Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807032199/sg2178sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807032199/sg2178Isup2.hkl |
CCDC reference: 657706
3-Chloroperbenzoic acid (77%, 291 mg, 1.30 mmol) was added in small portions to a stirred solution of 2-methyl-5-phenyl-3-phenylsulfanyl-1-benzofuran (379 mg, 1.20 mmol) in dichloromethane (30 ml) at 273 K. After being stirred at room temperature for 1hr, the mixture was washed with saturated sodium bicarbonate solution and the organic layer 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 78%, m.p. 425–426 K; Rf = 0.51 (hexane-ethyl acetate, 1:1 v/v)]. Single crystals suitable for X-ray diffraction were prepared by slow evaporation of a dilute solution of title compound (I) in acetone at room temperature.
All H atoms were geometrically located in ideal positions and refined using a riding model, with C—H = 0.93 Å for aromatic H atoms and C—H = 0.96 Å for methyl H atoms, and with Uiso(H) = 1.2Ueq(C) for aromatic H atoms, and Uiso(H) = 1.5Ueq(C) for methyl H atoms. The highest peak in the difference map is 1.21 Å from S and the largest hole is 0.34 Å from S.
As part of our continuing studies on the synthesis and structure of 5-phenyl-1-benzofuran analogues, the crystal structures of 3-methylsulfanyl-2,5-diphenyl-1-benzofuran (Choi, Seo, Kang et al., 2006) and 2-methyl-3-methylsulfinyl-5-phenyl-1-benzofuran (Choi, Seo, Lee et al., 2006) have been described to the literature. Herein we report the molecular and crystal structure of the title compound (I) (Fig. 1).
The benzofuran unit is essentially planar, with a mean deviation of 0.008 Å from the least-squares plane defined by the nine constituent atoms. The dihedral angle in (I) formed by the plane of the benzofuran ring and the plane of 5-phenyl ring is 21.0 (1)° and phenyl ring(C15—C20) with 80.4 (6)° lies toward benzofuran plane. The molecular packing (Fig. 2) is stabilized by CH2—H···π interactions between the methyl group and the benzene ring of benzofuran unit, with a C21—H21B···Cg1i separation of 2.94 Å. (Cg1 is the centroid of the C3—C8 benzene ring, symmetry code as in Fig. 2).
For the crystal structures of the isomers of the title compound, see: Choi, Seo, Kang et al. (2006); Choi, Seo, Lee et al. (2006).
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; 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.
C21H16O2S | F(000) = 696 |
Mr = 332.40 | Dx = 1.371 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -p_2yn | Cell parameters from 6665 reflections |
a = 9.8919 (5) Å | θ = 2.4–28.3° |
b = 9.6229 (5) Å | µ = 0.21 mm−1 |
c = 16.9226 (9) Å | T = 173 K |
β = 91.685 (1)° | Block, colorless |
V = 1610.15 (14) Å3 | 0.65 × 0.42 × 0.35 mm |
Z = 4 |
Bruker SMART CCD diffractometer | 2942 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.030 |
