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Acta Crystallogr Sect E Struct Rep Online. 2008 December 1; 64(Pt 12): o2431.
Published online 2008 November 26. doi:  10.1107/S1600536808038671
PMCID: PMC2960088

Isopropyl 2-(5-iodo-7-methyl-3-methyl­sulfinyl-1-benzofuran-2-yl)acetate

Abstract

In the title mol­ecule, C15H17IO4S, the O atom and the methyl group of the methyl­sulfinyl substituent lie on opposite sides of the plane of the benzofuran fragment. In the crystal structure, inter­molecular I(...)O [2.994 (3) Å] halogen bonding links the mol­ecules into centrosymmetric dimers, which are further packed into ribbons along the c axis by inter­molecular sulfin­yl–sulfinyl inter­actions [S(...)O 3.128 (3) Å].

Related literature

For the crystal structures of similar isopropyl 2-(3-methyl­sulfinyl-1-benzofuran-2-yl)acetate derivatives, see Choi et al. (2008a [triangle],b [triangle]). For a review of halogen bonding, see Politzer et al. (2007 [triangle]). For a review of carbon­yl–carbonyl inter­actions, see Allen et al. (1998 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-o2431-scheme1.jpg

Experimental

Crystal data

  • C15H17IO4S
  • M r = 420.25
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o2431-efi3.jpg
  • a = 17.615 (2) Å
  • b = 10.0905 (7) Å
  • c = 19.144 (1) Å
  • β = 99.177 (2)°
  • V = 3359.2 (5) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 2.04 mm−1
  • T = 298 (2) K
  • 0.40 × 0.30 × 0.20 mm

Data collection

  • Bruker SMART CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1999 [triangle]) T min = 0.480, T max = 0.667
  • 6667 measured reflections
  • 2897 independent reflections
  • 2172 reflections with I > 2σ(I)
  • R int = 0.030

Refinement

  • R[F 2 > 2σ(F 2)] = 0.033
  • wR(F 2) = 0.064
  • S = 1.24
  • 2897 reflections
  • 192 parameters
  • H-atom parameters constrained
  • Δρmax = 0.48 e Å−3
  • Δρmin = −0.37 e Å−3

Data collection: SMART (Bruker, 2001 [triangle]); cell refinement: SAINT (Bruker, 2001 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 (Farrugia, 1997 [triangle]) and DIAMOND (Brandenburg, 1998 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Selected interatomic distances (Å)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808038671/cv2478sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808038671/cv2478Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

This work is related to our previous communications on the synthesis and structure of isopropyl 2-(3-methylsulfinyl-1-benzofuran-2-yl)acetate analogues, viz. isopropyl 2-(5-methyl-3-methylsulfinyl-1-benzofuran-2-yl)acetate (Choi et al., 2008a) and isopropyl 2-(5-bromo-3-methylsulfinyl-1-benzofuran-2-yl)acetate (Choi et al., 2008b). Here we report the crystal structure of the title compound, isopropyl 2-(5-iodo-7-methyl-3-methylsulfinyl-1-benzofuran-2-yl)acetate (Fig. 1).

The benzofuran unit is essentially planar, with a mean deviation of 0.030 (3) Å from the least-squares plane defined by the nine constituent atoms. The molecular packing (Fig. 2) is stabilized by intermolecular I···O halogen bonding (Politzer et al., 2007) of 2.994 (3) Å and a nearly linear C—I···O angle of 168.51 (9)°, which link the molecules into centrosymmetric dimers (Table 1). These dimers are further packed into ribbons along the c axis by sulfinyl–sulfinyl interactions (Table 1) interpreted as simliar to a type–II carbonyl–carbonyl interaction (Allen et al., 1998).

Experimental

77% 3-Chloroperoxybenzoic acid (123 mg, 0.55 mmol) was added in small portions to a stirred solution of isopropyl 2-(5-iodo-7-methyl-3-methylsulfanyl-1-benzofuran-2-yl)acetate (202 mg, 0.5 mmol) in dichloromethane (30 ml) at 273 K. After being stirred for 3 h at room temperature, 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 81%, m.p. 396-397 K; Rf = 0.74 (ethyl acetate)]. Single crystals suitable for X-ray diffraction were prepared by evaporation of a solution of the title compound in acetone at room temperature. Spectroscopic analysis: 1H NMR (CDCl3, 400 MHz) δ 1.27 (d, J = 6.24 Hz, 6H), 2.46 (s, 3H), 3.06 (s, 3H), 4.00 (s, 2H), 5.03-5.09 (m, 1H), 7.49 (s, 1H), 8.10 (s, 1H); EI-MS 420 [M+].

