organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890

2-(3-Fluoro­phen­yl)-5-iodo-7-methyl-3-methyl­sulfinyl-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

(Received 24 April 2012; accepted 26 April 2012; online 5 May 2012)

In the title compound, C16H12FIO2S, the 3-fluoro­phenyl ring makes a dihedral angle of 34.93 (7)° with the mean plane [r.m.s. deviation = 0.019 (1) Å] of the benzofuran fragment. In the crystal, mol­ecules are linked via pairs of I⋯O contacts [3.088 (2) Å] into inversion dimers. These dimers are connected by weak C—H⋯O hydrogen bonds.

Related literature

For background information and the crystal structures of related compounds, see: Choi et al. (2008[Choi, H. D., Seo, P. J., Kim, B. K., Son, B. W. & Lee, U. (2008). Acta Cryst. E64, o1116.], 2010[Choi, H. D., Seo, P. J., Son, B. W. & Lee, U. (2010). Acta Cryst. E66, o1680.]). For a review of halogen bonding, see: Politzer et al. (2007[Politzer, P., Lane, P., Concha, M. C., Ma, Y. & Murray, J. S. (2007). J. Mol. Model. 13, 305-311.]).

[Scheme 1]

Experimental

Crystal data
  • C16H12FIO2S

  • Mr = 414.22

  • Monoclinic, P 21 /c

  • a = 7.8169 (1) Å

  • b = 23.9721 (3) Å

  • c = 8.0559 (1) Å

  • β = 99.748 (1)°

  • V = 1487.78 (3) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 2.30 mm−1

  • T = 173 K

  • 0.30 × 0.22 × 0.19 mm

Data collection
  • Bruker SMART APEXII CCD diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2009[Bruker (2009). APEX2, SADABS and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.570, Tmax = 0.746

  • 14066 measured reflections

  • 3424 independent reflections

  • 3226 reflections with I > 2σ(I)

  • Rint = 0.025

Refinement
  • R[F2 > 2σ(F2)] = 0.021

  • wR(F2) = 0.052

  • S = 1.10

  • 3424 reflections

  • 192 parameters

  • H-atom parameters constrained

  • Δρmax = 0.45 e Å−3

  • Δρmin = −0.55 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
C15—H15⋯O2i 0.95 2.44 3.183 (3) 135
Symmetry code: (i) x-1, y, z.

Data collection: APEX2 (Bruker, 2009[Bruker (2009). APEX2, SADABS and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2009[Bruker (2009). APEX2, SADABS and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]) and DIAMOND (Brandenburg, 1998[Brandenburg, K. (1998). DIAMOND. Crystal Impact GbR, Bonn, Germany.]); software used to prepare material for publication: SHELXL97.

Supporting information


Comment top

As a part of our ongoing study of 5-iodo-7-methyl-3-methylsulfinyl-1-benzofuran derivatives containing 2-phenyl (Choi et al., 2008) and 2-(4-fluorophenyl) (Choi et al., 2010) substituents, we report herein the crystal structure of the title compound.

In the title molecule (Fig. 1), the benzofuran unit is essentially planar, with a mean deviation of 0.019 (1) Å from the least-squares plane defined by the nine constituent atoms. The dihedral angle between the 3-fluorophenyl ring and the mean plane of the benzofuran fragment is 34.93 (7)°. In the crystal structure (Fig. 2), molecules are linked via pairs of I···O halogen-bondings (Politzer et al., 2007) between the iodine atom and the O atom of the SO unit [I1···O2i = 3.088 (2) Å, C4—I1···O2i = 169.86 (6)°], forming inversion dimers. These dimers are connected by weak intermolecular C—H···O hydrogen bonds (Table 1).

Related literature top

For background information and the crystal structures of related compounds, see: Choi et al. (2008, 2010). For a review of halogen bonding, see: Politzer et al. (2007).