Graphite monochromator | θmax = 26.0°, θmin = 2.4° |
Detector resolution: 10.00 pixels mm-1 | h = −12→12 |
φ and ω scans | k = −11→10 |
8853 measured reflections | l = −17→20 |
3154 independent 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)] = 0.047 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.111 | H-atom parameters constrained |
S = 1.16 | w = 1/[σ2(Fo2) + (0.042P)2 + 1.3632P] where P = (Fo2 + 2Fc2)/3 |
3154 reflections | (Δ/σ)max < 0.001 |
218 parameters | Δρmax = 0.62 e Å−3 |
0 restraints | Δρmin = −0.41 e Å−3 |
C21H16O2S | V = 1610.15 (14) Å3 |
Mr = 332.40 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.8919 (5) Å | µ = 0.21 mm−1 |
b = 9.6229 (5) Å | T = 173 K |
c = 16.9226 (9) Å | 0.65 × 0.42 × 0.35 mm |
β = 91.685 (1)° |
Bruker SMART CCD diffractometer | 2942 reflections with I > 2σ(I) |
8853 measured reflections | Rint = 0.030 |
3154 independent reflections |
R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
wR(F2) = 0.111 | H-atom parameters constrained |
S = 1.16 | Δρmax = 0.62 e Å−3 |
3154 reflections | Δρmin = −0.41 e Å−3 |
218 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 | ||
S | 0.08659 (5) | 0.14104 (5) | 0.34971 (3) | 0.02305 (15) | |
O1 | 0.45015 (14) | 0.03554 (15) | 0.28292 (8) | 0.0268 (3) | |
O2 | 0.00179 (15) | 0.02393 (16) | 0.37785 (9) | 0.0315 (4) | |
C1 | 0.25122 (19) | 0.0754 (2) | 0.33966 (11) | 0.0216 (4) | |
C2 | 0.3295 (2) | 0.1062 (2) | 0.27759 (11) | 0.0245 (4) | |
C3 | 0.4471 (2) | −0.0421 (2) | 0.35150 (11) | 0.0228 (4) | |
C4 | 0.5483 (2) | −0.1282 (2) | 0.38024 (12) | 0.0273 (4) | |
H4 | 0.6298 | −0.1412 | 0.3528 | 0.033* | |
C5 | 0.5256 (2) | −0.1948 (2) | 0.45110 (12) | 0.0253 (4) | |
H5 | 0.5940 | −0.2539 | 0.4729 | 0.030* | |
C6 | 0.40448 (19) | −0.1783 (2) | 0.49227 (11) | 0.0213 (4) | |
C7 | 0.30329 (19) | −0.0919 (2) | 0.46039 (11) | 0.0207 (4) | |
H7 | 0.2201 | −0.0811 | 0.4864 | 0.025* | |
C8 | 0.32614 (19) | −0.02158 (19) | 0.38991 (11) | 0.0207 (4) | |
C9 | 0.38708 (19) | −0.2488 (2) | 0.56998 (11) | 0.0219 (4) | |
C10 | 0.4633 (2) | −0.3664 (2) | 0.59166 (12) | 0.0291 (5) | |
H10 | 0.5261 | −0.4035 | 0.5558 | 0.035* | |
C11 | 0.4484 (2) | −0.4295 (2) | 0.66456 (13) | 0.0336 (5) | |
H11 | 0.5020 | −0.5083 | 0.6783 | 0.040* | |
C12 | 0.3565 (2) | −0.3791 (2) | 0.71746 (13) | 0.0340 (5) | |
H12 | 0.3464 | −0.4227 | 0.7673 | 0.041* | |
C13 | 0.2792 (2) | −0.2639 (2) | 0.69661 (12) | 0.0319 (5) | |
H13 | 0.2154 | −0.2286 | 0.7323 | 0.038* | |
C14 | 0.2945 (2) | −0.1996 (2) | 0.62387 (12) | 0.0260 (4) | |
H14 | 0.2408 | −0.1207 | 0.6106 | 0.031* | |
C15 | 0.11738 (19) | 0.2550 (2) | 0.43243 (11) | 0.0223 (4) | |
C16 | 0.0866 (2) | 0.2136 (2) | 0.50802 (12) | 0.0274 (4) | |
H16 | 0.0506 | 0.1238 | 0.5175 | 0.033* | |
C17 | 0.1093 (2) | 0.3064 (3) | 0.56983 (12) | 0.0331 (5) | |
