5-Bromo-2,4,6-trimethyl-3-methyl­sulfinyl-1-benzofuran

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

doi:10.1107/S1600536808032467

organic compounds

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ISSN: 2056-9890

Volume 64| Part 11| November 2008| Page o2117

doi:10.1107/S1600536808032467

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5-Bromo-2,4,6-trimethyl-3-methylsulfinyl-1-benzofuran

Hong Dae Choi,^a Pil Ja Seo,^a Byeng Wha Son ^b 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 1 October 2008; accepted 8 October 2008; online 15 October 2008)

In the title compound, C₁₂H₁₃BrO₂S, there are two symmetry-independent molecules, A and B, in the asymmetric unit. The crystal studied was an inversion twin with a 0.70 (2):0.30 (2) domain ratio. The methylsulfinyl group in molecule B is disordered over two positions with site-occupancy factors fixed at 0.6 and 0.4. The crystal structure is stabilized by C—H⋯O hydrogen bonds and intermolecular C—H⋯π interactions. In addition, the crystal structure exhibits C—Br⋯π interactions, with C—Br⋯Cg1 = 3.646 (8) Å where Cg1 is the centroid of the furan ring.

Related literature

For the crystal structures of similar 3-methylsulfinyl-1-benzofuran compounds, see: Choi et al. (2007a ,b ).

Experimental

Crystal data

C₁₂H₁₃BrO₂S
M_r = 301.19
Monoclinic, C c
a = 28.128 (4) Å
b = 11.013 (1) Å
c = 8.052 (1) Å
β = 102.290 (2)°
V = 2437.1 (5) Å³
Z = 8
Mo Kα radiation
μ = 3.53 mm⁻¹
T = 298 (2) K
0.40 × 0.40 × 0.30 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1999 ) T_min = 0.269, T_max = 0.345
7147 measured reflections
4360 independent reflections
3737 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.112
S = 1.09
4360 reflections
317 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.90 e Å⁻³
Absolute structure: Flack (1983 ), 1736 Friedel pairs
Flack parameter: 0.70 (2)

Table 1
Hydrogen-bond geometry (Å, °)

Cg2 is the centroid of the C2–C7 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12A⋯O2ⁱ	0.96	2.34	3.298 (9)	179
C12—H12C⋯O4Bⁱⁱ	0.96	2.42	3.168 (12)	134
C24A—H24A⋯O4Aⁱⁱⁱ	0.96	2.35	3.199 (13)	148
C9—H9A⋯Cg2ⁱⁱⁱ	0.96	3.30	3.943 (9)	124
Symmetry codes: (i) $[x, -y, z-{\script{1\over 2}}]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[x, -y+1, z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2001); 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: 10.1107/S1600536808032467/sj2545sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808032467/sj2545Isup2.hkl

checkCIF report

Comment top

This work is related to our previous communications on the synthesis and structure of 3-methylsulfinyl-1-benzofuran analogues, viz. 5-bromo-2-methyl-3-methylsulfinyl-1-benzofuran (Choi et al., 2007a) and 2,5-dimethyl-3-methylsulfinyl-1-benzofuran (Choi et al., 2007b). Here we report the crystal structure of the title compound, 5-bromo-2,4,6-trimethyl-3-methylsulfinyl-1-benzofuran which crystallizes with two unique molecules, A & B in the asymmetric unit (Fig. 1).