Refinement

All H atoms were geometrically positioned and refined using a riding model, with C—H = 0.93 Å for the aryl, 0.97 Å for the methylene, 0.98 Å for the methine, and 0.96 Å for the methyl H atoms. Uiso(H) = 1.2Ueq(C) for the aryl, methine and methylene H atoms, and 1.5Ueq(C) for methyl H atoms.

Figures

Fig. 1.
The molecular structure of the title compound, showing displacement ellipsoids drawn at the 30% probability level.
Fig. 2.
A portion of the crystal packing showing the I···O halogen bonding and S···O interactions by dotted lines [symmetry codes: (i) -x+1, -y+1, -z; (ii) -x+1, y, -z+1/2; (iii) x, -y+1, z-1/2].

Crystal data

C15H17IO4SF000 = 1664
Mr = 420.25Dx = 1.662 Mg m3
Monoclinic, C2/cMelting point = 420–421 K
Hall symbol: -C 2ycMo Kα radiation λ = 0.71073 Å
a = 17.615 (2) ÅCell parameters from 5394 reflections
b = 10.0905 (7) Åθ = 2.2–28.1º
c = 19.144 (1) ŵ = 2.04 mm1
β = 99.177 (2)ºT = 298 (2) K
V = 3359.2 (5) Å3Block, colourless
Z = 80.40 × 0.30 × 0.20 mm

Data collection

Bruker SMART CCD diffractometer2897 independent reflections
Radiation source: fine-focus sealed tube2172 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.030
Detector resolution: 10.0 pixels mm-1θmax = 26.0º
T = 298(2) Kθmin = 2.5º
[var phi] and ω scansh = −12→21
Absorption correction: multi-scan(SADABS; Sheldrick, 1999)k = −12→12
Tmin = 0.480, Tmax = 0.667l = −23→23
6667 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.033H-atom parameters constrained
wR(F2) = 0.064  w = 1/[σ2(Fo2)]
S = 1.24(Δ/σ)max < 0.001
2897 reflectionsΔρmax = 0.49 e Å3
192 parametersΔρmin = −0.37 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Special details

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)

