Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807048672/lw2038sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807048672/lw2038Isup2.hkl |
CCDC reference: 669135
3-Chloroperbenzoic acid (77%, 359 mg, 1.60 mmol) was added in small portions to a stirred solution of 2-(4-bromophenyl)-5,7-dimethyl-3-methyl-sulfanyl-1-benzofuran (521 mg, 1.50 mmol) in dichloromethane (30 ml) at 273 K. After being stirred at room temperature for 2 h, 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, 1:1 v/v) to afford the title compound as a colorless solid [yield 83%, m.p. 451–452 K; Rf = 0.65 (hexane-ethyl acetate, 1:1 v/v)]. Single crystals suitable for X-ray diffraction were prepared by slow evaporation of a dilute solution of the title compound in chloroform at room temperature.
All H atoms were geometrically located in ideal positions and refined using a riding model, with C—H = 0.95 Å for aromatic H atoms and 0.98 Å for methyl H atoms, and with Uiso(H) = 1.2Ueq(C) for aromatic and 1.5Ueq(C) for methyl H atoms.
As part of our ongoing studies on the synthesis and structure of 2-aryl-5-methyl-3-methylsulfinyl-1-benzofuran analogues, we have recently described 5-methyl-3-methylsulfinyl-2-phenyl-1-benzofuran (Choi et al., 2007a) and 2-(4-bromophenyl)-5-methyl-3-methylsulfinyl-1-benzofuran (Choi et al., 2007b). Herein we report the molecular and crystal structure of the title compound, 2-(4-bromophenyl)-5,7-dimethyl-3-methylsulfinyl-1-benzofuran (Fig. 1).
The benzofuran unit is essentially planar, with a mean deviation of 0.014 Å from the least-squares plane defined by the nine constituent atoms. In the title compound, the dihedral angle between the plane of the benzofuran and the 4-bromophenyl ring is 19.3 (2)°. The molecular packing is stabilized by a C—H···O hydrogen bond; between a methyl H and the S═O unit, i.e. C16—H16A···O2i (Table 1 & Fig. 2). The further stability comes from a weak C—Br···O halogen bond (Fig. 2) (Politzer et al., 2007); between the bromine atom and the oxygen of a neighbouring S═O unit, i.e. C12—Br···O2ii distance of 3.209 (6) Å and a nearly linear C—Br···O angle of 165.1 (2) Å (Symmetry codes as in Fig. 2).
For crystal structures of isomers of the title compound, see: Choi et al. (2007a,b). For a review of halogen bonding, see: Politzer et al. (2007).
Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 1998); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
C17H15BrO2S | Z = 2 |
Mr = 363.26 | F(000) = 368 |
Triclinic, P1 | Dx = 1.531 Mg m−3 |
Hall symbol: -p 1 | Melting point = 451–452 K |
a = 7.9802 (4) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.1652 (4) Å | Cell parameters from 3012 reflections |
c = 11.6042 (4) Å | θ = 2.6–22.3° |
α = 103.104 (3)° | µ = 2.74 mm−1 |