The benzofuran unit is essentially planar, with a mean deviation of 0.012 (6) Å for A and 0.0022 (7) Å for B, respectively, from the least-squares plane defined by the nine constituent atoms. The crystal studied was an inversion twin with a 0.70 (2):0.30 (2) domain ratio. The O4=S2—C24H₃ group in molecule B is disordered over two positions with site-occupancy factors fixed at 0.4 (for atoms labelled A) and 0.6 (for atoms labelled B) in Fig. 1. The crystal structure is stabilized by three intermolecular C—H···O hydrogen bonds (Fig. 2 and Table 1; symmetry codes as in Fig. 2). The molecular packing (Fig. 2) is further stabilized by a intermolecular C—H···π interactions, with a C9—H9A···Cg2ⁱⁱⁱ separation of 3.30 Å (Fig. 2 and Table 1; Cg2 is the centroid of the C2—C7 benzene ring, symmetry code as in Fig. 2). In addition, the molecular packing exhibits an intermolecular C—Br···π interaction between the Br atom and the furan ring, with a C16—Br2···Cg1^iv separation of 3.646 (8) Å (Fig. 2; Cg1 is the centroid of C13—C14/C19/O3/C20 furan ring, symmetry code as in Fig. 2).

Related literature top

For the crystal structures of similar 3-methylsulfinyl-1-benzofuran compounds, see: Choi et al. (2007a,b). Cg2 is the centroid of the C2–C7 benzene ring.

Experimental top

3-Chloroperoxybenzoic acid, 77% (197 mg, 0.88 mmol) was added in small portions to a stirred solution of 3-methylsulfanyl-2-phenyl-1-benzofuran (228 mg, 0.8 mmol) in dichloromethane (30 ml) at 273 K. After stirring for 3 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 under vacuum. The residue was purified by column chromatography (ethyl acetate) to afford the title compound as a colorless solid [yield 79%, m.p. 400–401 K; R_f = 0.61 (ethyl acetate)]. Single crystals suitable for X-ray diffraction were prepared by evaporation of a solution of the title compound in acetone at room temperature. Spectroscopic analysis: ¹H NMR (CDCl₃, 400 MHz) δ 2.51 (s, 3H), 2.68 (s, 3H), 2.83 (s, 3H), 2.95 (s, 3H), 7.21 (s, 1H); EI—MS 302 [M+2], 300 [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 asymmetric unit of the title compound, showing displacement ellipsoids drawn at the 30% probability level. Bonds to atoms of the major disorder component of the disordered methylsulfinyl group are drawn as double dashed lines.
	Fig. 2. C—H···O, C—H···π and C—Br···π interactions (dotted lines) in the title compound. Cg denotes a ring centroid. [Symmetry code: (i) x, -y, z - 1/2; (ii) x - 1/2, -y + 1/2, z + 1/2; (iii) x, -y + 1, z + 1/2; (iv) x, -y, z - 1/2.]

5-Bromo-2,4,6-trimethyl-3-methylsulfinyl-1-benzofuran top

Crystal data top

C₁₂H₁₃BrO₂S	F(000) = 1216
M_r = 301.19	D_x = 1.642 Mg m⁻³
Monoclinic, Cc	Melting point = 401–400 K
Hall symbol: C -2yc	Mo Kα radiation, λ = 0.71073 Å
a = 28.128 (4) Å	Cell parameters from 3249 reflections
b = 11.013 (1) Å	θ = 2.9–26.1°
c = 8.052 (1) Å	µ = 3.53 mm⁻¹
β = 102.290 (2)°	T = 298 K
V = 2437.1 (5) Å³	Block, colorless
Z = 8	0.40 × 0.40 × 0.30 mm

Data collection top

Bruker SMART CCD diffractometer	4360 independent reflections
Radiation source: fine-focus sealed tube	3737 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
Detector resolution: 10.0 pixels mm^-1	θ_max = 27.0°, θ_min = 1.5°
ϕ and ω scans	h = −35→28
Absorption correction: multi-scan (SADABS; Sheldrick, 1999)	k = −14→12
T_min = 0.269, T_max = 0.345	l = −9→10
7147 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.042	H-atom parameters constrained
wR(F²) = 0.112	w = 1/[σ²(F_o²) + (0.0294P)² + 6.0617P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max = 0.001
4360 reflections	Δρ_max = 0.45 e Å⁻³
317 parameters	Δρ_min = −0.90 e Å⁻³
2 restraints	Absolute structure: Flack (1983), 1736 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.70 (2)

Crystal data top

C₁₂H₁₃BrO₂S	V = 2437.1 (5) Å³
M_r = 301.19	Z = 8
Monoclinic, Cc	Mo Kα radiation
a = 28.128 (4) Å	µ = 3.53 mm⁻¹
b = 11.013 (1) Å	T = 298 K
c = 8.052 (1) Å	0.40 × 0.40 × 0.30 mm
β = 102.290 (2)°

Data collection top

Bruker SMART CCD diffractometer	4360 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1999)	3737 reflections with I > 2σ(I)
T_min = 0.269, T_max = 0.345	R_int = 0.020
7147 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	H-atom parameters constrained
wR(F²) = 0.112	Δρ_max = 0.45 e Å⁻³
S = 1.09	Δρ_min = −0.90 e Å⁻³
4360 reflections	Absolute structure: Flack (1983), 1736 Friedel pairs
317 parameters	Absolute structure parameter: 0.70 (2)
2 restraints

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	Occ. (<1)
Br1	0.21922 (3)	0.71294 (6)	0.66785 (9)	0.0659 (2)
Br2	0.50554 (3)	−0.18594 (8)	0.33653 (9)	0.0854 (3)
S1	0.17522 (7)	0.15294 (19)	0.6928 (2)	0.0577 (5)
S2A	0.5460 (2)	0.4107 (6)	0.3537 (10)	0.0523 (16)	0.40
O4A	0.5400 (5)	0.4962 (11)	0.2811 (18)	0.067 (4)	0.40
C24A	0.5884 (2)	0.3483 (7)	0.5252 (9)	0.0616 (19)	0.40
H24A	0.5790	0.3678	0.6298	0.092*	0.40
H24B	0.6201	0.3813	0.5265	0.092*	0.40
H24C	0.5893	0.2617	0.5126	0.092*	0.40
S2B	0.5499 (2)	0.3607 (6)	0.3149 (7)	0.081 (2)	0.60
O4B	0.5586 (3)	0.3734 (12)	0.1963 (14)	0.099 (4)	0.60
C24B	0.5884 (2)	0.3483 (7)	0.5252 (9)	0.0616 (19)	0.60
H24D	0.5945	0.4278	0.5740	0.092*	0.60
H24E	0.6187	0.3109	0.5173	0.092*	0.60
H24F	0.5724	0.2996	0.5957	0.092*	0.60
O1	0.30391 (17)	0.2256 (4)	0.5845 (6)	0.0485 (11)
O2	0.1830 (2)	0.0201 (6)	0.7294 (9)	0.097 (3)
O3	0.42047 (19)	0.2988 (4)	0.4257 (7)	0.0614 (14)
C1	0.2298 (2)	0.2149 (5)	0.6484 (9)	0.0366 (15)
C2	0.2427 (2)	0.3433 (5)	0.6439 (7)	0.0354 (12)
C3	0.2204 (3)	0.4548 (5)	0.6687 (10)	0.0403 (12)
C4	0.2487 (2)	0.5563 (5)	0.6445 (8)	0.0413 (14)
C5	0.2937 (3)	0.5551 (5)	0.6073 (8)	0.0462 (16)
C6	0.3146 (2)	0.4447 (6)	0.5866 (9)	0.0467 (15)
H6	0.3451	0.4398	0.5603	0.056*