xyzUiso*/Ueq
I0.513353 (18)0.743648 (18)−0.024404 (13)0.04774 (10)
S0.60070 (6)0.34161 (6)0.23510 (5)0.0450 (2)
O10.61238 (16)0.71392 (18)0.29955 (13)0.0445 (7)
O20.71791 (17)0.4874 (2)0.48324 (13)0.0503 (7)
O30.7643 (2)0.5249 (3)0.38247 (15)0.0783 (10)
O40.53494 (17)0.3086 (2)0.17899 (13)0.0554 (7)
C10.6014 (2)0.5163 (3)0.24557 (19)0.0408 (9)
C20.5868 (2)0.6160 (2)0.19074 (19)0.0382 (9)
C30.5656 (2)0.6170 (3)0.11784 (18)0.0389 (9)
H30.56040.53860.09200.047*
C40.5524 (2)0.7395 (2)0.0848 (2)0.0394 (8)
C50.5640 (2)0.8584 (3)0.12417 (19)0.0430 (9)
H50.55670.93880.10030.052*
C60.5853 (2)0.8597 (3)0.19600 (19)0.0414 (9)
C70.5950 (2)0.7356 (2)0.2277 (2)0.0385 (8)
C80.6142 (2)0.5781 (3)0.30852 (19)0.0409 (9)
C90.6276 (2)0.5310 (3)0.3828 (2)0.0470 (10)
H9A0.60210.44630.38510.056*
H9B0.60420.59320.41160.056*
C100.7106 (3)0.5155 (3)0.4138 (2)0.0452 (10)
C110.7939 (3)0.4653 (4)0.5226 (2)0.0575 (11)
H110.82620.42170.49220.069*
C120.7830 (3)0.3742 (4)0.5829 (2)0.0690 (13)
H12A0.75930.29330.56420.083*
H12B0.75070.41660.61210.083*
H12C0.83210.35480.61060.083*
C130.8288 (3)0.5958 (5)0.5478 (3)0.0918 (17)
H13A0.79710.63820.57750.110*
H13B0.83250.65130.50770.110*
H13C0.87920.58130.57410.110*
C140.5999 (3)0.9856 (3)0.2391 (2)0.0615 (12)
H14A0.59010.96980.28630.092*
H14B0.56641.05440.21760.092*
H14C0.65251.01250.24070.092*
C150.6855 (3)0.3293 (4)0.1950 (3)0.0887 (19)
H15A0.69470.23810.18480.133*
H15B0.72860.36360.22690.133*
H15C0.67870.37960.15190.133*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
I0.0565 (2)0.04572 (12)0.04033 (15)−0.00107 (11)0.00570 (13)−0.00037 (10)
S0.0481 (7)0.0287 (3)0.0571 (6)−0.0014 (4)0.0050 (5)0.0060 (3)
O10.056 (2)0.0353 (10)0.0405 (15)−0.0035 (10)0.0028 (14)0.0011 (9)
O20.0467 (19)0.0623 (14)0.0407 (16)0.0041 (13)0.0029 (14)0.0026 (12)
O30.050 (2)0.133 (2)0.054 (2)0.0157 (18)0.0137 (18)0.0208 (17)
O40.073 (2)0.0443 (11)0.0475 (17)−0.0087 (12)0.0045 (16)−0.0040 (11)
C10.042 (2)0.0309 (13)0.048 (2)−0.0029 (14)0.0013 (18)0.0044 (13)
C20.036 (2)0.0290 (13)0.049 (2)−0.0007 (13)0.0047 (19)0.0011 (13)
C30.041 (2)0.0303 (13)0.044 (2)−0.0048 (13)0.0030 (19)−0.0053 (13)
C40.038 (2)0.0395 (15)0.040 (2)−0.0008 (14)0.0057 (18)0.0016 (13)
C50.049 (3)0.0282 (13)0.051 (2)−0.0017 (14)0.007 (2)0.0047 (14)
C60.049 (3)0.0318 (14)0.042 (2)−0.0027 (14)0.0035 (19)−0.0004 (13)
C70.040 (2)0.0319 (14)0.041 (2)−0.0033 (13)0.0007 (18)−0.0019 (13)
C80.038 (2)0.0351 (14)0.048 (2)−0.0014 (14)0.0022 (19)0.0053 (14)
C90.046 (3)0.0473 (16)0.047 (2)−0.0063 (17)0.004 (2)0.0062 (15)
C100.047 (3)0.0417 (15)0.047 (2)0.0019 (16)0.008 (2)0.0035 (15)
C110.047 (3)0.078 (2)0.045 (3)0.019 (2)−0.002 (2)0.0008 (19)
C120.084 (4)0.068 (2)0.051 (3)0.014 (2)−0.002 (3)0.0033 (19)
C130.077 (4)0.117 (4)0.076 (4)−0.037 (3)−0.004 (3)0.007 (3)
C140.086 (4)0.0306 (14)0.064 (3)−0.0021 (17)−0.002 (2)−0.0057 (15)
C150.073 (4)0.052 (2)0.151 (6)0.006 (2)0.049 (4)−0.001 (2)

Geometric parameters (Å, °)