β = 91.737 (3)° | T = 298 K |
γ = 106.648 (3)° | Block, colourless |
V = 787.84 (6) Å3 | 0.24 × 0.20 × 0.12 mm |
Bruker SMART CCD diffractometer | 2736 independent reflections |
Radiation source: fine-focus sealed tube | 2061 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.031 |
Detector resolution: 10.0 pixels mm-1 | θmax = 25.0°, θmin = 1.8° |
φ and ω scans | h = −9→9 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2000) | k = −10→10 |
Tmin = 0.519, Tmax = 0.715 | l = −12→13 |
10316 measured reflections |
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)] = 0.055 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.168 | H-atom parameters constrained |
S = 1.13 | w = 1/[σ2(Fo2) + (0.0641P)2 + 1.64P] where P = (Fo2 + 2Fc2)/3 |
2736 reflections | (Δ/σ)max < 0.001 |
193 parameters | Δρmax = 0.78 e Å−3 |
0 restraints | Δρmin = −0.41 e Å−3 |
C17H15BrO2S | γ = 106.648 (3)° |
Mr = 363.26 | V = 787.84 (6) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.9802 (4) Å | Mo Kα radiation |
b = 9.1652 (4) Å | µ = 2.74 mm−1 |
c = 11.6042 (4) Å | T = 298 K |
α = 103.104 (3)° | 0.24 × 0.20 × 0.12 mm |
β = 91.737 (3)° |
Bruker SMART CCD diffractometer | 2736 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2000) | 2061 reflections with I > 2σ(I) |
Tmin = 0.519, Tmax = 0.715 | Rint = 0.031 |
10316 measured reflections |
R[F2 > 2σ(F2)] = 0.055 | 0 restraints |
wR(F2) = 0.168 | H-atom parameters constrained |
S = 1.13 | Δρmax = 0.78 e Å−3 |
2736 reflections | Δρmin = −0.41 e Å−3 |
193 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Br | 0.24607 (10) | 0.77634 (9) | 0.54104 (6) | 0.0801 (3) | |
S | 0.4003 (2) | 0.80276 (18) | −0.08002 (15) | 0.0678 (5) | |
O1 | 0.1883 (5) | 0.3767 (4) | −0.0363 (4) | 0.0616 (10) | |
O2 | 0.2966 (8) | 0.8282 (6) | −0.1757 (5) | 0.0988 (17) | |
C1 | 0.3260 (7) | 0.6002 (6) | −0.0870 (5) | 0.0561 (14) | |
C2 | 0.2894 (7) | 0.4718 (7) | −0.1935 (5) | 0.0559 (14) | |
C3 | 0.3138 (8) | 0.4579 (7) | −0.3137 (6) | 0.0626 (15) | |
H3 | 0.3701 | 0.5454 | −0.3411 | 0.075* | |
C4 | 0.2525 (8) | 0.3116 (8) | −0.3901 (6) | 0.0671 (16) | |
C5 | 0.1636 (8) | 0.1822 (8) | −0.3474 (6) | 0.0707 (18) | |
H5 | 0.1211 | 0.0849 | −0.4015 | 0.085* | |
C6 | 0.1352 (8) | 0.1907 (7) | −0.2292 (6) | 0.0621 (15) | |
C7 | 0.2024 (7) | 0.3401 (7) | −0.1565 (5) | 0.0593 (14) | |
C8 | 0.2648 (7) | 0.5352 (6) | 0.0048 (5) | 0.0555 (14) | |
C9 | 0.2613 (7) | 0.5978 (7) | 0.1328 (5) | 0.0562 (14) | |
C10 | 0.1400 (8) | 0.5092 (7) | 0.1941 (6) | 0.0626 (15) | |
H10 | 0.0624 | 0.4130 | 0.1534 | 0.075* | |
C11 | 0.1346 (8) | 0.5633 (8) | 0.3141 (6) | 0.0636 (15) | |
H11 | 0.0548 | 0.5030 | 0.3545 | 0.076* | |
C12 | 0.2480 (8) | 0.7075 (7) | 0.3748 (5) | 0.0601 (14) | |