Experimental top

3-Chloroperoxybenzoic acid (77%, 202 mg, 0.9 mmol) was added in small portions to a stirred solution of 2-(3-fluorophenyl)-5-iodo-7-methyl-3-methylsulfanyl-1-benzofuran (326 mg, 0.8 mmol) in dichloromethane (30 mL) at 273 K. After being stirred at room temperature for 4h, 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 column chromatography (hexane/ethyl acetate, 1:1 v/v) to afford the title compound as a colorless solid [yield 70%, m.p. 459–460 K; Rf = 0.56 (hexane?ethyl acetate, 1:1 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.

Refinement top

All H atoms were positioned geometrically and refined using a riding model, with C—H = 0.95 Å for aryl and 0.98 Å for methyl H atoms. Uiso(H) was set to 1.2Ueq(C) for aryl and 1.5Ueq(C) for methyl H atoms. The positions of methyl hydrogens were optimized rotationally.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: 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 (Farrugia, 1997) and DIAMOND (Brandenburg, 1998); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are presented as small spheres of arbitrary radius.
[Figure 2] Fig. 2. A view of the C—H···O and I···O interactions (dotted lines) in the crystal structure of the title compound. H atoms non-participating in hydrogen-bonding were omitted for clarity. [Symmetry codes: (i) - x + 2, - y + 1, - z + 2; (ii) x - 1, y, z; (iii) x + 1, y, z.]
2-(3-Fluorophenyl)-5-iodo-7-methyl-3-methylsulfinyl-1-benzofuran top
Crystal data top
C16H12FIO2SF(000) = 808
Mr = 414.22Dx = 1.849 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 8987 reflections
a = 7.8169 (1) Åθ = 2.7–27.5°
b = 23.9721 (3) ŵ = 2.30 mm1
c = 8.0559 (1) ÅT = 173 K
β = 99.748 (1)°Block, colourless
V = 1487.78 (3) Å30.30 × 0.22 × 0.19 mm
Z = 4
Data collection top
Bruker SMART APEXII CCD
diffractometer
3424 independent reflections
Radiation source: rotating anode3226 reflections with I > 2σ(I)
Graphite multilayer monochromatorRint = 0.025
Detector resolution: 10.0 pixels mm-1θmax = 27.5°, θmin = 1.7°
ϕ and ω scansh = 108
Absorption correction: multi-scan
(SADABS; Bruker, 2009)
k = 3130
Tmin = 0.570, Tmax = 0.746l = 1010
14066 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.021Hydrogen site location: difference Fourier map
wR(F2) = 0.052H-atom parameters constrained
S = 1.10 w = 1/[σ2(Fo2) + (0.0225P)2 + 1.0726P]
where P = (Fo2 + 2Fc2)/3
3424 reflections(Δ/σ)max = 0.002
192 parametersΔρmax = 0.45 e Å3
0 restraintsΔρmin = 0.55 e Å3
Crystal data top
C16H12FIO2SV = 1487.78 (3) Å3
Mr = 414.22Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.8169 (1) ŵ = 2.30 mm1
b = 23.9721 (3) ÅT = 173 K
c = 8.0559 (1) Å0.30 × 0.22 × 0.19 mm
β = 99.748 (1)°
Data collection top
Bruker SMART APEXII CCD
diffractometer
3424 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2009)
3226 reflections with I > 2σ(I)
Tmin = 0.570, Tmax = 0.746Rint = 0.025
