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Acta Crystallogr Sect E Struct Rep Online. 2008 May 1; 64(Pt 5): o849.
Published online 2008 April 16. doi:  10.1107/S160053680800980X
PMCID: PMC2961259

2-Methyl-5,6-methyl­enedi­oxy-3-phenyl­sulfonyl-1-benzofuran

Abstract

The title compound, C16H12O5S, was prepared by oxidation of 2-methyl-5,6-methyl­ene­di­oxy-3-phenyl­sulfanyl-1-benzo­furan with 3-chloro­peroxy­benzoic acid. The phenyl ring makes a dihedral angle of 83.64 (4)° with the mean plane of the 5,6-(methyl­ene­di­oxy)­benzo­furan fragment. The crystal structure is stabilized by C—H(...)π inter­actions between a benzene H atom of the 5,6-(methyl­ene­di­oxy)­benzo­furan unit and the phenyl ring of the phenyl­sulfonyl substituent. Additionally, the crystal structure exhibits inter- and intra­molecular C—H(...)O inter­actions.

Related literature

For the crystal structures of similar 5,6-(methyl­ene­di­oxy)­benzo­furan compounds, see: Choi et al. (2007a [triangle],b [triangle]).

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Object name is e-64-0o849-scheme1.jpg

Experimental

Crystal data

  • C16H12O5S
  • M r = 316.32
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o849-efi1.jpg
  • a = 7.4401 (3) Å
  • b = 8.8505 (4) Å
  • c = 11.2406 (5) Å
  • α = 89.801 (1)°
  • β = 72.565 (1)°
  • γ = 79.257 (1)°
  • V = 692.71 (5) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.26 mm−1
  • T = 173 (2) K
  • 0.40 × 0.20 × 0.20 mm

Data collection

  • Bruker SMART CCD diffractometer
  • Absorption correction: none
  • 6000 measured reflections
  • 2983 independent reflections
  • 2746 reflections with I > 2σ(I)
  • R int = 0.026

Refinement

  • R[F 2 > 2σ(F 2)] = 0.036
  • wR(F 2) = 0.096
  • S = 1.05
  • 2983 reflections
  • 200 parameters
  • H-atom parameters constrained
  • Δρmax = 0.32 e Å−3
  • Δρmin = −0.38 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
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680800980X/bh2167sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680800980X/bh2167Isup2.hkl

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

supplementary crystallographic information

Comment

As part of our ongoing studies on the synthesis and structure of 5,6-(methylenedioxy)benzofuran derivatives, the crystal structures of 5,6-methylenedioxy-3-methylsulfinyl-2-phenylbenzofuran (Choi et al., 2007a) and 2-methyl-5,6-methylenedioxy-3-methylsulfinyl-1-benzofuran (Choi et al., 2007b) have been described to the literatures. Herein we report the molecular and crystal structure of the title compound, 2-methyl-5,6-methylenedioxy-3-phenylsulfonyl-1-benzofuran (Fig. 1).

The 5,6-(methylenedioxy)benzofuran unit is almost planar, with a mean deviation of 0.032 Å from the least-squares plane defined by the twelve constituent atoms. The crystal packing (Fig. 2) is stabilized by C—H···π interactions between a benzene H atom of 5,6-(methylenedioxy)benzofuran unit and the phenyl ring of the phenylsulfonyl substituent, with a C6—H6···Cgi separation of 2.83 Å (Fig. 2 and Table 1; Cg is the centroid of the C9–C14 benzene ring, symmetry code as in Fig. 2). The molecular packing (Fig. 2) is further stabilized by intermolecular and intramolecular C—H···O interactions (Table 1 and Fig.2; symmetry codes as in Fig. 2).

Experimental

3-Chloroperoxybenzoic acid (77%, 560 mg, 2.50 mmol) was added in small portions to a stirred solution of 2-methyl-5,6-methylenedioxy-3-phenyl-sulfonyl-1-benzofuran (341 mg, 1.20 mmol) in dichloromethane (30 ml) at room temperature. After being stirred for 4 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 (hexane–ethyl acetate, 2:1 v/v) to afford the title compound as a colorless solid [yield 76%, m.p. 442–443 K; Rf = 0.54 (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 acetone at room temperature.

Refinement

All H atoms were positioned geometrically and refined using a riding model, with C—H = 0.95 Å for aromatic H atoms, 0.99 Å for methylene H atoms and 0.98 Å for methyl H atoms, respectively, and with Uiso(H) = 1.2Ueq(C) for aromatic and methylene, Uiso(H) = 1.5Ueq(C) for methyl H atoms.

