




Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807038822/zl2044sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S1600536807038822/zl2044Isup2.hkl |
CCDC reference: 660239
3-Chloroperbenzoic acid (77%, 359 mg, 1.60 mmol) was added in small portions to a stirred solution of 5-iodo-3-methylsulfanyl-2-phenyl-1-benzofuran (549 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 (ethyl acetate) to afford the title compound as a colorless solid [yield 84%, m.p. 464–465 K; Rf = 0.70 (hexane-ethyl acetate, 1:2 v/v)]. Single crystals suitable for X-ray diffraction were prepared by slow evaporation of a dilute solution of the title compound in tetrahydrofuran at room temperature.
All H atoms were positioned geometrically and refined using a riding model, with C—H = 0.95 Å for aromatic H atoms and 0.98 Å for methyl H atoms, respectively, 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 1.29 Å from S and the largest hole is 0.67 Å from I.
As part of our continuing studies on the synthesis and structure of 5-halo-1-benzofuran analogues, we have recently described the crystal structures of 5-chloro-3-methylsulfinyl-2-phenyl-1-benzofuran (Choi et al., 2007a) and 5-bromo-3-methylsulfinyl-2-phenyl-1-benzofuran (Choi et al., 2007b). Herein we report the molecular and crystal structure of the title compound, 5-iodo-3-methylsulfinyl-2-phenyl-1-benzofuran (Fig. 1).
The benzofuran unit is essentially planar, with a mean deviation of 0.012 Å from the least-squares plane defined by the nine constituent atoms. In the title compound, the dihedral angle between the planes of the benzofuran and the phenyl ring is 29.84 (6)°. The molecular packing (Fig. 2) is stabilized by π···π stacking interactions between adjacent furan units. The Cg···Cgi distance is 3.836 (3) Å (Cg is the centroid of the O1/C8/C1/C2/C7 furan ring; symmetry code as in Fig. 2), which is in the usual range when compared to other such interactions (Choi et al., 2007a, b). The molecular packing (Fig. 2) is further stabilized by a weak C—H···O hydrogen bond (Table 1) and by a halogen bond between the iodine atom and the oxygen of the S═O unit. This type of strong electrostatic interaction, which is often compared to hydrogen bonding, relies on an unusually strong attraction between the positively charged outermost region of the halogen atom (the "σ-hole") and one of the lone pairs of the acceptor, here at the S═O oxygen atom (Politzer et al., 2007). The observed I···O separation in the structure of the title compound of 3.209 (2) Å and also the nearly linear C—I···O angle of 169.12 (6)° are in the typical range for a such a halogen bond and compare well with values of similar compounds found in the 2007 release of the Cambridge Crystallographic Database V5.28 (Allen, 2002), which revealed 39 compounds with C—I···O═S contacts equal or less than 3.3 Å.
For the 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). For related literature, see: Allen (2002).
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.