C13 | 0.3688 (9) | 0.7959 (8) | 0.3167 (6) | 0.0676 (16) | |
H13 | 0.4454 | 0.8923 | 0.3578 | 0.081* | |
C14 | 0.3755 (8) | 0.7397 (7) | 0.1955 (6) | 0.0651 (16) | |
H14 | 0.4584 | 0.7988 | 0.1562 | 0.078* | |
C15 | 0.2770 (10) | 0.2897 (10) | −0.5207 (6) | 0.086 (2) | |
H15A | 0.1642 | 0.2483 | −0.5665 | 0.129* | |
H15B | 0.3441 | 0.2178 | −0.5429 | 0.129* | |
H15C | 0.3383 | 0.3891 | −0.5357 | 0.129* | |
C16 | 0.0351 (10) | 0.0533 (8) | −0.1832 (7) | 0.087 (2) | |
H16A | 0.1152 | 0.0027 | −0.1589 | 0.130* | |
H16B | −0.0507 | −0.0201 | −0.2448 | 0.130* | |
H16C | −0.0231 | 0.0897 | −0.1163 | 0.130* | |
C17 | 0.6124 (10) | 0.8137 (9) | −0.1298 (8) | 0.093 (2) | |
H17A | 0.6019 | 0.7284 | −0.1979 | 0.139* | |
H17B | 0.6892 | 0.8070 | −0.0672 | 0.139* | |
H17C | 0.6600 | 0.9117 | −0.1510 | 0.139* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br | 0.0910 (6) | 0.0872 (5) | 0.0626 (4) | 0.0333 (4) | 0.0112 (3) | 0.0107 (3) |
S | 0.0821 (11) | 0.0505 (8) | 0.0690 (10) | 0.0158 (8) | 0.0107 (8) | 0.0162 (7) |
O1 | 0.059 (2) | 0.053 (2) | 0.069 (3) | 0.0082 (18) | 0.0044 (19) | 0.018 (2) |
O2 | 0.123 (4) | 0.087 (4) | 0.099 (4) | 0.046 (3) | −0.008 (3) | 0.034 (3) |
C1 | 0.058 (3) | 0.047 (3) | 0.061 (3) | 0.013 (3) | 0.006 (3) | 0.010 (3) |
C2 | 0.049 (3) | 0.051 (3) | 0.066 (4) | 0.014 (3) | 0.006 (3) | 0.013 (3) |
C3 | 0.059 (4) | 0.063 (4) | 0.065 (4) | 0.020 (3) | 0.006 (3) | 0.014 (3) |
C4 | 0.057 (4) | 0.070 (4) | 0.069 (4) | 0.023 (3) | 0.006 (3) | 0.002 (3) |
C5 | 0.060 (4) | 0.061 (4) | 0.077 (4) | 0.018 (3) | −0.002 (3) | −0.008 (3) |
C6 | 0.052 (3) | 0.049 (3) | 0.078 (4) | 0.014 (3) | 0.001 (3) | 0.005 (3) |
C7 | 0.053 (3) | 0.059 (4) | 0.063 (4) | 0.015 (3) | 0.007 (3) | 0.010 (3) |
C8 | 0.051 (3) | 0.049 (3) | 0.062 (4) | 0.012 (2) | 0.000 (3) | 0.011 (3) |
C9 | 0.051 (3) | 0.061 (3) | 0.057 (3) | 0.015 (3) | 0.003 (3) | 0.017 (3) |
C10 | 0.052 (3) | 0.063 (4) | 0.068 (4) | 0.011 (3) | 0.004 (3) | 0.014 (3) |
C11 | 0.062 (4) | 0.072 (4) | 0.062 (4) | 0.022 (3) | 0.014 (3) | 0.023 (3) |
C12 | 0.062 (4) | 0.064 (4) | 0.058 (3) | 0.026 (3) | 0.003 (3) | 0.015 (3) |
C13 | 0.070 (4) | 0.060 (4) | 0.063 (4) | 0.014 (3) | −0.006 (3) | 0.007 (3) |
C14 | 0.057 (4) | 0.061 (4) | 0.072 (4) | 0.009 (3) | 0.003 (3) | 0.019 (3) |
C15 | 0.083 (5) | 0.095 (5) | 0.073 (5) | 0.027 (4) | 0.008 (4) | 0.008 (4) |
C16 | 0.082 (5) | 0.058 (4) | 0.103 (6) | −0.001 (4) | 0.005 (4) | 0.012 (4) |
C17 | 0.077 (5) | 0.069 (4) | 0.125 (7) | 0.005 (4) | 0.020 (5) | 0.029 (4) |
Br—C12 | 1.891 (6) | C9—C14 | 1.379 (8) |
Br—O2i | 3.209 (6) | C9—C10 | 1.399 (8) |
S—O2 | 1.464 (5) | C10—C11 | 1.374 (8) |
S—C1 | 1.762 (6) | C10—H10 | 0.9300 |
S—C17 | 1.788 (8) | C11—C12 | 1.384 (9) |
O1—C8 | 1.368 (7) | C11—H11 | 0.9300 |
O1—C7 | 1.375 (7) | C12—C13 | 1.371 (9) |