Figures

Fig. 1.
The molecular structure of the title compound, showing displacement ellipsoids drawn at the 50% probability level.
Fig. 2.
C—H···π and intra- and intermolecular C—H···O interactions (dotted lines) in the title compound. Cg denotes the ring centroids. [Symmetry code: (i) -x, -y + 2, -z + 1; (ii) -x + 1, ...

Crystal data

C16H12O5SZ = 2
Mr = 316.32F000 = 328
Triclinic, P1Dx = 1.517 Mg m3
Hall symbol: -P 1Melting point = 442–443 K
a = 7.4401 (3) ÅMo Kα radiation λ = 0.71073 Å
b = 8.8505 (4) ÅCell parameters from 4646 reflections
c = 11.2406 (5) Åθ = 2.4–28.2º
α = 89.801 (1)ºµ = 0.26 mm1
β = 72.565 (1)ºT = 173 (2) K
γ = 79.257 (1)ºBlock, colourless
V = 692.71 (5) Å30.40 × 0.20 × 0.20 mm

Data collection

Bruker SMART CCD diffractometer2983 independent reflections
Radiation source: fine-focus sealed tube2746 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.026
Detector resolution: 10.0 pixels mm-1θmax = 27.0º
T = 173(2) Kθmin = 2.9º
[var phi] and ω scansh = −9→9
Absorption correction: nonek = −11→11
6000 measured reflectionsl = −14→13

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.036H-atom parameters constrained
wR(F2) = 0.096  w = 1/[σ2(Fo2) + (0.0449P)2 + 0.3658P] where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max < 0.001
2983 reflectionsΔρmax = 0.32 e Å3
200 parametersΔρmin = −0.38 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
S0.36347 (5)0.72181 (4)0.70730 (3)0.02587 (12)
O10.16796 (16)1.11741 (12)0.58768 (11)0.0317 (3)
O20.46615 (19)0.74239 (14)0.16742 (10)0.0364 (3)
O30.3156 (2)0.98837 (15)0.14228 (11)0.0399 (3)
O40.52005 (16)0.61904 (13)0.62032 (10)0.0313 (3)
O50.38566 (18)0.77361 (16)0.82216 (11)0.0388 (3)
C10.2989 (2)0.88120 (17)0.62765 (14)0.0250 (3)
C20.3186 (2)0.88013 (17)0.49576 (14)0.0236 (3)
C30.4015 (2)0.76992 (17)0.39479 (13)0.0249 (3)
H30.46090.66760.40390.030*
C40.3893 (2)0.82284 (18)0.28230 (14)0.0266 (3)
C50.3014 (2)0.97239 (19)0.26672 (15)0.0290 (3)
C60.2216 (2)1.08254 (18)0.36244 (16)0.0311 (3)
H60.16311.18470.35210.037*
C70.2350 (2)1.02901 (17)0.47682 (15)0.0263 (3)
C80.2083 (2)1.02469 (19)0.67807 (15)0.0299 (3)
C90.1598 (2)0.63445 (17)0.74530 (14)0.0259 (3)