C15H11IO2S | Z = 2 |
Mr = 382.20 | F(000) = 372 |
Triclinic, P1 | Dx = 1.845 Mg m−3 |
Hall symbol: -p 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.1495 (4) Å | Cell parameters from 5532 reflections |
b = 8.1823 (4) Å | θ = 2.7–28.3° |
c = 11.2007 (6) Å | µ = 2.47 mm−1 |
α = 93.584 (1)° | T = 173 K |
β = 92.941 (1)° | Block, colourless |
γ = 112.197 (1)° | 0.40 × 0.20 × 0.10 mm |
V = 687.91 (6) Å3 |
Bruker SMART CCD area-detector diffractometer | 2648 independent reflections |
Radiation source: fine-focus sealed tube | 2587 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.014 |
Detector resolution: 10.00 pixels mm-1 | θmax = 26.0°, θmin = 1.8° |
φ and ω scans | h = −9→10 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1999) | k = −10→10 |
Tmin = 0.556, Tmax = 0.783 | l = −13→13 |
5403 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)] = 0.017 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.044 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0213P)2 + 0.4423P] where P = (Fo2 + 2Fc2)/3 |
2648 reflections | (Δ/σ)max < 0.001 |
173 parameters | Δρmax = 0.58 e Å−3 |
0 restraints | Δρmin = −0.52 e Å−3 |
C15H11IO2S | γ = 112.197 (1)° |
Mr = 382.20 | V = 687.91 (6) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.1495 (4) Å | Mo Kα radiation |
b = 8.1823 (4) Å | µ = 2.47 mm−1 |
c = 11.2007 (6) Å | T = 173 K |
α = 93.584 (1)° | 0.40 × 0.20 × 0.10 mm |
β = 92.941 (1)° |
Bruker SMART CCD area-detector diffractometer | 2648 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1999) | 2587 reflections with I > 2σ(I) |
Tmin = 0.556, Tmax = 0.783 | Rint = 0.014 |
5403 measured reflections |
R[F2 > 2σ(F2)] = 0.017 | 0 restraints |
wR(F2) = 0.044 | H-atom parameters constrained |
S = 1.09 | Δρmax = 0.58 e Å−3 |
2648 reflections | Δρmin = −0.52 e Å−3 |
173 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 | ||
I | 0.380751 (18) | 0.189438 (16) | −0.025139 (11) | 0.02710 (6) | |
S | 0.80496 (6) | 0.78490 (6) | 0.39542 (4) | 0.02225 (10) | |
O1 | 0.64855 (18) | 0.30463 (17) | 0.51101 (12) | 0.0222 (3) | |
O2 | 0.67054 (19) | 0.80987 (19) | 0.31109 (14) | 0.0296 (3) | |
C1 | 0.7264 (2) | 0.5567 (2) | 0.41861 (17) | 0.0205 (4) | |
C2 | 0.6197 (2) | 0.4117 (2) | 0.33198 (17) | 0.0193 (4) | |
C3 | 0.5622 (3) | 0.3940 (3) | 0.21014 (17) | 0.0215 (4) | |
H3 | 0.5904 | 0.4940 | 0.1648 | 0.026* | |
C4 | 0.4628 (3) | 0.2248 (3) | 0.15866 (17) | 0.0221 (4) | |
C5 | 0.4178 (3) | 0.0753 (3) | 0.22367 (18) | 0.0237 (4) | |
H5 | 0.3480 | −0.0384 | 0.1848 | 0.028* | |
C6 | 0.4743 (3) | 0.0916 (3) | 0.34438 (18) | 0.0239 (4) | |
H6 | 0.4456 | −0.0082 | 0.3901 | 0.029* | |
C7 | 0.5747 (3) | 0.2610 (3) | 0.39414 (17) | 0.0205 (4) | |
C8 | 0.7399 (2) | 0.4864 (2) | 0.52391 (18) | 0.0205 (4) | |
C9 | 0.8318 (3) | 0.5574 (3) | 0.64242 (18) | 0.0212 (4) | |
C10 | 0.9897 (3) | 0.7066 (3) | 0.65581 (19) | 0.0253 (4) | |
H10 | 1.0377 | 0.7645 | 0.5873 | 0.030* | |
C11 | 1.0773 (3) | 0.7714 (3) | 0.7686 (2) | 0.0293 (4) | |
H11 | 1.1846 | 0.8737 | 0.7773 | 0.035* | |
C12 | 1.0082 (3) | 0.6868 (3) | 0.86842 (19) | 0.0309 (5) | |
H12 | 1.0683 | 0.7311 | 0.9456 | 0.037* | |
C13 | 0.8517 (3) | 0.5375 (3) | 0.85625 (19) | 0.0291 (4) | |
H13 | 0.8051 | 0.4800 | 0.9252 | 0.035* | |
C14 | 0.7626 (3) | 0.4716 (3) | 0.74390 (18) | 0.0244 (4) | |
H14 | 0.6554 | 0.3692 | 0.7358 | 0.029* | |
C15 | 0.9862 (3) | 0.7957 (3) | 0.3080 (2) | 0.0364 (5) | |
H15A | 0.9416 | 0.7108 | 0.2369 | 0.055* | |
H15B | 1.0735 | 0.7666 | 0.3564 | 0.055* | |
H15C | 1.0428 | 0.9157 | 0.2830 | 0.055* |
U11 | U22 | U33 | U12 | U13 | U23 | |
I | 0.03718 (9) | 0.02394 (8) | 0.01870 (8) | 0.01122 (6) | −0.00362 (5) | −0.00127 (5) |
S | 0.0234 (2) | 0.0155 (2) | 0.0264 (2) | 0.00579 (18) | 0.00115 (18) | 0.00217 (18) |
O1 | 0.0271 (7) | 0.0176 (7) | 0.0184 (7) | 0.0050 (5) | −0.0008 (5) | 0.0021 (5) |
O2 | 0.0276 (7) | 0.0255 (7) | 0.0369 (8) | 0.0106 (6) | 0.0000 (6) | 0.0103 (6) |
C1 | 0.0217 (9) | 0.0162 (9) | 0.0224 (9) | 0.0061 (7) | 0.0012 (7) | 0.0017 (7) |
C2 | 0.0195 (9) | 0.0164 (9) | 0.0212 (9) | 0.0061 (7) | 0.0012 (7) | 0.0007 (7) |
C3 | 0.0262 (10) | 0.0182 (9) | 0.0206 (9) | 0.0090 (8) | 0.0014 (7) | 0.0035 (7) |
C4 | 0.0255 (9) | 0.0240 (10) | 0.0170 (9) | 0.0103 (8) | −0.0004 (7) | 0.0004 (7) |
C5 | 0.0258 (10) | 0.0174 (9) | 0.0238 (10) | 0.0045 (7) | 0.0008 (8) | −0.0016 (8) |
C6 | 0.0289 (10) | 0.0171 (9) | 0.0237 (10) | 0.0059 (8) | 0.0028 (8) | 0.0052 (8) |
C7 | 0.0227 (9) | 0.0214 (9) | 0.0173 (9) | 0.0083 (7) | 0.0016 (7) | 0.0020 (7) |
C8 | 0.0202 (9) | 0.0169 (9) | 0.0232 (10) | 0.0059 (7) | 0.0021 (7) | 0.0008 (7) |
C9 | 0.0235 (9) | 0.0218 (9) | 0.0202 (9) | 0.0111 (8) | 0.0002 (7) | 0.0013 (7) |
C10 | 0.0244 (10) | 0.0256 (10) | 0.0245 (10) | 0.0081 (8) | 0.0003 (8) | 0.0022 (8) |
C11 | 0.0248 (10) | 0.0276 (11) | 0.0306 (11) | 0.0061 (8) | −0.0043 (8) | −0.0029 (9) |
C12 | 0.0325 (11) | 0.0349 (12) | 0.0234 (10) | 0.0126 (9) | −0.0063 (8) | −0.0038 (9) |
C13 | 0.0334 (11) | 0.0335 (11) | 0.0209 (10) | 0.0133 (9) | 0.0017 (8) | 0.0031 (8) |
C14 | 0.0254 (10) | 0.0231 (10) | 0.0240 (10) | 0.0088 (8) | 0.0009 (8) | 0.0013 (8) |
C15 | 0.0295 (11) | 0.0360 (12) | 0.0496 (14) | 0.0155 (10) | 0.0155 (10) | 0.0161 (11) |
I—C4 | 2.099 (2) | C6—H6 | 0.9500 |
I—O2i | 3.209 (2) | C8—C9 | 1.461 (3) |
S—O2 | 1.490 (2) | C9—C10 | 1.392 (3) |
S—C1 | 1.771 (2) | C9—C14 | 1.403 (3) |
S—C15 | 1.791 (2) | C10—C11 | 1.388 (3) |
O1—C7 | 1.379 (2) | C10—H10 | 0.9500 |
O1—C8 | 1.383 (2) | C11—C12 | 1.383 (3) |
C1—C8 | 1.361 (3) | C11—H11 | 0.9500 |
C1—C2 | 1.448 (3) | C12—C13 | 1.386 (3) |