C1—C8 | 1.371 (8) | C13—C14 | 1.392 (9) |
C1—C2 | 1.456 (8) | C13—H13 | 0.9300 |
C2—C7 | 1.378 (8) | C14—H14 | 0.9300 |
C2—C3 | 1.396 (8) | C15—H15A | 0.9600 |
C3—C4 | 1.372 (9) | C15—H15B | 0.9600 |
C3—H3 | 0.9300 | C15—H15C | 0.9600 |
C4—C5 | 1.400 (10) | C16—H16A | 0.9600 |
C4—C15 | 1.509 (10) | C16—H16B | 0.9600 |
C5—C6 | 1.385 (9) | C16—H16C | 0.9600 |
C5—H5 | 0.9300 | C17—H17A | 0.9600 |
C6—C7 | 1.380 (8) | C17—H17B | 0.9600 |
C6—C16 | 1.505 (9) | C17—H17C | 0.9600 |
C8—C9 | 1.470 (8) | ||
C12—Br—O2i | 165.1 (2) | C11—C10—H10 | 119.8 |
O2—S—C1 | 106.6 (3) | C9—C10—H10 | 119.8 |
O2—S—C17 | 106.1 (4) | C10—C11—C12 | 120.0 (6) |
C1—S—C17 | 98.6 (3) | C10—C11—H11 | 120.0 |
C8—O1—C7 | 107.1 (4) | C12—C11—H11 | 120.0 |
C8—C1—C2 | 106.9 (5) | C13—C12—C11 | 120.5 (6) |
C8—C1—S | 125.5 (4) | C13—C12—Br | 119.8 (5) |
C2—C1—S | 126.8 (4) | C11—C12—Br | 119.5 (5) |
C7—C2—C3 | 119.3 (6) | C12—C13—C14 | 119.3 (6) |
C7—C2—C1 | 104.7 (5) | C12—C13—H13 | 120.3 |
C3—C2—C1 | 135.9 (5) | C14—C13—H13 | 120.3 |
C4—C3—C2 | 118.2 (6) | C9—C14—C13 | 121.1 (6) |
C4—C3—H3 | 120.9 | C9—C14—H14 | 119.4 |
C2—C3—H3 | 120.9 | C13—C14—H14 | 119.4 |
C3—C4—C5 | 120.0 (6) | C4—C15—H15A | 109.5 |
C3—C4—C15 | 120.3 (7) | C4—C15—H15B | 109.5 |
C5—C4—C15 | 119.7 (6) | H15A—C15—H15B | 109.5 |
C6—C5—C4 | 123.8 (6) | C4—C15—H15C | 109.5 |
C6—C5—H5 | 118.1 | H15A—C15—H15C | 109.5 |
C4—C5—H5 | 118.1 | H15B—C15—H15C | 109.5 |
C7—C6—C5 | 113.5 (6) | C6—C16—H16A | 109.5 |
C7—C6—C16 | 122.2 (6) | C6—C16—H16B | 109.5 |
C5—C6—C16 | 124.2 (6) | H16A—C16—H16B | 109.5 |
O1—C7—C2 | 111.1 (5) | C6—C16—H16C | 109.5 |
O1—C7—C6 | 123.7 (5) | H16A—C16—H16C | 109.5 |
C2—C7—C6 | 125.2 (6) | H16B—C16—H16C | 109.5 |
O1—C8—C1 | 110.2 (5) | S—C17—H17A | 109.5 |
O1—C8—C9 | 115.2 (5) | S—C17—H17B | 109.5 |
C1—C8—C9 | 134.6 (5) | H17A—C17—H17B | 109.5 |
C14—C9—C10 | 118.5 (6) | S—C17—H17C | 109.5 |
C14—C9—C8 | 122.5 (5) | H17A—C17—H17C | 109.5 |
C10—C9—C8 | 119.0 (5) | H17B—C17—H17C | 109.5 |
C11—C10—C9 | 120.5 (6) | ||
O2—S—C1—C8 | −124.5 (6) | C16—C6—C7—O1 | 1.6 (10) |
C17—S—C1—C8 | 125.7 (6) | C5—C6—C7—C2 | 0.3 (9) |
O2—S—C1—C2 | 44.1 (6) | C16—C6—C7—C2 | −177.5 (6) |
C17—S—C1—C2 | −65.7 (6) | C7—O1—C8—C1 | 0.5 (6) |
C8—C1—C2—C7 | 2.2 (6) | C7—O1—C8—C9 | 179.5 (5) |
S—C1—C2—C7 | −168.1 (5) | C2—C1—C8—O1 | −1.7 (6) |
C8—C1—C2—C3 | 178.5 (7) | S—C1—C8—O1 | 168.8 (4) |
S—C1—C2—C3 | 8.1 (10) | C2—C1—C8—C9 | 179.6 (6) |
C7—C2—C3—C4 | −1.3 (9) | S—C1—C8—C9 | −9.9 (10) |
C1—C2—C3—C4 | −177.1 (6) | O1—C8—C9—C14 | 159.4 (5) |
C2—C3—C4—C5 | 1.9 (9) | C1—C8—C9—C14 | −21.9 (10) |
C2—C3—C4—C15 | −179.4 (6) | O1—C8—C9—C10 | −19.5 (8) |
C3—C4—C5—C6 | −1.5 (10) | C1—C8—C9—C10 | 159.2 (7) |
C15—C4—C5—C6 | 179.8 (6) | C14—C9—C10—C11 | 0.3 (9) |