C100.1304 (2)0.54383 (18)0.65468 (16)0.0311 (3)
H100.22290.52300.57450.037*
C11−0.0363 (3)0.4846 (2)0.6836 (2)0.0397 (4)
H11−0.05950.42360.62250.048*
C12−0.1687 (3)0.5136 (2)0.8009 (2)0.0443 (5)
H12−0.28360.47390.81940.053*
C13−0.1355 (3)0.6000 (2)0.89174 (19)0.0455 (5)
H13−0.22530.61620.97310.055*
C140.0288 (3)0.6630 (2)0.86401 (16)0.0366 (4)
H140.05120.72450.92520.044*
C150.4011 (3)0.8388 (2)0.08173 (17)0.0467 (5)
H15A0.30560.79520.05460.056*
H15B0.51030.84630.00710.056*
C160.1447 (3)1.0983 (2)0.80603 (17)0.0421 (4)
H16A0.00641.10360.84300.063*
H16B0.17201.20270.80210.063*
H16C0.21371.03740.85740.063*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S0.0256 (2)0.0340 (2)0.01994 (19)−0.00685 (15)−0.00916 (14)0.00132 (14)
O10.0297 (6)0.0249 (5)0.0371 (6)−0.0040 (4)−0.0060 (5)−0.0037 (5)
O20.0539 (8)0.0377 (6)0.0213 (5)−0.0141 (6)−0.0137 (5)0.0014 (5)
O30.0539 (8)0.0439 (7)0.0329 (6)−0.0191 (6)−0.0238 (6)0.0157 (5)
O40.0265 (6)0.0366 (6)0.0286 (6)−0.0008 (5)−0.0082 (4)0.0029 (5)
O50.0428 (7)0.0556 (8)0.0249 (6)−0.0163 (6)−0.0164 (5)0.0010 (5)
C10.0237 (7)0.0285 (7)0.0236 (7)−0.0070 (6)−0.0071 (5)−0.0009 (6)
C20.0223 (7)0.0257 (7)0.0243 (7)−0.0070 (5)−0.0080 (5)0.0024 (5)
C30.0284 (7)0.0238 (7)0.0236 (7)−0.0054 (6)−0.0091 (6)0.0014 (6)
C40.0299 (7)0.0295 (8)0.0236 (7)−0.0124 (6)−0.0090 (6)0.0024 (6)
C50.0296 (8)0.0355 (8)0.0291 (8)−0.0148 (6)−0.0145 (6)0.0115 (6)
C60.0284 (8)0.0262 (7)0.0418 (9)−0.0072 (6)−0.0142 (7)0.0107 (7)
C70.0226 (7)0.0244 (7)0.0319 (8)−0.0065 (5)−0.0069 (6)−0.0002 (6)
C80.0252 (7)0.0329 (8)0.0304 (8)−0.0093 (6)−0.0044 (6)−0.0045 (6)
C90.0254 (7)0.0273 (7)0.0257 (7)−0.0053 (6)−0.0089 (6)0.0048 (6)
C100.0328 (8)0.0276 (8)0.0336 (8)−0.0028 (6)−0.0131 (7)0.0014 (6)
C110.0406 (9)0.0276 (8)0.0580 (11)−0.0083 (7)−0.0244 (9)0.0041 (8)
C120.0325 (9)0.0333 (9)0.0694 (13)−0.0113 (7)−0.0160 (9)0.0172 (9)
C130.0332 (9)0.0470 (11)0.0467 (11)−0.0073 (8)0.0017 (8)0.0132 (8)
C140.0366 (9)0.0406 (9)0.0290 (8)−0.0078 (7)−0.0045 (7)0.0023 (7)
C150.0520 (11)0.0598 (12)0.0258 (9)−0.0075 (9)−0.0105 (8)0.0105 (8)
C160.0381 (9)0.0464 (10)0.0364 (9)−0.0107 (8)−0.0017 (7)−0.0164 (8)

Geometric parameters (Å, °)

S—O51.4369 (12)C6—H60.9500
S—O41.4384 (12)C8—C161.484 (2)
S—C11.7374 (16)C9—C141.388 (2)
S—C91.7674 (15)C9—C101.390 (2)
O1—C81.371 (2)C10—C111.385 (2)
O1—C71.3794 (18)C10—H100.9500
O2—C41.3833 (18)C11—C121.380 (3)
O2—C151.418 (2)C11—H110.9500
O3—C51.3797 (19)C12—C131.384 (3)
O3—C151.433 (2)C12—H120.9500
C1—C81.358 (2)C13—C141.388 (3)
C1—C21.445 (2)C13—H130.9500
C2—C71.393 (2)C14—H140.9500
C2—C31.409 (2)C15—H15A0.9900
C3—C41.369 (2)C15—H15B0.9900
C3—H30.9500C16—H16A0.9800
C4—C51.398 (2)C16—H16B0.9800
C5—C61.367 (2)C16—H16C0.9800
C6—C71.394 (2)
O5—S—O4119.53 (7)O1—C8—C16115.53 (15)
O5—S—C1108.96 (8)C14—C9—C10121.50 (15)
O4—S—C1107.55 (7)C14—C9—S118.94 (13)
O5—S—C9107.76 (7)C10—C9—S119.51 (12)
O4—S—C9108.26 (7)C11—C10—C9118.71 (16)
C1—S—C9103.65 (7)C11—C10—H10120.6
C8—O1—C7107.02 (12)C9—C10—H10120.6
C4—O2—C15105.85 (13)C12—C11—C10120.33 (17)
C5—O3—C15105.87 (13)C12—C11—H11119.8
C8—C1—C2107.71 (14)C10—C11—H11119.8
C8—C1—S126.84 (12)C11—C12—C13120.56 (17)
C2—C1—S125.26 (11)C11—C12—H12119.7
C7—C2—C3120.48 (14)C13—C12—H12119.7
C7—C2—C1104.66 (13)C12—C13—C14120.04 (18)
C3—C2—C1134.85 (14)C12—C13—H13120.0
C4—C3—C2114.24 (14)C14—C13—H13120.0
C4—C3—H3122.9C9—C14—C13118.81 (17)
C2—C3—H3122.9C9—C14—H14120.6
C3—C4—O2126.58 (14)C13—C14—H14120.6
C3—C4—C5123.90 (14)O2—C15—O3108.47 (14)
O2—C4—C5109.48 (13)O2—C15—H15A110.0
C6—C5—O3127.47 (15)O3—C15—H15A110.0
C6—C5—C4123.31 (14)O2—C15—H15B110.0
O3—C5—C4109.19 (14)O3—C15—H15B110.0
C5—C6—C7112.80 (14)H15A—C15—H15B108.4
C5—C6—H6123.6C8—C16—H16A109.5
C7—C6—H6123.6C8—C16—H16B109.5
O1—C7—C2110.33 (13)H16A—C16—H16B109.5
O1—C7—C6124.42 (14)C8—C16—H16C109.5
C2—C7—C6125.25 (15)H16A—C16—H16C109.5
C1—C8—O1110.29 (14)H16B—C16—H16C109.5
C1—C8—C16134.18 (17)
O5—S—C1—C8−25.07 (16)C1—C2—C7—O10.06 (16)
O4—S—C1—C8−156.01 (14)C3—C2—C7—C61.1 (2)
C9—S—C1—C889.47 (15)C1—C2—C7—C6179.64 (14)
O5—S—C1—C2160.50 (12)C5—C6—C7—O1179.15 (13)
O4—S—C1—C229.55 (15)C5—C6—C7—C2−0.4 (2)
C9—S—C1—C2−84.96 (14)C2—C1—C8—O1−0.16 (17)
C8—C1—C2—C70.06 (16)S—C1—C8—O1−175.39 (11)
S—C1—C2—C7175.39 (11)C2—C1—C8—C16179.14 (17)
C8—C1—C2—C3178.25 (16)S—C1—C8—C163.9 (3)
S—C1—C2—C3−6.4 (3)C7—O1—C8—C10.19 (17)
C7—C2—C3—C4−0.6 (2)C7—O1—C8—C16−179.25 (13)
C1—C2—C3—C4−178.60 (15)O5—S—C9—C1417.03 (15)
C2—C3—C4—O2176.68 (14)O4—S—C9—C14147.62 (13)
C2—C3—C4—C5−0.5 (2)C1—S—C9—C14−98.37 (14)
C15—O2—C4—C3174.65 (16)O5—S—C9—C10−165.42 (12)
C15—O2—C4—C5−7.83 (18)O4—S—C9—C10−34.83 (14)
C15—O3—C5—C6−177.05 (17)C1—S—C9—C1079.18 (13)
C15—O3—C5—C44.93 (18)C14—C9—C10—C111.7 (2)
C3—C4—C5—C61.3 (2)S—C9—C10—C11−175.83 (12)
O2—C4—C5—C6−176.29 (14)C9—C10—C11—C12−0.9 (2)
C3—C4—C5—O3179.42 (14)C10—C11—C12—C13−1.1 (3)
O2—C4—C5—O31.82 (17)C11—C12—C13—C142.3 (3)
O3—C5—C6—C7−178.56 (14)C10—C9—C14—C13−0.5 (3)
C4—C5—C6—C7−0.8 (2)S—C9—C14—C13177.04 (14)
C8—O1—C7—C2−0.15 (16)C12—C13—C14—C9−1.5 (3)
C8—O1—C7—C6−179.74 (14)C4—O2—C15—O310.86 (19)
C3—C2—C7—O1−178.45 (12)C5—O3—C15—O2−9.81 (19)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C6—H6···Cgi0.952.833.722 (3)152
C3—H3···O4ii0.952.533.379 (2)150
C12—H12···O2iii0.952.533.398 (2)153
C16—H16C···O50.982.423.127 (3)129

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BH2167).

References

  • Brandenburg, K. (1998). DIAMOND Crystal Impact GbR, Bonn, Germany.
  • Bruker (2001). SAINT and SMART Bruker AXS Inc., Madison, Wisconsin, USA.
  • Choi, H. D., Seo, P. J., Lee, H. K., Son, B. W. & Lee, U. (2007a). Acta Cryst. E63, o519–o520.
  • Choi, H. D., Seo, P. J., Lee, J. B., Son, B. W. & Lee, U. (2007b). Acta Cryst. E63, o2050–o2051.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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