H17 | 0.0904 | 0.2792 | 0.6223 | 0.040* | |
C18 | 0.1594 (2) | 0.4382 (2) | 0.55570 (13) | 0.0337 (5) | |
H18 | 0.1739 | 0.5012 | 0.5983 | 0.040* | |
C19 | 0.1883 (2) | 0.4783 (2) | 0.47930 (14) | 0.0338 (5) | |
H19 | 0.2225 | 0.5687 | 0.4696 | 0.041* | |
C20 | 0.1674 (2) | 0.3867 (2) | 0.41729 (13) | 0.0281 (4) | |
H20 | 0.1871 | 0.4137 | 0.3649 | 0.034* | |
C21 | 0.3119 (2) | 0.2026 (2) | 0.20968 (12) | 0.0317 (5) | |
H21A | 0.2160 | 0.2266 | 0.2026 | 0.047* | |
H21B | 0.3435 | 0.1577 | 0.1616 | 0.047* | |
H21C | 0.3646 | 0.2873 | 0.2199 | 0.047* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S | 0.0224 (3) | 0.0228 (3) | 0.0238 (3) | 0.00043 (18) | −0.00299 (18) | 0.00061 (19) |
O1 | 0.0292 (8) | 0.0299 (8) | 0.0215 (7) | 0.0001 (6) | 0.0057 (6) | 0.0012 (6) |
O2 | 0.0272 (8) | 0.0300 (8) | 0.0374 (8) | −0.0067 (6) | −0.0001 (6) | −0.0012 (6) |
C1 | 0.0244 (10) | 0.0202 (9) | 0.0200 (9) | −0.0009 (8) | −0.0010 (7) | −0.0011 (7) |
C2 | 0.0288 (10) | 0.0218 (10) | 0.0228 (10) | −0.0014 (8) | −0.0005 (8) | −0.0024 (8) |
C3 | 0.0258 (10) | 0.0231 (10) | 0.0195 (9) | −0.0022 (8) | 0.0024 (7) | −0.0018 (7) |
C4 | 0.0234 (10) | 0.0305 (11) | 0.0284 (10) | 0.0027 (8) | 0.0069 (8) | −0.0038 (9) |
C5 | 0.0218 (10) | 0.0268 (10) | 0.0274 (10) | 0.0043 (8) | −0.0002 (8) | −0.0029 (8) |
C6 | 0.0230 (9) | 0.0205 (9) | 0.0204 (9) | −0.0012 (7) | −0.0007 (7) | −0.0024 (7) |
C7 | 0.0209 (9) | 0.0219 (9) | 0.0194 (9) | −0.0007 (7) | 0.0019 (7) | −0.0021 (7) |
C8 | 0.0219 (9) | 0.0190 (9) | 0.0211 (9) | −0.0007 (7) | −0.0020 (7) | −0.0046 (7) |
C9 | 0.0199 (9) | 0.0223 (9) | 0.0234 (9) | −0.0023 (7) | −0.0038 (7) | −0.0011 (8) |
C10 | 0.0273 (11) | 0.0301 (11) | 0.0296 (11) | 0.0040 (9) | −0.0010 (8) | 0.0014 (9) |
C11 | 0.0335 (12) | 0.0316 (12) | 0.0353 (12) | 0.0056 (9) | −0.0077 (9) | 0.0068 (9) |
C12 | 0.0382 (12) | 0.0380 (12) | 0.0254 (10) | −0.0054 (10) | −0.0034 (9) | 0.0097 (9) |
C13 | 0.0335 (11) | 0.0373 (12) | 0.0250 (10) | −0.0006 (9) | 0.0036 (8) | 0.0020 (9) |
C14 | 0.0267 (10) | 0.0252 (10) | 0.0261 (10) | 0.0016 (8) | 0.0003 (8) | 0.0017 (8) |
C15 | 0.0169 (9) | 0.0232 (10) | 0.0267 (10) | 0.0037 (7) | −0.0013 (7) | −0.0019 (8) |
C16 | 0.0226 (10) | 0.0311 (11) | 0.0287 (10) | 0.0008 (8) | 0.0034 (8) | 0.0020 (9) |
C17 | 0.0245 (11) | 0.0491 (14) | 0.0257 (10) | 0.0069 (10) | 0.0022 (8) | −0.0011 (10) |
C18 | 0.0256 (11) | 0.0399 (13) | 0.0354 (12) | 0.0061 (9) | −0.0050 (9) | −0.0141 (10) |
C19 | 0.0345 (12) | 0.0260 (11) | 0.0405 (12) | −0.0026 (9) | −0.0041 (9) | −0.0032 (9) |
C20 | 0.0295 (11) | 0.0254 (10) | 0.0296 (11) | −0.0005 (8) | −0.0002 (8) | 0.0024 (8) |
C21 | 0.0397 (12) | 0.0300 (11) | 0.0254 (10) | −0.0016 (9) | 0.0028 (9) | 0.0045 (9) |
S—O2 | 1.491 (2) | C11—C12 | 1.383 (3) |
S—C1 | 1.760 (2) | C11—H11 | 0.9500 |
S—C15 | 1.797 (2) | C12—C13 | 1.386 (3) |
O1—C2 | 1.374 (2) | C12—H12 | 0.9500 |
O1—C3 | 1.381 (2) | C13—C14 | 1.390 (3) |
C1—C2 | 1.356 (3) | C13—H13 | 0.9500 |
C1—C8 | 1.451 (3) | C14—H14 | 0.9500 |
C2—C21 | 1.483 (3) | C15—C16 | 1.382 (3) |
C3—C4 | 1.377 (3) | C15—C20 | 1.387 (3) |
C3—C8 | 1.392 (3) | C16—C17 | 1.388 (3) |
C4—C5 | 1.384 (3) | C16—H16 | 0.9500 |
C4—H4 | 0.9500 | C17—C18 | 1.385 (3) |
C5—C6 | 1.412 (3) | C17—H17 | 0.9500 |
C5—H5 | 0.9500 | C18—C19 | 1.387 (3) |
C6—C7 | 1.397 (3) | C18—H18 | 0.9500 |
C6—C9 | 1.494 (3) | C19—C20 | 1.381 (3) |
C7—C8 | 1.395 (3) | C19—H19 | 0.9500 |
C7—H7 | 0.9500 | C20—H20 | 0.9500 |
C9—C14 | 1.394 (3) | C21—H21A | 0.9800 |
C9—C10 | 1.403 (3) | C21—H21B | 0.9800 |
C10—C11 | 1.387 (3) | C21—H21C | 0.9800 |
C10—H10 | 0.9500 | ||
O2—S—C1 | 106.89 (9) | C12—C11—H11 | 119.6 |
O2—S—C15 | 107.25 (9) | C10—C11—H11 | 119.6 |
C1—S—C15 | 99.10 (9) | C11—C12—C13 | 118.9 (2) |
C2—O1—C3 | 106.39 (15) | C11—C12—H12 | 120.5 |
C2—C1—C8 | 107.53 (17) | C13—C12—H12 | 120.5 |
C2—C1—S | 123.21 (15) | C12—C13—C14 | 120.5 (2) |
C8—C1—S | 129.21 (15) | C12—C13—H13 | 119.7 |
C1—C2—O1 | 110.83 (17) | C14—C13—H13 | 119.7 |
C1—C2—C21 | 132.87 (19) | C13—C14—C9 | 121.25 (19) |
O1—C2—C21 | 116.25 (17) | C13—C14—H14 | 119.4 |
C4—C3—O1 | 126.03 (17) | C9—C14—H14 | 119.4 |
C4—C3—C8 | 123.11 (18) | C16—C15—C20 | 121.57 (19) |
O1—C3—C8 | 110.86 (17) | C16—C15—S | 120.54 (16) |
C3—C4—C5 | 116.71 (18) | C20—C15—S | 117.84 (15) |
C3—C4—H4 | 121.6 | C15—C16—C17 | 118.5 (2) |
C5—C4—H4 | 121.6 | C15—C16—H16 | 120.8 |
C4—C5—C6 | 122.48 (18) | C17—C16—H16 | 120.8 |
C4—C5—H5 | 118.8 | C18—C17—C16 | 120.6 (2) |
C6—C5—H5 | 118.8 | C18—C17—H17 | 119.7 |
C7—C6—C5 | 119.01 (17) | C16—C17—H17 | 119.7 |
C7—C6—C9 | 120.69 (17) | C17—C18—C19 | 120.0 (2) |
C5—C6—C9 | 120.27 (17) | C17—C18—H18 | 120.0 |
C8—C7—C6 | 119.09 (17) | C19—C18—H18 | 120.0 |
C8—C7—H7 | 120.5 | C20—C19—C18 | 120.0 (2) |
C6—C7—H7 | 120.5 | C20—C19—H19 | 120.0 |
C3—C8—C7 | 119.57 (18) | C18—C19—H19 | 120.0 |
C3—C8—C1 | 104.39 (17) | C19—C20—C15 | 119.3 (2) |
C7—C8—C1 | 136.04 (18) | C19—C20—H20 | 120.4 |
C14—C9—C10 | 117.47 (18) | C15—C20—H20 | 120.4 |
C14—C9—C6 | 121.08 (17) | C2—C21—H21A | 109.5 |
C10—C9—C6 | 121.45 (18) | C2—C21—H21B | 109.5 |
C11—C10—C9 | 121.0 (2) | H21A—C21—H21B | 109.5 |
C11—C10—H10 | 119.5 | C2—C21—H21C | 109.5 |
C9—C10—H10 | 119.5 | H21A—C21—H21C | 109.5 |
C12—C11—C10 | 120.8 (2) | H21B—C21—H21C | 109.5 |
O2—S—C1—C2 | 137.76 (17) | C2—C1—C8—C7 | −179.6 (2) |
C15—S—C1—C2 | −110.99 (18) | S—C1—C8—C7 | −2.3 (3) |
O2—S—C1—C8 | −39.2 (2) | C7—C6—C9—C14 | −20.5 (3) |
C15—S—C1—C8 | 72.04 (19) | C5—C6—C9—C14 | 157.58 (19) |
C8—C1—C2—O1 | 0.5 (2) | C7—C6—C9—C10 | 159.74 (19) |
S—C1—C2—O1 | −177.00 (13) | C5—C6—C9—C10 | −22.2 (3) |
C8—C1—C2—C21 | −176.5 (2) | C14—C9—C10—C11 | −1.1 (3) |
S—C1—C2—C21 | 5.9 (3) | C6—C9—C10—C11 | 178.67 (19) |
C3—O1—C2—C1 | −0.3 (2) | C9—C10—C11—C12 | 0.9 (3) |
C3—O1—C2—C21 | 177.31 (17) | C10—C11—C12—C13 | −0.2 (3) |
C2—O1—C3—C4 | −179.52 (19) | C11—C12—C13—C14 | −0.4 (3) |
C2—O1—C3—C8 | −0.1 (2) | C12—C13—C14—C9 | 0.1 (3) |
O1—C3—C4—C5 | 178.85 (18) | C10—C9—C14—C13 | 0.6 (3) |
C8—C3—C4—C5 | −0.5 (3) | C6—C9—C14—C13 | −179.17 (18) |
C3—C4—C5—C6 | 0.9 (3) | O2—S—C15—C16 | 11.79 (18) |
C4—C5—C6—C7 | 0.2 (3) | C1—S—C15—C16 | −99.18 (17) |
C4—C5—C6—C9 | −177.89 (18) | O2—S—C15—C20 | −165.60 (15) |
C5—C6—C7—C8 | −1.7 (3) | C1—S—C15—C20 | 83.43 (16) |
C9—C6—C7—C8 | 176.44 (17) | C20—C15—C16—C17 | −1.3 (3) |
C4—C3—C8—C7 | −0.9 (3) | S—C15—C16—C17 | −178.60 (15) |
O1—C3—C8—C7 | 179.63 (16) | C15—C16—C17—C18 | 1.2 (3) |
C4—C3—C8—C1 | 179.85 (19) | C16—C17—C18—C19 | −0.5 (3) |
O1—C3—C8—C1 | 0.4 (2) | C17—C18—C19—C20 | −0.1 (3) |
C6—C7—C8—C3 | 2.0 (3) | C18—C19—C20—C15 | 0.0 (3) |
C6—C7—C8—C1 | −179.1 (2) | C16—C15—C20—C19 | 0.7 (3) |
C2—C1—C8—C3 | −0.6 (2) | S—C15—C20—C19 | 178.06 (16) |
S—C1—C8—C3 | 176.78 (15) |
Experimental details
Crystal data | |
Chemical formula | C21H16O2S |
Mr | 332.40 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 173 |
a, b, c (Å) | 9.8919 (5), 9.6229 (5), 16.9226 (9) |
β (°) | 91.685 (1) |
V (Å3) | 1610.15 (14) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.21 |
Crystal size (mm) | 0.65 × 0.42 × 0.35 |
Data collection | |
Diffractometer | Bruker SMART CCD |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8853, 3154, 2942 |
Rint | 0.030 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.111, 1.16 |
No. of reflections | 3154 |
No. of parameters | 218 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.62, −0.41 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 1998), SHELXL97.
As part of our continuing studies on the synthesis and structure of 5-phenyl-1-benzofuran analogues, the crystal structures of 3-methylsulfanyl-2,5-diphenyl-1-benzofuran (Choi, Seo, Kang et al., 2006) and 2-methyl-3-methylsulfinyl-5-phenyl-1-benzofuran (Choi, Seo, Lee et al., 2006) have been described to the literature. Herein we report the molecular and crystal structure of the title compound (I) (Fig. 1).
The benzofuran unit is essentially planar, with a mean deviation of 0.008 Å from the least-squares plane defined by the nine constituent atoms. The dihedral angle in (I) formed by the plane of the benzofuran ring and the plane of 5-phenyl ring is 21.0 (1)° and phenyl ring(C15—C20) with 80.4 (6)° lies toward benzofuran plane. The molecular packing (Fig. 2) is stabilized by CH2—H···π interactions between the methyl group and the benzene ring of benzofuran unit, with a C21—H21B···Cg1i separation of 2.94 Å. (Cg1 is the centroid of the C3—C8 benzene ring, symmetry code as in Fig. 2).