C2—C7 | 1.390 (3) | C12—H12 | 0.9500 |
C2—C3 | 1.400 (3) | C13—C14 | 1.388 (3) |
C3—C4 | 1.382 (3) | C13—H13 | 0.9500 |
C3—H3 | 0.9500 | C14—H14 | 0.9500 |
C4—C5 | 1.400 (3) | C15—H15A | 0.9800 |
C5—C6 | 1.388 (3) | C15—H15B | 0.9800 |
C5—H5 | 0.9500 | C15—H15C | 0.9800 |
C6—C7 | 1.379 (3) | ||
C4—I—O2i | 169.12 (6) | C1—C8—C9 | 135.0 (2) |
O2—S—C1 | 107.16 (9) | O1—C8—C9 | 114.7 (2) |
O2—S—C15 | 105.6 (1) | C10—C9—C14 | 119.5 (2) |
C1—S—C15 | 98.5 (1) | C10—C9—C8 | 120.9 (2) |
C7—O1—C8 | 106.8 (1) | C14—C9—C8 | 119.6 (2) |
C8—C1—C2 | 107.3 (1) | C11—C10—C9 | 120.4 (2) |
C8—C1—S | 126.4 (2) | C11—C10—H10 | 119.8 |
C2—C1—S | 126.0 (2) | C9—C10—H10 | 119.8 |
C7—C2—C3 | 119.1 (2) | C12—C11—C10 | 119.9 (2) |
C7—C2—C1 | 105.2 (2) | C12—C11—H11 | 120.1 |
C3—C2—C1 | 135.7 (2) | C10—C11—H11 | 120.1 |
C4—C3—C2 | 117.2 (2) | C11—C12—C13 | 120.3 (2) |
C4—C3—H3 | 121.4 | C11—C12—H12 | 119.9 |
C2—C3—H3 | 121.4 | C13—C12—H12 | 119.9 |
C3—C4—C5 | 122.6 (2) | C12—C13—C14 | 120.4 (2) |
C3—C4—I | 118.8 (1) | C12—C13—H13 | 119.8 |
C5—C4—I | 118.6 (1) | C14—C13—H13 | 119.8 |
C6—C5—C4 | 120.6 (2) | C13—C14—C9 | 119.5 (2) |
C6—C5—H5 | 119.7 | C13—C14—H14 | 120.2 |
C4—C5—H5 | 119.7 | C9—C14—H14 | 120.2 |
C7—C6—C5 | 116.1 (2) | S—C15—H15A | 109.5 |
C7—C6—H6 | 122.0 | S—C15—H15B | 109.5 |
C5—C6—H6 | 122.0 | H15A—C15—H15B | 109.5 |
O1—C7—C6 | 125.1 (2) | S—C15—H15C | 109.5 |
O1—C7—C2 | 110.4 (2) | H15A—C15—H15C | 109.5 |
C6—C7—C2 | 124.5 (2) | H15B—C15—H15C | 109.5 |
C1—C8—O1 | 110.3 (2) | ||
O2—S—C1—C8 | −141.49 (17) | C1—C2—C7—O1 | −0.9 (2) |
C15—S—C1—C8 | 109.18 (19) | C3—C2—C7—C6 | −0.5 (3) |
O2—S—C1—C2 | 31.55 (19) | C1—C2—C7—C6 | −179.18 (19) |
C15—S—C1—C2 | −77.78 (19) | C2—C1—C8—O1 | 0.0 (2) |
C8—C1—C2—C7 | 0.5 (2) | S—C1—C8—O1 | 174.13 (14) |
S—C1—C2—C7 | −173.63 (14) | C2—C1—C8—C9 | 177.4 (2) |
C8—C1—C2—C3 | −177.8 (2) | S—C1—C8—C9 | −8.5 (3) |
S—C1—C2—C3 | 8.1 (3) | C7—O1—C8—C1 | −0.6 (2) |
C7—C2—C3—C4 | −0.1 (3) | C7—O1—C8—C9 | −178.51 (16) |
C1—C2—C3—C4 | 178.1 (2) | C1—C8—C9—C10 | −29.1 (3) |
C2—C3—C4—C5 | 0.7 (3) | O1—C8—C9—C10 | 148.17 (18) |
C2—C3—C4—I | −177.86 (14) | C1—C8—C9—C14 | 152.5 (2) |
O2i—I—C4—C3 | 40.4 (4) | O1—C8—C9—C14 | −30.3 (3) |
O2i—I—C4—C5 | −138.2 (3) | C14—C9—C10—C11 | −0.6 (3) |
C3—C4—C5—C6 | −0.7 (3) | C8—C9—C10—C11 | −179.03 (19) |
I—C4—C5—C6 | 177.79 (15) | C9—C10—C11—C12 | 0.4 (3) |
C4—C5—C6—C7 | 0.2 (3) | C10—C11—C12—C13 | 0.0 (3) |
C8—O1—C7—C6 | 179.20 (19) | C11—C12—C13—C14 | −0.1 (3) |
C8—O1—C7—C2 | 0.9 (2) | C12—C13—C14—C9 | −0.1 (3) |
C5—C6—C7—O1 | −177.60 (18) | C10—C9—C14—C13 | 0.5 (3) |
C5—C6—C7—C2 | 0.5 (3) | C8—C9—C14—C13 | 178.93 (18) |
C3—C2—C7—O1 | 177.79 (16) |
Symmetry code: (i) −x+1, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6···O1ii | 0.95 | 2.59 | 3.536 (2) | 173 |
Symmetry code: (ii) −x+1, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C15H11IO2S |
Mr | 382.20 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 173 |
a, b, c (Å) | 8.1495 (4), 8.1823 (4), 11.2007 (6) |
α, β, γ (°) | 93.584 (1), 92.941 (1), 112.197 (1) |
V (Å3) | 687.91 (6) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 2.47 |
Crystal size (mm) | 0.40 × 0.20 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1999) |
Tmin, Tmax | 0.556, 0.783 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5403, 2648, 2587 |
Rint | 0.014 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.017, 0.044, 1.09 |
No. of reflections | 2648 |
No. of parameters | 173 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.58, −0.52 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 1998), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6···O1i | 0.95 | 2.59 | 3.536 (2) | 172.7 |
Symmetry code: (i) −x+1, −y, −z+1. |
As part of our continuing studies on the synthesis and structure of 5-halo-1-benzofuran analogues, we have recently described the crystal structures of 5-chloro-3-methylsulfinyl-2-phenyl-1-benzofuran (Choi et al., 2007a) and 5-bromo-3-methylsulfinyl-2-phenyl-1-benzofuran (Choi et al., 2007b). Herein we report the molecular and crystal structure of the title compound, 5-iodo-3-methylsulfinyl-2-phenyl-1-benzofuran (Fig. 1).
The benzofuran unit is essentially planar, with a mean deviation of 0.012 Å from the least-squares plane defined by the nine constituent atoms. In the title compound, the dihedral angle between the planes of the benzofuran and the phenyl ring is 29.84 (6)°. The molecular packing (Fig. 2) is stabilized by π···π stacking interactions between adjacent furan units. The Cg···Cgi distance is 3.836 (3) Å (Cg is the centroid of the O1/C8/C1/C2/C7 furan ring; symmetry code as in Fig. 2), which is in the usual range when compared to other such interactions (Choi et al., 2007a, b). The molecular packing (Fig. 2) is further stabilized by a weak C—H···O hydrogen bond (Table 1) and by a halogen bond between the iodine atom and the oxygen of the S═O unit. This type of strong electrostatic interaction, which is often compared to hydrogen bonding, relies on an unusually strong attraction between the positively charged outermost region of the halogen atom (the "σ-hole") and one of the lone pairs of the acceptor, here at the S═O oxygen atom (Politzer et al., 2007). The observed I···O separation in the structure of the title compound of 3.209 (2) Å and also the nearly linear C—I···O angle of 169.12 (6)° are in the typical range for a such a halogen bond and compare well with values of similar compounds found in the 2007 release of the Cambridge Crystallographic Database V5.28 (Allen, 2002), which revealed 39 compounds with C—I···O═S contacts equal or less than 3.3 Å.