C7	0.2887 (2)	0.3417 (5)	0.6061 (8)	0.0412 (14)
C8	0.2665 (3)	0.1512 (6)	0.6131 (9)	0.0485 (17)
C9	0.1720 (2)	0.4603 (6)	0.7129 (10)	0.0507 (17)
H9A	0.1729	0.5172	0.8038	0.076*
H9B	0.1635	0.3814	0.7483	0.076*
H9C	0.1481	0.4858	0.6154	0.076*
C10	0.3211 (3)	0.6695 (7)	0.5822 (11)	0.075 (3)
H10A	0.3019	0.7171	0.4926	0.112*
H10B	0.3514	0.6482	0.5526	0.112*
H10C	0.3275	0.7158	0.6856	0.112*
C11	0.2774 (3)	0.0181 (6)	0.5924 (12)	0.071 (3)
H11A	0.2569	−0.0305	0.6468	0.107*
H11B	0.3109	0.0022	0.6436	0.107*
H11C	0.2715	−0.0017	0.4737	0.107*
C12	0.1395 (2)	0.1660 (6)	0.4814 (9)	0.0512 (15)
H12A	0.1524	0.1130	0.4072	0.077*
H12B	0.1405	0.2483	0.4431	0.077*
H12C	0.1065	0.1437	0.4806	0.077*
C13	0.4940 (3)	0.3120 (8)	0.3690 (11)	0.064 (2)
C14	0.4821 (3)	0.1834 (6)	0.3652 (8)	0.0507 (17)
C15	0.5031 (3)	0.0711 (7)	0.3397 (11)	0.0552 (16)
C16	0.4782 (3)	−0.0334 (7)	0.3580 (10)	0.0565 (19)
C17	0.4301 (3)	−0.0306 (7)	0.4013 (10)	0.059 (2)
C18	0.4098 (3)	0.0785 (7)	0.4214 (10)	0.060 (2)
H18	0.3788	0.0834	0.4447	0.072*
C19	0.4362 (2)	0.1824 (7)	0.4064 (9)	0.0511 (17)
C20	0.4563 (3)	0.3746 (8)	0.4063 (11)	0.065 (2)
C21	0.5530 (3)	0.0662 (10)	0.2927 (12)	0.084 (3)
H21A	0.5767	0.0361	0.3877	0.126*
H21B	0.5622	0.1462	0.2639	0.126*
H21C	0.5515	0.0131	0.1971	0.126*
C22	0.4033 (3)	−0.1465 (8)	0.4158 (11)	0.079 (3)
H22A	0.3716	−0.1282	0.4355	0.118*
H22B	0.4211	−0.1936	0.5089	0.118*
H22C	0.4001	−0.1920	0.3123	0.118*
C23	0.4473 (4)	0.5046 (8)	0.4241 (14)	0.085 (3)
H23A	0.4274	0.5347	0.3204	0.128*
H23B	0.4778	0.5473	0.4477	0.128*
H23C	0.4309	0.5168	0.5158	0.128*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0783 (5)	0.0482 (3)	0.0674 (4)	0.0096 (4)	0.0070 (3)	−0.0056 (3)
Br2	0.0915 (7)	0.0859 (5)	0.0720 (6)	0.0122 (5)	0.0022 (5)	−0.0039 (4)
S1	0.0518 (11)	0.0758 (13)	0.0445 (10)	−0.0326 (9)	0.0081 (8)	0.0092 (8)
S2A	0.026 (2)	0.063 (4)	0.063 (4)	−0.006 (2)	0.000 (2)	0.000 (3)
O4A	0.067 (8)	0.048 (6)	0.085 (10)	−0.015 (6)	0.011 (7)	0.037 (6)