14066 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0210 restraints
wR(F2) = 0.052H-atom parameters constrained
S = 1.10Δρmax = 0.45 e Å3
3424 reflectionsΔρmin = 0.55 e Å3
192 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
I10.830625 (17)0.412987 (6)1.026115 (17)0.02457 (6)
S10.70761 (6)0.66239 (2)0.72019 (6)0.02102 (11)
F10.11935 (17)0.70760 (6)0.33734 (19)0.0382 (3)
O10.31305 (17)0.56234 (6)0.56108 (17)0.0187 (3)
O20.88641 (19)0.64247 (7)0.7119 (2)0.0298 (3)
C10.5622 (3)0.60638 (8)0.6682 (2)0.0192 (4)
C20.5730 (2)0.54990 (8)0.7341 (2)0.0185 (4)
C30.6967 (3)0.51834 (8)0.8398 (3)0.0212 (4)
H30.80580.53360.88860.025*
C40.6524 (3)0.46397 (8)0.8699 (2)0.0204 (4)
C50.4901 (3)0.44112 (8)0.8021 (2)0.0207 (4)
H50.46520.40370.82830.025*
C60.3652 (2)0.47188 (8)0.6978 (2)0.0193 (4)
C70.4151 (2)0.52550 (8)0.6654 (2)0.0182 (4)
C80.4067 (2)0.61080 (8)0.5635 (2)0.0177 (4)
C90.1873 (3)0.44943 (9)0.6296 (3)0.0272 (5)
H9A0.10000.47060.67740.041*
H9B0.18130.41000.66030.041*
H9C0.16480.45310.50670.041*
C100.3182 (2)0.65543 (8)0.4579 (2)0.0184 (4)
C110.4081 (3)0.69255 (9)0.3707 (3)0.0240 (4)
H110.53010.68900.37720.029*
C120.3186 (3)0.73475 (10)0.2744 (3)0.0301 (5)
H120.38020.76000.21530.036*
C130.1406 (3)0.74046 (10)0.2636 (3)0.0300 (5)
H130.07920.76980.20010.036*
C140.0562 (3)0.70246 (9)0.3474 (3)0.0253 (4)
C150.1381 (3)0.65996 (9)0.4442 (2)0.0203 (4)
H150.07430.63440.50020.024*
C160.6965 (3)0.66712 (10)0.9404 (3)0.0308 (5)
H16A0.73820.63220.99640.046*
H16B0.57600.67360.95450.046*
H16C0.76910.69810.99050.046*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
I10.02277 (8)0.02225 (8)0.02801 (8)0.00522 (5)0.00230 (6)0.00455 (5)
S10.0205 (2)0.0182 (2)0.0234 (2)0.00496 (18)0.00100 (19)0.00187 (18)
F10.0224 (7)0.0458 (9)0.0453 (8)0.0121 (6)0.0022 (6)0.0103 (7)
O10.0175 (6)0.0161 (7)0.0213 (6)0.0019 (5)0.0002 (5)0.0015 (5)
O20.0183 (7)0.0381 (9)0.0330 (8)0.0056 (6)0.0044 (6)0.0003 (7)
C10.0189 (9)0.0177 (9)0.0211 (9)0.0020 (7)0.0033 (7)0.0010 (7)
C20.0185 (9)0.0158 (9)0.0215 (9)0.0006 (7)0.0045 (7)0.0007 (7)
C30.0166 (9)0.0213 (10)0.0250 (10)0.0002 (7)0.0018 (8)0.0002 (8)
C40.0210 (9)0.0201 (10)0.0201 (9)0.0040 (7)0.0033 (8)0.0024 (7)
C50.0224 (10)0.0163 (10)0.0246 (10)0.0008 (7)0.0071 (8)0.0002 (7)
C60.0191 (9)0.0180 (10)0.0211 (9)0.0021 (7)0.0040 (7)0.0020 (7)
C70.0169 (9)0.0185 (10)0.0191 (9)0.0004 (7)0.0032 (7)0.0007 (7)
C80.0177 (9)0.0168 (9)0.0193 (9)0.0019 (7)0.0050 (7)0.0000 (7)
C90.0212 (10)0.0232 (11)0.0353 (11)0.0064 (8)0.0002 (9)0.0009 (9)
C100.0203 (9)0.0169 (9)0.0173 (9)0.0003 (7)0.0012 (7)0.0003 (7)
C110.0222 (10)0.0252 (11)0.0249 (10)0.0013 (8)0.0050 (8)0.0026 (8)
C120.0346 (12)0.0257 (11)0.0305 (11)0.0036 (9)0.0070 (9)0.0091 (9)
C130.0361 (12)0.0248 (11)0.0274 (10)0.0060 (9)0.0004 (9)0.0068 (9)
C140.0213 (10)0.0283 (11)0.0251 (10)0.0064 (8)0.0010 (8)0.0002 (8)
C150.0210 (9)0.0198 (10)0.0200 (9)0.0009 (7)0.0030 (7)0.0011 (7)