C4—C5—C6—C7 | 0.3 (9) | C8—C9—C10—C11 | 179.2 (6) |
C4—C5—C6—C16 | 178.1 (6) | C9—C10—C11—C12 | 1.0 (9) |
C8—O1—C7—C2 | 1.0 (6) | C10—C11—C12—C13 | −1.4 (9) |
C8—O1—C7—C6 | −178.2 (6) | C10—C11—C12—Br | −177.3 (5) |
C3—C2—C7—O1 | −179.0 (5) | C11—C12—C13—C14 | 0.5 (9) |
C1—C2—C7—O1 | −2.0 (6) | Br—C12—C13—C14 | 176.4 (5) |
C3—C2—C7—C6 | 0.1 (9) | C10—C9—C14—C13 | −1.2 (9) |
C1—C2—C7—C6 | 177.2 (6) | C8—C9—C14—C13 | 179.9 (6) |
C5—C6—C7—O1 | 179.4 (5) | C12—C13—C14—C9 | 0.8 (10) |
Symmetry code: (i) x, y, z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C16—H16A···O2ii | 0.96 | 2.43 | 3.340 (10) | 159 |
Symmetry code: (ii) x, y−1, z. |
Experimental details
Crystal data | |
Chemical formula | C17H15BrO2S |
Mr | 363.26 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 298 |
a, b, c (Å) | 7.9802 (4), 9.1652 (4), 11.6042 (4) |
α, β, γ (°) | 103.104 (3), 91.737 (3), 106.648 (3) |
V (Å3) | 787.84 (6) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 2.74 |
Crystal size (mm) | 0.24 × 0.20 × 0.12 |
Data collection | |
Diffractometer | Bruker SMART CCD |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2000) |
Tmin, Tmax | 0.519, 0.715 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10316, 2736, 2061 |
Rint | 0.031 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.055, 0.168, 1.13 |
No. of reflections | 2736 |
No. of parameters | 193 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.78, −0.41 |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 1998).
D—H···A | D—H | H···A | D···A | D—H···A |
C16—H16A···O2i | 0.96 | 2.43 | 3.340 (10) | 158.7 |
Symmetry code: (i) x, y−1, z. |
As part of our ongoing studies on the synthesis and structure of 2-aryl-5-methyl-3-methylsulfinyl-1-benzofuran analogues, we have recently described 5-methyl-3-methylsulfinyl-2-phenyl-1-benzofuran (Choi et al., 2007a) and 2-(4-bromophenyl)-5-methyl-3-methylsulfinyl-1-benzofuran (Choi et al., 2007b). Herein we report the molecular and crystal structure of the title compound, 2-(4-bromophenyl)-5,7-dimethyl-3-methylsulfinyl-1-benzofuran (Fig. 1).
The benzofuran unit is essentially planar, with a mean deviation of 0.014 Å from the least-squares plane defined by the nine constituent atoms. In the title compound, the dihedral angle between the plane of the benzofuran and the 4-bromophenyl ring is 19.3 (2)°. The molecular packing is stabilized by a C—H···O hydrogen bond; between a methyl H and the S═O unit, i.e. C16—H16A···O2i (Table 1 & Fig. 2). The further stability comes from a weak C—Br···O halogen bond (Fig. 2) (Politzer et al., 2007); between the bromine atom and the oxygen of a neighbouring S═O unit, i.e. C12—Br···O2ii distance of 3.209 (6) Å and a nearly linear C—Br···O angle of 165.1 (2) Å (Symmetry codes as in Fig. 2).