I—C42.095 (4)C6—C141.514 (4)
I—O4i2.994 (3)C8—C91.483 (5)
S—O41.486 (3)C9—C101.496 (5)
S—O4ii3.128 (3)C9—H9A0.9700
S—C11.773 (3)C9—H9B0.9700
S—C151.789 (4)C11—C131.500 (6)
O1—C71.378 (4)C11—C121.511 (5)
O1—C81.381 (3)C11—H110.9800
O2—C101.346 (4)C12—H12A0.9600
O2—C111.445 (6)C12—H12B0.9600
O3—C101.201 (4)C12—H12C0.9600
C1—C81.344 (5)C13—H13A0.9600
C1—C21.447 (5)C13—H13B0.9600
C2—C31.386 (5)C13—H13C0.9600
C2—C71.395 (4)C14—H14A0.9600
C3—C41.392 (4)C14—H14B0.9600
C3—H30.9300C14—H14C0.9600
C4—C51.414 (4)C15—H15A0.9600
C5—C61.367 (5)C15—H15B0.9600
C5—H50.9300C15—H15C0.9600
C6—C71.390 (4)
I···O4i2.994 (3)S···O4ii3.128 (3)
O4—S—C1107.19 (17)H9A—C9—H9B107.6
C4—I—O4i168.51 (9)O3—C10—O2123.5 (4)
O4—S—C15106.4 (2)O3—C10—C9126.3 (4)
C1—S—C1597.22 (16)O2—C10—C9110.3 (3)
C7—O1—C8106.2 (2)O2—C11—C13109.3 (3)
C10—O2—C11118.8 (3)O2—C11—C12105.8 (4)
C8—C1—C2108.2 (3)C13—C11—C12112.6 (4)
C8—C1—S124.1 (3)O2—C11—H11109.7
C2—C1—S127.7 (3)C13—C11—H11109.7
C3—C2—C7119.6 (3)C12—C11—H11109.7
C3—C2—C1136.4 (3)C11—C12—H12A109.5
C7—C2—C1104.0 (3)C11—C12—H12B109.5
C2—C3—C4117.6 (3)H12A—C12—H12B109.5
C2—C3—H3121.2C11—C12—H12C109.5
C4—C3—H3121.2H12A—C12—H12C109.5
C3—C4—C5120.8 (4)H12B—C12—H12C109.5
C3—C4—I118.4 (2)C11—C13—H13A109.5
C5—C4—I120.7 (2)C11—C13—H13B109.5
C6—C5—C4122.5 (3)H13A—C13—H13B109.5
C6—C5—H5118.7C11—C13—H13C109.5
C4—C5—H5118.7H13A—C13—H13C109.5
C5—C6—C7115.2 (3)H13B—C13—H13C109.5
C5—C6—C14123.5 (3)C6—C14—H14A109.5
C7—C6—C14121.3 (3)C6—C14—H14B109.5
O1—C7—C6124.8 (3)H14A—C14—H14B109.5
O1—C7—C2110.9 (2)C6—C14—H14C109.5
C6—C7—C2124.2 (4)H14A—C14—H14C109.5
C1—C8—O1110.6 (3)H14B—C14—H14C109.5
C1—C8—C9133.6 (3)S—C15—H15A109.5
O1—C8—C9115.8 (3)S—C15—H15B109.5
C8—C9—C10114.2 (3)H15A—C15—H15B109.5
C8—C9—H9A108.7S—C15—H15C109.5
C10—C9—H9A108.7H15A—C15—H15C109.5
C8—C9—H9B108.7H15B—C15—H15C109.5
C10—C9—H9B108.7
O4—S—C1—C8137.8 (3)C5—C6—C7—C22.3 (6)
C15—S—C1—C8−112.5 (4)C14—C6—C7—C2−176.2 (4)
O4—S—C1—C2−40.3 (4)C3—C2—C7—O1176.9 (3)
C15—S—C1—C269.4 (4)C1—C2—C7—O1−0.6 (4)
C8—C1—C2—C3−175.0 (4)C3—C2—C7—C6−1.9 (6)
S—C1—C2—C33.4 (7)C1—C2—C7—C6−179.4 (4)
C8—C1—C2—C71.9 (4)C2—C1—C8—O1−2.5 (4)
S—C1—C2—C7−179.8 (3)S—C1—C8—O1179.1 (3)
C7—C2—C3—C4−0.8 (5)C2—C1—C8—C9175.8 (4)
C1—C2—C3—C4175.7 (4)S—C1—C8—C9−2.6 (6)
C2—C3—C4—C53.0 (5)C7—O1—C8—C12.1 (4)
C2—C3—C4—I−176.1 (2)C7—O1—C8—C9−176.6 (3)
C3—C4—C5—C6−2.7 (6)C1—C8—C9—C1093.3 (5)
I—C4—C5—C6176.4 (3)O1—C8—C9—C10−88.4 (4)
C4—C5—C6—C70.1 (5)C11—O2—C10—O3−0.9 (5)
C4—C5—C6—C14178.5 (4)C11—O2—C10—C9178.4 (3)
C8—O1—C7—C6178.0 (4)C8—C9—C10—O3−7.7 (5)
C8—O1—C7—C2−0.8 (4)C8—C9—C10—O2172.9 (2)
C5—C6—C7—O1−176.4 (3)C10—O2—C11—C1386.0 (4)
C14—C6—C7—O15.1 (6)C10—O2—C11—C12−152.5 (3)

Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+1, y, −z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CV2478).

References

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  • Choi, H. D., Seo, P. J., Son, B. W. & Lee, U. (2008b). Acta Cryst. E64, o2250. [PMC free article] [PubMed]
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