C160.0372 (12)0.0309 (12)0.0245 (10)0.0044 (10)0.0063 (9)0.0049 (9)
Geometric parameters (Å, º) top
I1—C42.1034 (19)C6—C91.505 (3)
I1—O2i3.0876 (16)C8—C101.466 (3)
S1—O21.4891 (16)C9—H9A0.9800
S1—C11.763 (2)C9—H9B0.9800
S1—C161.795 (2)C9—H9C0.9800
F1—C141.366 (2)C10—C111.395 (3)
O1—C81.371 (2)C10—C151.398 (3)
O1—C71.376 (2)C11—C121.390 (3)
C1—C81.361 (3)C11—H110.9500
C1—C21.451 (3)C12—C131.386 (3)
C2—C71.393 (3)C12—H120.9500
C2—C31.397 (3)C13—C141.368 (3)
C3—C41.380 (3)C13—H130.9500
C3—H30.9500C14—C151.374 (3)
C4—C51.405 (3)C15—H150.9500
C5—C61.388 (3)C16—H16A0.9800
C5—H50.9500C16—H16B0.9800
C6—C71.381 (3)C16—H16C0.9800
C4—I1—O2i169.86 (6)C6—C9—H9B109.5
O2—S1—C1108.51 (9)H9A—C9—H9B109.5
O2—S1—C16105.52 (10)C6—C9—H9C109.5
C1—S1—C1698.38 (10)H9A—C9—H9C109.5
C8—O1—C7106.39 (14)H9B—C9—H9C109.5
C8—C1—C2106.86 (17)C11—C10—C15119.85 (18)
C8—C1—S1124.05 (15)C11—C10—C8121.95 (18)
C2—C1—S1128.91 (14)C15—C10—C8118.20 (17)
C7—C2—C3119.33 (18)C12—C11—C10119.7 (2)
C7—C2—C1104.67 (16)C12—C11—H11120.1
C3—C2—C1136.00 (18)C10—C11—H11120.1
C4—C3—C2116.76 (18)C13—C12—C11120.8 (2)
C4—C3—H3121.6C13—C12—H12119.6
C2—C3—H3121.6C11—C12—H12119.6
C3—C4—C5122.44 (18)C14—C13—C12117.8 (2)
C3—C4—I1119.57 (14)C14—C13—H13121.1
C5—C4—I1117.98 (15)C12—C13—H13121.1
C6—C5—C4121.68 (19)F1—C14—C13118.30 (19)
C6—C5—H5119.2F1—C14—C15117.87 (19)
C4—C5—H5119.2C13—C14—C15123.8 (2)
C7—C6—C5114.62 (18)C14—C15—C10117.96 (19)
C7—C6—C9122.47 (18)C14—C15—H15121.0
C5—C6—C9122.89 (19)C10—C15—H15121.0
O1—C7—C6124.02 (17)S1—C16—H16A109.5
O1—C7—C2110.87 (17)S1—C16—H16B109.5
C6—C7—C2125.11 (18)H16A—C16—H16B109.5
C1—C8—O1111.17 (17)S1—C16—H16C109.5
C1—C8—C10134.49 (18)H16A—C16—H16C109.5
O1—C8—C10114.33 (16)H16B—C16—H16C109.5
C6—C9—H9A109.5
O2—S1—C1—C8136.08 (17)C3—C2—C7—O1178.14 (17)
C16—S1—C1—C8114.37 (19)C1—C2—C7—O11.4 (2)
O2—S1—C1—C249.5 (2)C3—C2—C7—C62.5 (3)
C16—S1—C1—C260.0 (2)C1—C2—C7—C6177.92 (19)
C8—C1—C2—C72.2 (2)C2—C1—C8—O12.2 (2)
S1—C1—C2—C7172.98 (16)S1—C1—C8—O1173.22 (14)
C8—C1—C2—C3177.3 (2)C2—C1—C8—C10179.2 (2)
S1—C1—C2—C37.6 (4)S1—C1—C8—C105.3 (3)
C7—C2—C3—C40.2 (3)C7—O1—C8—C11.4 (2)
C1—C2—C3—C4179.6 (2)C7—O1—C8—C10179.76 (16)
C2—C3—C4—C51.5 (3)C1—C8—C10—C1137.1 (3)
C2—C3—C4—I1179.60 (14)O1—C8—C10—C11144.37 (18)
O2i—I1—C4—C331.2 (5)C1—C8—C10—C15143.5 (2)
O2i—I1—C4—C5147.7 (3)O1—C8—C10—C1535.0 (2)
C3—C4—C5—C61.1 (3)C15—C10—C11—C121.7 (3)
I1—C4—C5—C6179.97 (15)C8—C10—C11—C12178.94 (19)
C4—C5—C6—C71.0 (3)C10—C11—C12—C130.1 (3)
C4—C5—C6—C9177.2 (2)C11—C12—C13—C141.5 (3)
C8—O1—C7—C6179.23 (18)C12—C13—C14—F1179.9 (2)
C8—O1—C7—C20.1 (2)C12—C13—C14—C151.5 (3)
C5—C6—C7—O1177.90 (18)F1—C14—C15—C10178.52 (18)
C9—C6—C7—O13.9 (3)C13—C14—C15—C100.1 (3)
C5—C6—C7—C22.8 (3)C11—C10—C15—C141.7 (3)
C9—C6—C7—C2175.3 (2)C8—C10—C15—C14178.90 (18)
Symmetry code: (i) x+2, y+1, z+2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C15—H15···O2ii0.952.443.183 (3)135
Symmetry code: (ii) x1, y, z.