C24A	0.044 (4)	0.080 (4)	0.056 (5)	−0.009 (3)	−0.001 (3)	−0.005 (3)
S2B	0.075 (3)	0.112 (5)	0.053 (3)	−0.062 (3)	0.006 (2)	0.018 (3)
O4B	0.065 (6)	0.163 (11)	0.075 (7)	−0.021 (6)	0.027 (5)	0.026 (7)
C24B	0.044 (4)	0.080 (4)	0.056 (5)	−0.009 (3)	−0.001 (3)	−0.005 (3)
O1	0.040 (3)	0.041 (2)	0.066 (3)	0.0064 (17)	0.013 (2)	0.0089 (19)
O2	0.091 (5)	0.082 (4)	0.103 (5)	−0.044 (4)	−0.015 (4)	0.058 (4)
O3	0.038 (3)	0.068 (3)	0.075 (4)	−0.005 (2)	0.005 (2)	0.004 (2)
C1	0.035 (4)	0.040 (3)	0.036 (3)	−0.013 (2)	0.009 (3)	0.006 (2)
C2	0.024 (3)	0.046 (3)	0.033 (3)	−0.008 (2)	0.000 (2)	0.002 (2)
C3	0.029 (3)	0.055 (3)	0.034 (3)	−0.006 (3)	0.000 (2)	−0.001 (3)
C4	0.041 (4)	0.045 (3)	0.036 (3)	−0.009 (3)	0.005 (3)	0.000 (2)
C5	0.049 (4)	0.044 (3)	0.043 (4)	−0.013 (3)	0.003 (3)	−0.002 (2)
C6	0.030 (3)	0.059 (4)	0.052 (4)	−0.014 (3)	0.010 (3)	0.004 (3)
C7	0.037 (3)	0.041 (3)	0.044 (3)	−0.005 (2)	0.006 (3)	0.004 (2)
C8	0.051 (4)	0.043 (4)	0.045 (4)	−0.006 (3)	−0.003 (3)	0.003 (3)
C9	0.041 (4)	0.058 (4)	0.055 (4)	0.000 (3)	0.015 (3)	−0.008 (3)
C10	0.069 (6)	0.061 (4)	0.090 (6)	−0.035 (4)	0.010 (5)	0.016 (4)
C11	0.078 (6)	0.045 (4)	0.082 (6)	−0.005 (4)	−0.002 (5)	0.007 (4)
C12	0.038 (4)	0.058 (3)	0.056 (4)	−0.012 (3)	0.008 (3)	−0.007 (3)
C13	0.043 (5)	0.084 (5)	0.058 (5)	−0.020 (3)	−0.004 (4)	0.016 (4)
C14	0.042 (4)	0.069 (4)	0.040 (4)	−0.021 (3)	0.004 (3)	0.009 (3)
C15	0.043 (4)	0.087 (5)	0.035 (3)	−0.005 (4)	0.008 (3)	0.008 (4)
C16	0.046 (4)	0.070 (4)	0.046 (4)	−0.001 (3)	−0.005 (3)	0.003 (3)
C17	0.047 (5)	0.066 (4)	0.061 (5)	−0.017 (3)	0.003 (4)	0.011 (3)
C18	0.038 (4)	0.072 (5)	0.067 (5)	−0.022 (3)	0.007 (3)	0.009 (3)
C19	0.029 (3)	0.070 (4)	0.051 (4)	−0.015 (3)	0.001 (3)	0.007 (3)
C20	0.047 (4)	0.081 (5)	0.066 (5)	−0.014 (4)	0.006 (4)	0.006 (4)
C21	0.055 (5)	0.132 (9)	0.069 (6)	−0.004 (5)	0.023 (4)	−0.006 (5)
C22	0.073 (6)	0.089 (6)	0.068 (5)	−0.039 (5)	0.004 (4)	0.014 (4)
C23	0.096 (7)	0.070 (6)	0.089 (7)	−0.019 (5)	0.018 (6)	−0.001 (5)

Geometric parameters (Å, º) top

Br1—C4	1.941 (6)	C9—H9C	0.9600
Br2—C16	1.871 (8)	C10—H10A	0.9600
S1—O2	1.499 (7)	C10—H10B	0.9600
S1—C1	1.783 (6)	C10—H10C	0.9600
S1—C12	1.788 (7)	C11—H11A	0.9600
S2A—O4A	1.102 (13)	C11—H11B	0.9600
S2A—C24A	1.761 (10)	C11—H11C	0.9600
S2A—C13	1.848 (10)	C12—H12A	0.9600
C24A—H24A	0.9600	C12—H12B	0.9600
C24A—H24B	0.9600	C12—H12C	0.9600
C24A—H24C	0.9600	C13—C20	1.352 (14)
S2B—O4B	1.044 (11)	C13—C14	1.454 (10)
S2B—C13	1.801 (10)	C14—C19	1.401 (10)
O1—C7	1.372 (7)	C14—C15	1.405 (11)
O1—C8	1.392 (9)	C15—C16	1.372 (10)
O3—C20	1.344 (10)	C15—C21	1.530 (12)
O3—C19	1.375 (10)	C16—C17	1.469 (12)
C1—C8	1.328 (10)	C17—C18	1.355 (11)
C1—C2	1.462 (7)	C17—C22	1.498 (10)
C2—C7	1.389 (9)	C18—C19	1.383 (9)
C2—C3	1.413 (9)	C18—H18	0.9300
C3—C4	1.411 (9)	C20—C23	1.466 (12)
C3—C9	1.479 (11)	C21—H21A	0.9600
C4—C5	1.362 (10)	C21—H21B	0.9600
C5—C6	1.375 (9)	C21—H21C	0.9600
C5—C10	1.513 (8)	C22—H22A	0.9600
C6—C7	1.375 (8)	C22—H22B	0.9600
C6—H6	0.9300	C22—H22C	0.9600
C8—C11	1.514 (10)	C23—H23A	0.9600
C9—H9A	0.9600	C23—H23B	0.9600
C9—H9B	0.9600	C23—H23C	0.9600

O2—S1—C1	108.4 (4)	S1—C12—H12A	109.5
O2—S1—C12	107.1 (4)	S1—C12—H12B	109.5
C1—S1—C12	96.4 (3)	H12A—C12—H12B	109.5
O4A—S2A—C24A	138.7 (9)	S1—C12—H12C	109.5
O4A—S2A—C13	120.3 (8)	H12A—C12—H12C	109.5
C24A—S2A—C13	97.6 (5)	H12B—C12—H12C	109.5
O4B—S2B—C13	130.4 (7)	C20—C13—C14	108.3 (7)
C7—O1—C8	105.1 (5)	C20—C13—S2B	132.0 (7)
C20—O3—C19	107.4 (7)	C14—C13—S2B	119.6 (8)
C8—C1—C2	107.2 (5)	C20—C13—S2A	112.6 (7)
C8—C1—S1	125.6 (4)	C14—C13—S2A	138.9 (8)
C2—C1—S1	127.2 (5)	C19—C14—C15	117.8 (6)
C7—C2—C3	120.3 (5)	C19—C14—C13	102.9 (7)
C7—C2—C1	104.1 (5)	C15—C14—C13	139.3 (7)
C3—C2—C1	135.7 (6)	C16—C15—C14	118.8 (7)
C4—C3—C2	112.8 (7)	C16—C15—C21	120.9 (8)
C4—C3—C9	125.2 (6)	C14—C15—C21	120.3 (7)
C2—C3—C9	122.0 (5)	C15—C16—C17	121.8 (7)
C5—C4—C3	127.0 (6)	C15—C16—Br2	120.9 (6)
C5—C4—Br1	117.8 (4)	C17—C16—Br2	117.3 (5)
C3—C4—Br1	115.2 (5)	C18—C17—C16	118.6 (6)
C4—C5—C6	118.4 (5)	C18—C17—C22	121.0 (8)
C4—C5—C10	123.1 (6)	C16—C17—C22	120.3 (8)
C6—C5—C10	118.5 (7)	C17—C18—C19	118.4 (7)
C7—C6—C5	117.7 (6)	C17—C18—H18	120.8
C7—C6—H6	121.1	C19—C18—H18	120.8
C5—C6—H6	121.1	O3—C19—C18	124.8 (7)
O1—C7—C6	124.5 (6)	O3—C19—C14	110.7 (6)
O1—C7—C2	111.7 (5)	C18—C19—C14	124.5 (8)
C6—C7—C2	123.7 (6)	O3—C20—C13	110.6 (7)
C1—C8—O1	112.0 (5)	O3—C20—C23	116.5 (8)
C1—C8—C11	136.1 (7)	C13—C20—C23	132.8 (8)
O1—C8—C11	111.9 (7)	C15—C21—H21A	109.5
C3—C9—H9A	109.5	C15—C21—H21B	109.5
C3—C9—H9B	109.5	H21A—C21—H21B	109.5
H9A—C9—H9B	109.5	C15—C21—H21C	109.5
C3—C9—H9C	109.5	H21A—C21—H21C	109.5
H9A—C9—H9C	109.5	H21B—C21—H21C	109.5
H9B—C9—H9C	109.5	C17—C22—H22A	109.5
C5—C10—H10A	109.5	C17—C22—H22B	109.5
C5—C10—H10B	109.5	H22A—C22—H22B	109.5
H10A—C10—H10B	109.5	C17—C22—H22C	109.5
C5—C10—H10C	109.5	H22A—C22—H22C	109.5
H10A—C10—H10C	109.5	H22B—C22—H22C	109.5
H10B—C10—H10C	109.5	C20—C23—H23A	109.5
C8—C11—H11A	109.5	C20—C23—H23B	109.5
C8—C11—H11B	109.5	H23A—C23—H23B	109.5
H11A—C11—H11B	109.5	C20—C23—H23C	109.5
C8—C11—H11C	109.5	H23A—C23—H23C	109.5
H11A—C11—H11C	109.5	H23B—C23—H23C	109.5
H11B—C11—H11C	109.5

O2—S1—C1—C8	14.9 (8)	O4A—S2A—C13—C14	139.6 (14)
C12—S1—C1—C8	−95.6 (7)	C24A—S2A—C13—C14	−57.7 (11)
O2—S1—C1—C2	−165.0 (6)	O4A—S2A—C13—S2B	115.7 (17)
C12—S1—C1—C2	84.5 (6)	C24A—S2A—C13—S2B	−81.5 (10)
C8—C1—C2—C7	−0.7 (7)	C20—C13—C14—C19	−1.2 (9)
S1—C1—C2—C7	179.2 (5)	S2B—C13—C14—C19	−177.5 (6)
C8—C1—C2—C3	179.8 (8)	S2A—C13—C14—C19	173.1 (9)
S1—C1—C2—C3	−0.3 (11)	C20—C13—C14—C15	−178.4 (9)
C7—C2—C3—C4	2.2 (9)	S2B—C13—C14—C15	5.3 (14)
C1—C2—C3—C4	−178.3 (7)	S2A—C13—C14—C15	−4.2 (18)
C7—C2—C3—C9	−178.6 (7)	C19—C14—C15—C16	−0.7 (11)
C1—C2—C3—C9	0.9 (12)	C13—C14—C15—C16	176.2 (9)
C2—C3—C4—C5	−2.3 (11)	C19—C14—C15—C21	179.4 (7)
C9—C3—C4—C5	178.5 (7)	C13—C14—C15—C21	−3.6 (15)
C2—C3—C4—Br1	177.7 (5)	C14—C15—C16—C17	0.7 (11)
C9—C3—C4—Br1	−1.5 (10)	C21—C15—C16—C17	−179.4 (8)
C3—C4—C5—C6	1.5 (11)	C14—C15—C16—Br2	−176.9 (6)
Br1—C4—C5—C6	−178.6 (4)	C21—C15—C16—Br2	3.0 (10)
C3—C4—C5—C10	179.5 (7)	C15—C16—C17—C18	0.9 (11)
Br1—C4—C5—C10	−0.5 (9)	Br2—C16—C17—C18	178.6 (5)
C4—C5—C6—C7	−0.5 (9)	C15—C16—C17—C22	178.4 (7)
C10—C5—C6—C7	−178.6 (6)	Br2—C16—C17—C22	−3.9 (10)
C8—O1—C7—C6	−178.8 (6)	C16—C17—C18—C19	−2.4 (11)
C8—O1—C7—C2	−1.2 (7)	C22—C17—C18—C19	−179.9 (7)
C5—C6—C7—O1	177.9 (6)	C20—O3—C19—C18	178.4 (7)
C5—C6—C7—C2	0.6 (10)	C20—O3—C19—C14	−3.1 (8)
C3—C2—C7—O1	−179.2 (6)	C17—C18—C19—O3	−179.2 (7)
C1—C2—C7—O1	1.2 (7)	C17—C18—C19—C14	2.6 (11)
C3—C2—C7—C6	−1.5 (10)	C15—C14—C19—O3	−179.4 (6)
C1—C2—C7—C6	178.8 (6)	C13—C14—C19—O3	2.6 (8)
C2—C1—C8—O1	0.0 (8)	C15—C14—C19—C18	−1.0 (11)
S1—C1—C8—O1	−179.9 (5)	C13—C14—C19—C18	−178.9 (7)
C2—C1—C8—C11	−178.3 (8)	C19—O3—C20—C13	2.2 (9)
S1—C1—C8—C11	1.8 (13)	C19—O3—C20—C23	−179.3 (7)
C7—O1—C8—C1	0.7 (8)	C14—C13—C20—O3	−0.6 (10)
C7—O1—C8—C11	179.5 (6)	S2B—C13—C20—O3	175.1 (7)
O4B—S2B—C13—C20	−94.9 (16)	S2A—C13—C20—O3	−176.5 (6)
O4B—S2B—C13—C14	80.3 (15)	C14—C13—C20—C23	−178.7 (9)
O4B—S2B—C13—S2A	−117.4 (19)	S2B—C13—C20—C23	−3.1 (16)
O4A—S2A—C13—C20	−46.3 (13)	S2A—C13—C20—C23	5.3 (13)
C24A—S2A—C13—C20	116.4 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12A···O2ⁱ	0.96	2.34	3.298 (9)	179
C12—H12C···O4Bⁱⁱ	0.96	2.42	3.168 (12)	134
C24A—H24A···O4Aⁱⁱⁱ	0.96	2.35	3.199 (13)	148
C9—H9A···Cg2ⁱⁱⁱ	0.96	3.30	3.943 (9)	124

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

Experimental details

Crystal data
Chemical formula	C₁₂H₁₃BrO₂S
M_r	301.19
Crystal system, space group	Monoclinic, Cc
Temperature (K)	298
a, b, c (Å)	28.128 (4), 11.013 (1), 8.052 (1)
β (°)	102.290 (2)
V (Å³)	2437.1 (5)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	3.53
Crystal size (mm)	0.40 × 0.40 × 0.30

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1999)
T_min, T_max	0.269, 0.345
No. of measured, independent and observed [I > 2σ(I)] reflections	7147, 4360, 3737
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.112, 1.09
No. of reflections	4360
No. of parameters	317
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.45, −0.90
Absolute structure	Flack (1983), 1736 Friedel pairs
Absolute structure parameter	0.70 (2)

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), 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
C12—H12A···O2ⁱ	0.96	2.34	3.298 (9)	178.6
C12—H12C···O4Bⁱⁱ	0.96	2.42	3.168 (12)	134.4
C24A—H24A···O4Aⁱⁱⁱ	0.96	2.35	3.199 (13)	147.8
C9—H9A···Cg2ⁱⁱⁱ	0.96	3.30	3.943 (9)	123.6

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

References

Brandenburg, K. (1998). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2001). SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Choi, H. D., Seo, P. J., Son, B. W. & Lee, U. (2007a). Acta Cryst. E63, o521–o522. Web of Science CSD CrossRef IUCr Journals Google Scholar
Choi, H. D., Seo, P. J., Son, B. W. & Lee, U. (2007b). Acta Cryst. E63, o1823–o1824. Web of Science CSD CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Sheldrick, G. M. (1999). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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Volume 64| Part 11| November 2008| Page o2117

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