organic compounds
5-Bromo-2-methyl-3-(3-methylphenylsulfinyl)-1-benzofuran
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
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
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Data collection: APEX2 (Bruker, 2009); cell 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
10.1107/S1600536814003365/su2700sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536814003365/su2700Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536814003365/su2700Isup3.cml
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
(hexane–ethyl acetate, 2:1 v/v) to afford the title compound as a colorless solid [Yield 78%, M.p. 413–414 K; Rf = 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.All the H atoms were positioned geometrically and refined using a riding model: C—H = 0.95 Å for aryl and 0.99 Å for methyl H atoms with Uiso(H) = 1.2Ueq(C-aryl) and = 1.5Ueq(C-methyl). The positions of the methyl hydrogens were optimized rotationally.
Data collection: APEX2 (Bruker, 2009); cell
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).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]. |
C16H13BrO2S | Z = 2 |
Mr = 349.23 | F(000) = 352 |
Triclinic, P1 | Dx = 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 |
Bruker SMART APEXII CCD diffractometer | 3667 independent reflections |
Radiation source: rotating anode | 3391 reflections with I > 2σ(I) |
Graphite multilayer monochromator | Rint = 0.034 |
Detector resolution: 10.0 pixels mm-1 | θmax = 28.4°, θmin = 2.0° |
φ and ω scans | h = −11→11 |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | k = −11→11 |
Tmin = 0.365, Tmax = 0.746 | l = −14→14 |
13736 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)] = 0.025 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.066 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0306P)2 + 0.2396P] where P = (Fo2 + 2Fc2)/3 |
3667 reflections | (Δ/σ)max = 0.001 |
183 parameters | Δρmax = 0.36 e Å−3 |
0 restraints | Δρmin = −0.54 e Å−3 |
C16H13BrO2S | γ = 108.900 (1)° |
Mr = 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)° |
Bruker SMART APEXII CCD diffractometer | 3667 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | 3391 reflections with I > 2σ(I) |
Tmin = 0.365, Tmax = 0.746 | Rint = 0.034 |
13736 measured reflections |
R[F2 > 2σ(F2)] = 0.025 | 0 restraints |
wR(F2) = 0.066 | H-atom parameters constrained |
S = 1.09 | Δρmax = 0.36 e Å−3 |
3667 reflections | Δρmin = −0.54 e Å−3 |
183 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
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* |
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) |
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. |
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. |
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
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
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).