Experimental details

Crystal data
Chemical formulaC16H12FIO2S
Mr414.22
Crystal system, space groupMonoclinic, P21/c
Temperature (K)173
a, b, c (Å)7.8169 (1), 23.9721 (3), 8.0559 (1)
β (°) 99.748 (1)
V3)1487.78 (3)
Z4
Radiation typeMo Kα
µ (mm1)2.30
Crystal size (mm)0.30 × 0.22 × 0.19
Data collection
DiffractometerBruker SMART APEXII CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2009)
Tmin, Tmax0.570, 0.746
No. of measured, independent and
observed [I > 2σ(I)] reflections
14066, 3424, 3226
Rint0.025
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.021, 0.052, 1.10
No. of reflections3424
No. of parameters192
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.45, 0.55

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 1998).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C15—H15···O2i0.952.443.183 (3)135.0
Symmetry code: (i) x1, y, z.
 

References

First citationBrandenburg, K. (1998). DIAMOND. Crystal Impact GbR, Bonn, Germany.  Google Scholar
First citationBruker (2009). APEX2, SADABS and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationChoi, H. D., Seo, P. J., Kim, B. K., Son, B. W. & Lee, U. (2008). Acta Cryst. E64, o1116.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationChoi, H. D., Seo, P. J., Son, B. W. & Lee, U. (2010). Acta Cryst. E66, o1680.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationFarrugia, L. J. (1997). J. Appl. Cryst. 30, 565.  CrossRef IUCr Journals Google Scholar
First citationPolitzer, P., Lane, P., Concha, M. C., Ma, Y. & Murray, J. S. (2007). J. Mol. Model. 13, 305–311.  Web of Science CrossRef PubMed CAS Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds