 (8)
C13	0.0287 (9)	0.0246 (9)	0.0189 (8)	0.0057 (7)	−0.0013 (7)	0.0022 (7)
C14	0.0215 (9)	0.0316 (10)	0.0337 (10)	0.0067 (8)	0.0054 (8)	0.0026 (8)
C15	0.0251 (9)	0.0290 (10)	0.0323 (10)	0.0090 (8)	0.0087 (8)	−0.0005 (8)

Geometric parameters (Å, º) top

Br1—C13	1.895 (2)	C5—H5	0.9500
Br1—Br1ⁱ	3.6446 (4)	C6—C7	1.379 (3)
Cl1—C4	1.738 (2)	C6—H6	0.9500
Cl1—Cl1ⁱⁱ	3.3576 (15)	C8—C9	1.482 (3)
S1—O2	1.4973 (16)	C9—H9A	0.9800
S1—C1	1.7522 (19)	C9—H9B	0.9800
S1—C10	1.798 (2)	C9—H9C	0.9800
O1—C8	1.369 (2)	C10—C11	1.380 (3)
O1—C7	1.375 (2)	C10—C15	1.388 (3)
C1—C8	1.360 (3)	C11—C12	1.387 (3)
C1—C2	1.444 (3)	C11—H11	0.9500
C2—C7	1.393 (3)	C12—C13	1.385 (3)
C2—C3	1.396 (3)	C12—H12	0.9500
C3—C4	1.386 (3)	C13—C14	1.383 (3)
C3—H3	0.9500	C14—C15	1.383 (3)
C4—C5	1.392 (3)	C14—H14	0.9500
C5—C6	1.378 (4)	C15—H15	0.9500

C13—Br1—Br1ⁱ	129.17 (6)	C1—C8—O1	110.68 (17)
C4—Cl1—Cl1ⁱⁱ	147.84 (10)	C1—C8—C9	132.7 (2)
O2—S1—C1	108.52 (9)	O1—C8—C9	116.58 (17)
O2—S1—C10	106.57 (9)	C8—C9—H9A	109.5
C1—S1—C10	98.01 (9)	C8—C9—H9B	109.5
C8—O1—C7	106.55 (14)	H9A—C9—H9B	109.5
C8—C1—C2	107.50 (16)	C8—C9—H9C	109.5
C8—C1—S1	123.01 (15)	H9A—C9—H9C	109.5
C2—C1—S1	129.49 (14)	H9B—C9—H9C	109.5
C7—C2—C3	119.56 (18)	C11—C10—C15	120.93 (18)
C7—C2—C1	104.41 (16)	C11—C10—S1	119.38 (15)
C3—C2—C1	136.02 (18)	C15—C10—S1	119.34 (15)
C4—C3—C2	116.62 (19)	C10—C11—C12	119.95 (18)
C4—C3—H3	121.7	C10—C11—H11	120.0
C2—C3—H3	121.7	C12—C11—H11	120.0
C3—C4—C5	122.8 (2)	C13—C12—C11	118.80 (18)
C3—C4—Cl1	118.67 (18)	C13—C12—H12	120.6
C5—C4—Cl1	118.47 (17)	C11—C12—H12	120.6
C6—C5—C4	120.8 (2)	C14—C13—C12	121.50 (19)
C6—C5—H5	119.6	C14—C13—Br1	118.71 (15)
C4—C5—H5	119.6	C12—C13—Br1	119.75 (15)
C5—C6—C7	116.4 (2)	C13—C14—C15	119.41 (18)
C5—C6—H6	121.8	C13—C14—H14	120.3
C7—C6—H6	121.8	C15—C14—H14	120.3
O1—C7—C6	125.35 (18)	C14—C15—C10	119.37 (18)
O1—C7—C2	110.85 (17)	C14—C15—H15	120.3
C6—C7—C2	123.8 (2)	C10—C15—H15	120.3

O2—S1—C1—C8	−144.10 (17)	C1—C2—C7—C6	−179.82 (19)
C10—S1—C1—C8	105.36 (17)	C2—C1—C8—O1	0.7 (2)
O2—S1—C1—C2	35.8 (2)	S1—C1—C8—O1	−179.37 (13)
C10—S1—C1—C2	−74.70 (18)	C2—C1—C8—C9	179.8 (2)
C8—C1—C2—C7	−0.4 (2)	S1—C1—C8—C9	−0.3 (3)
S1—C1—C2—C7	179.69 (15)	C7—O1—C8—C1	−0.7 (2)
C8—C1—C2—C3	178.4 (2)	C7—O1—C8—C9	−179.98 (17)
S1—C1—C2—C3	−1.6 (3)	O2—S1—C10—C11	11.79 (19)
C7—C2—C3—C4	−0.2 (3)	C1—S1—C10—C11	123.91 (16)
C1—C2—C3—C4	−178.8 (2)	O2—S1—C10—C15	−174.93 (16)
C2—C3—C4—C5	−0.9 (3)	C1—S1—C10—C15	−62.81 (18)
C2—C3—C4—Cl1	178.31 (14)	C15—C10—C11—C12	1.4 (3)
Cl1ⁱⁱ—Cl1—C4—C3	8.9 (3)	S1—C10—C11—C12	174.58 (16)
Cl1ⁱⁱ—Cl1—C4—C5	−171.87 (13)	C10—C11—C12—C13	0.3 (3)
C3—C4—C5—C6	1.1 (3)	C11—C12—C13—C14	−1.0 (3)
Cl1—C4—C5—C6	−178.09 (17)	C11—C12—C13—Br1	−178.79 (15)
C4—C5—C6—C7	−0.2 (3)	Br1ⁱ—Br1—C13—C14	−52.56 (18)
C8—O1—C7—C6	−179.8 (2)	Br1ⁱ—Br1—C13—C12	125.32 (15)
C8—O1—C7—C2	0.5 (2)	C12—C13—C14—C15	0.0 (3)
C5—C6—C7—O1	179.31 (19)	Br1—C13—C14—C15	177.84 (16)
C5—C6—C7—C2	−1.0 (3)	C13—C14—C15—C10	1.7 (3)
C3—C2—C7—O1	−179.05 (16)	C11—C10—C15—C14	−2.4 (3)
C1—C2—C7—O1	−0.1 (2)	S1—C10—C15—C14	−175.55 (16)
C3—C2—C7—C6	1.2 (3)

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

Experimental details

Crystal data
Chemical formula	C₁₅H₁₀BrClO₂S
M_r	369.65
Crystal system, space group	Triclinic, P1
Temperature (K)	173
a, b, c (Å)	6.4192 (1), 9.9185 (2), 11.7755 (2)
α, β, γ (°)	100.681 (1), 92.113 (1), 104.168 (1)
V (Å³)	711.67 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	3.22
Crystal size (mm)	0.38 × 0.31 × 0.27

Data collection
Diffractometer	Bruker SMART APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.374, 0.475
No. of measured, independent and observed [I > 2σ(I)] reflections	13131, 3529, 3236
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.081, 1.12
No. of reflections	3529
No. of parameters	182
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.55, −0.76

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

References

Brandenburg, K. (1998). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2009). APEX2, SADABS and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Choi, H. D., Seo, P. J., Son, B. W. & Lee, U. (2008). Acta Cryst. E64, o1190. Web of Science CSD CrossRef IUCr Journals Google Scholar
Choi, H. D., Seo, P. J., Son, B. W. & Lee, U. (2010). Acta Cryst. E66, o2350. Web of Science CSD CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar