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Acta Crystallogr Sect E Struct Rep Online. 2009 September 1; 65(Pt 9): o2267.
Published online 2009 August 29. doi:  10.1107/S1600536809033492
PMCID: PMC2970158

Isopropyl 2-[5-(4-hydroxy­phen­yl)-3-methyl­sulfanyl-1-benzofuran-2-yl]acetate

Abstract

In the title compound, C20H20O4S, the 4-hydroxy­phenyl ring is rotated out of the plane of the benzofuran unit by 32.87 (8)°. The S—Cmeth­yl bond is almost perpendicular to the plane of the benzofuran fragment [77.8 (1)°] and is slightly tilted towards it. The crystal structure is stabilized by inter­molecular O—H(...)O and C—H(...)O hydrogen bonds.

Related literature

For the crystal structure of a similar alkyl 2-[5-(4-hydroxy­phen­yl)-3-methyl­sulfanyl-1-benzofuran-2-yl]acetate derivative, see: Choi et al. (2006 [triangle]). For the pharmacological activity of benzofuran compounds, see: Howlett et al. (1999 [triangle]); Twyman & Allsop (1999 [triangle]). For natural products containing the benzofuran unit, see: Akgul & Anil (2003 [triangle]); von Reuss & König (2004 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o2267-scheme1.jpg

Experimental

Crystal data

  • C20H20O4S
  • M r = 356.42
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2267-efi10.jpg
  • a = 31.375 (3) Å
  • b = 8.0055 (7) Å
  • c = 15.274 (1) Å
  • β = 107.727 (1)°
  • V = 3654.2 (5) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 0.20 mm−1
  • T = 173 K
  • 0.45 × 0.40 × 0.10 mm

Data collection

  • Bruker SMART CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 2000 [triangle]) T min = 0.916, T max = 0.981
  • 15589 measured reflections
  • 4158 independent reflections
  • 2474 reflections with I > 2σ(I)
  • R int = 0.051

Refinement

  • R[F 2 > 2σ(F 2)] = 0.042
  • wR(F 2) = 0.111
  • S = 1.06
  • 4158 reflections
  • 233 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.17 e Å−3
  • Δρmin = −0.25 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/S1600536809033492/bt5043sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809033492/bt5043Isup2.hkl

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

supplementary crystallographic information

Comment

Hetero aromatic compounds containing the benzofuran skeleton have attracted particular interest in the view of their pharmacological properties (Howlett et al., 1999; Twyman & Allsop, 1999), and these compounds are occurring in natural products (Akgul & Anil, 2003; von Reuss & König, 2004). As a part of our ongoing studies of the effect of side chain substituents on the solid state structures of alkyl 2-[5-(4-hydroxyphenyl)-3-methylsulfanyl-1-benzofuran-2-yl]acetate analogues (Choi et al., 2006), the crystal structure of the title compound has been determined (Fig. 1).

The benzofuran unit is essentially planar, with a mean deviation of 0.007 (2) Å from the least-squares plane defined by the nine constituent atoms. The 4-hydroxyphenyl ring is rotated out of the benzofuran plane, with a dihedral angle of 32.87 (8)°. The crystal packing (Fig. 2) is stabilized by intermolecular O–H···O and C–H···O hydrogen bonds; the first between the H atom of the hydroxy group and the oxygen of the C═O unit, with a O4–H4···O3i, the second between the methyl H atom of the methylsulfinyl substituent and the H atom of the hydroxy group, with a C13–H13B···O4ii, respectively (Table 1).

Experimental

2-[5-(4-Hydroxyphenyl)-3-methylsulfanyl-1-benzofuran-2-yl]acetic acid (377 mg, 1.2 mmol) was added to a solution of concentrated sulfuric acid (3 drops) in isopropanol (15 ml), and the mixture was refluxed for 6h, then cooled. The solvent was evaporated and the residue was poured into water. The mixture was extracted with dichloromethane, dried over magnesium sulfate, filtered and concentrated under vacuum. The residue was purified by column chromatography (benzene-acetone, 9:1 v/v) to afford the title compound as a colorless solid [yield 91%, m.p. 410-411 K; Rf = 0.51 (benzene-acetone, 9:1 v/v)]. Single crystals suitable for X–ray diffraction were prepared by evaporation of a solution of the title compound in benzene at room temperature.

Refinement

The hydroxyl H atom was found in a difference Fourier map and refined freely. The other H atoms were positioned geometrically and refined using a riding model, with C–H = 0.93 Å for the aryl, 0.97 Å for the methine and methylene, 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 with the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are presented as a small cycles of arbitrary radius.
Fig. 2.
O–H···O and C–H···O interactions (dotted lines) in the title compound. [Symmetry codes: (i) - x + 1/2, y - 1/2, - z + 3/2; (ii) x - 1/2, - y + 3/2, z - 1/2 (iii) -x + 1/2, y + 1/2, - z+ 3/2.] ...

Crystal data

C20H20O4SF(000) = 1504
Mr = 356.42Dx = 1.296 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 4594 reflections
a = 31.375 (3) Åθ = 2.6–27.3°
b = 8.0055 (7) ŵ = 0.20 mm1
c = 15.274 (1) ÅT = 173 K
β = 107.727 (1)°Block, colorless
V = 3654.2 (5) Å30.45 × 0.40 × 0.10 mm
Z = 8

Data collection

Bruker SMART CCD diffractometer4158 independent reflections
Radiation source: fine-focus sealed tube2474 reflections with I > 2σ(I)
graphiteRint = 0.051
Detector resolution: 10.0 pixels mm-1θmax = 27.5°, θmin = 1.4°
[var phi] and ω scansh = −39→40
Absorption correction: multi-scan (SADABS; Sheldrick, 2000)k = −10→10
Tmin = 0.916, Tmax = 0.981l = −19→19
15589 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.042Hydrogen site location: difference Fourier map
wR(F2) = 0.111H atoms treated by a mixture of independent and constrained refinement
S = 1.06w = 1/[σ2(Fo2) + (0.024P)2 + 3.8686P] where P = (Fo2 + 2Fc2)/3
4158 reflections(Δ/σ)max < 0.001
233 parametersΔρmax = 0.17 e Å3
0 restraintsΔρmin = −0.24 e Å3

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
S0.15080 (2)0.69811 (7)0.43431 (4)0.0571 (2)
O10.11004 (5)0.2623 (2)0.49946 (11)0.0540 (4)
O20.00249 (5)0.6432 (2)0.36507 (10)0.0547 (4)
O30.04570 (5)0.6124 (2)0.51076 (10)0.0588 (5)
O40.43182 (6)0.2543 (2)0.81139 (14)0.0639 (5)
H40.4366 (11)0.204 (4)0.860 (2)0.097 (12)*
C10.14460 (8)0.4954 (3)0.47235 (15)0.0471 (6)
C20.17779 (8)0.3928 (3)0.53678 (14)0.0430 (5)
C30.22327 (7)0.4045 (3)0.58158 (14)0.0427 (5)
H30.23930.49730.57280.051*
C40.24484 (7)0.2758 (3)0.64005 (14)0.0421 (5)
C50.21960 (8)0.1362 (3)0.65124 (16)0.0501 (6)
H50.23410.05030.68990.060*
C60.17442 (8)0.1219 (3)0.60733 (16)0.0531 (6)
H60.15820.02930.61560.064*
C70.15455 (8)0.2522 (3)0.55045 (16)0.0475 (6)
C80.10569 (8)0.4117 (3)0.45225 (16)0.0517 (6)
C90.06007 (8)0.4503 (3)0.39027 (16)0.0571 (6)
H9A0.04270.34800.37750.069*
H9B0.06250.49240.33240.069*
C100.03578 (7)0.5767 (3)0.43027 (15)0.0459 (5)
C11−0.02201 (8)0.7816 (3)0.39016 (17)0.0596 (7)
H11−0.02510.76150.45120.072*
C12−0.06727 (9)0.7810 (4)0.31955 (19)0.0779 (9)
H12A−0.06400.79790.25970.117*
H12B−0.08520.86920.33270.117*
H12C−0.08160.67560.32110.117*
C130.00498 (10)0.9398 (4)0.3919 (2)0.0810 (9)
H13A0.03360.92960.43790.121*
H13B−0.01081.03370.40600.121*
H13C0.00920.95610.33280.121*
C140.29366 (7)0.2806 (2)0.68845 (14)0.0412 (5)
C150.31181 (8)0.2046 (3)0.77431 (15)0.0482 (6)
H150.29270.15830.80370.058*
C160.35724 (8)0.1966 (3)0.81618 (15)0.0489 (6)
H160.36840.14440.87300.059*
C170.38628 (8)0.2652 (3)0.77459 (15)0.0462 (5)
C180.36918 (8)0.3480 (3)0.69133 (15)0.0472 (5)
H180.38850.39920.66400.057*
C190.32372 (7)0.3543 (2)0.64927 (14)0.0429 (5)
H190.31280.40910.59320.051*
C200.18438 (10)0.6628 (3)0.3595 (2)0.0753 (8)
H20A0.21320.62100.39470.113*
H20B0.18800.76590.33060.113*
H20C0.16990.58250.31340.113*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S0.0746 (5)0.0372 (3)0.0542 (4)0.0154 (3)0.0118 (3)0.0026 (3)
O10.0501 (10)0.0527 (10)0.0582 (10)0.0071 (8)0.0151 (8)0.0052 (8)
O20.0574 (10)0.0634 (10)0.0371 (8)0.0202 (8)0.0051 (7)−0.0031 (7)
O30.0536 (10)0.0758 (12)0.0392 (9)0.0075 (9)0.0023 (8)−0.0064 (8)
O40.0525 (11)0.0710 (12)0.0578 (12)−0.0048 (9)0.0013 (9)0.0086 (10)
C10.0551 (15)0.0395 (12)0.0441 (13)0.0103 (11)0.0113 (11)−0.0003 (10)
C20.0521 (14)0.0363 (11)0.0416 (12)0.0091 (10)0.0157 (10)0.0003 (9)
C30.0533 (14)0.0339 (11)0.0420 (12)0.0062 (10)0.0162 (11)0.0003 (9)
C40.0509 (13)0.0382 (11)0.0396 (12)0.0093 (10)0.0176 (10)0.0027 (9)
C50.0528 (15)0.0460 (13)0.0554 (14)0.0114 (11)0.0223 (12)0.0146 (11)
C60.0553 (16)0.0467 (13)0.0628 (15)0.0053 (11)0.0262 (13)0.0137 (12)
C70.0440 (14)0.0493 (13)0.0505 (13)0.0080 (10)0.0162 (11)0.0023 (11)
C80.0576 (16)0.0459 (13)0.0490 (14)0.0128 (12)0.0124 (12)−0.0014 (11)
C90.0569 (15)0.0560 (15)0.0518 (14)0.0118 (12)0.0066 (12)−0.0075 (12)
C100.0420 (13)0.0497 (13)0.0405 (13)0.0015 (10)0.0043 (10)−0.0011 (10)
C110.0624 (16)0.0686 (17)0.0468 (14)0.0251 (14)0.0150 (12)−0.0004 (12)
C120.0672 (19)0.096 (2)0.0622 (17)0.0311 (17)0.0075 (14)0.0046 (16)
C130.092 (2)0.0672 (19)0.078 (2)0.0169 (17)0.0178 (18)−0.0034 (15)
C140.0531 (14)0.0326 (11)0.0390 (11)0.0071 (10)0.0154 (10)0.0007 (9)
C150.0576 (15)0.0453 (12)0.0441 (12)0.0056 (11)0.0190 (11)0.0084 (11)
C160.0592 (15)0.0457 (13)0.0381 (12)0.0053 (11)0.0090 (11)0.0048 (10)
C170.0494 (14)0.0392 (12)0.0444 (12)0.0006 (10)0.0059 (11)−0.0040 (10)
C180.0560 (15)0.0417 (12)0.0447 (13)−0.0034 (11)0.0164 (11)−0.0004 (10)
C190.0558 (15)0.0349 (11)0.0373 (11)0.0057 (10)0.0133 (11)0.0033 (9)
C200.099 (2)0.0535 (16)0.0803 (19)0.0075 (15)0.0382 (18)0.0049 (14)

Geometric parameters (Å, °)

S—C11.754 (2)C9—H9B0.9700
S—C201.796 (3)C11—C121.499 (3)
O1—C71.379 (3)C11—C131.519 (4)
O1—C81.381 (3)C11—H110.9800
O2—C101.316 (3)C12—H12A0.9600
O2—C111.465 (3)C12—H12B0.9600
O3—C101.207 (2)C12—H12C0.9600
O4—C171.370 (3)C13—H13A0.9600
O4—H40.81 (3)C13—H13B0.9600
C1—C81.344 (3)C13—H13C0.9600
C1—C21.450 (3)C14—C191.393 (3)
C2—C31.385 (3)C14—C151.400 (3)
C2—C71.391 (3)C15—C161.374 (3)
C3—C41.396 (3)C15—H150.9300
C3—H30.9300C16—C171.374 (3)
C4—C51.409 (3)C16—H160.9300
C4—C141.485 (3)C17—C181.389 (3)
C5—C61.376 (3)C18—C191.375 (3)
C5—H50.9300C18—H180.9300
C6—C71.379 (3)C19—H190.9300
C6—H60.9300C20—H20A0.9600
C8—C91.489 (3)C20—H20B0.9600
C9—C101.504 (3)C20—H20C0.9600
C9—H9A0.9700
C1—S—C20102.15 (11)O2—C11—H11109.7
C7—O1—C8105.56 (18)C12—C11—H11109.7
C10—O2—C11117.84 (17)C13—C11—H11109.7
C17—O4—H4106 (2)C11—C12—H12A109.5
C8—C1—C2106.7 (2)C11—C12—H12B109.5
C8—C1—S124.77 (18)H12A—C12—H12B109.5
C2—C1—S128.29 (18)C11—C12—H12C109.5
C3—C2—C7119.2 (2)H12A—C12—H12C109.5
C3—C2—C1135.7 (2)H12B—C12—H12C109.5
C7—C2—C1105.0 (2)C11—C13—H13A109.5
C2—C3—C4119.5 (2)C11—C13—H13B109.5
C2—C3—H3120.3H13A—C13—H13B109.5
C4—C3—H3120.3C11—C13—H13C109.5
C3—C4—C5118.8 (2)H13A—C13—H13C109.5
C3—C4—C14121.7 (2)H13B—C13—H13C109.5
C5—C4—C14119.53 (19)C19—C14—C15116.8 (2)
C6—C5—C4122.7 (2)C19—C14—C4121.87 (19)
C6—C5—H5118.6C15—C14—C4121.2 (2)
C4—C5—H5118.6C16—C15—C14121.6 (2)
C5—C6—C7116.4 (2)C16—C15—H15119.2
C5—C6—H6121.8C14—C15—H15119.2
C7—C6—H6121.8C17—C16—C15120.4 (2)
O1—C7—C6125.9 (2)C17—C16—H16119.8
O1—C7—C2110.76 (19)C15—C16—H16119.8
C6—C7—C2123.3 (2)O4—C17—C16122.7 (2)
C1—C8—O1112.0 (2)O4—C17—C18118.0 (2)
C1—C8—C9132.3 (2)C16—C17—C18119.2 (2)
O1—C8—C9115.8 (2)C19—C18—C17120.1 (2)
C8—C9—C10112.92 (19)C19—C18—H18119.9
C8—C9—H9A109.0C17—C18—H18119.9
C10—C9—H9A109.0C18—C19—C14121.7 (2)
C8—C9—H9B109.0C18—C19—H19119.2
C10—C9—H9B109.0C14—C19—H19119.2
H9A—C9—H9B107.8S—C20—H20A109.5
O3—C10—O2125.0 (2)S—C20—H20B109.5
O3—C10—C9124.6 (2)H20A—C20—H20B109.5
O2—C10—C9110.39 (19)S—C20—H20C109.5
O2—C11—C12105.5 (2)H20A—C20—H20C109.5
O2—C11—C13107.5 (2)H20B—C20—H20C109.5
C12—C11—C13114.6 (2)
C20—S—C1—C8−113.8 (2)C7—O1—C8—C1−1.1 (2)
C20—S—C1—C272.8 (2)C7—O1—C8—C9179.05 (19)
C8—C1—C2—C3178.3 (2)C1—C8—C9—C10−77.0 (3)
S—C1—C2—C3−7.3 (4)O1—C8—C9—C10102.7 (2)
C8—C1—C2—C7−0.6 (2)C11—O2—C10—O35.8 (4)
S—C1—C2—C7173.76 (17)C11—O2—C10—C9−173.8 (2)
C7—C2—C3—C4−0.5 (3)C8—C9—C10—O3−18.4 (4)
C1—C2—C3—C4−179.3 (2)C8—C9—C10—O2161.2 (2)
C2—C3—C4—C50.5 (3)C10—O2—C11—C12−155.9 (2)
C2—C3—C4—C14178.91 (19)C10—O2—C11—C1381.4 (3)
C3—C4—C5—C6−0.4 (3)C3—C4—C14—C19−33.2 (3)
C14—C4—C5—C6−178.9 (2)C5—C4—C14—C19145.2 (2)
C4—C5—C6—C70.3 (3)C3—C4—C14—C15149.6 (2)
C8—O1—C7—C6−178.9 (2)C5—C4—C14—C15−32.0 (3)
C8—O1—C7—C20.7 (2)C19—C14—C15—C16−2.7 (3)
C5—C6—C7—O1179.3 (2)C4—C14—C15—C16174.6 (2)
C5—C6—C7—C2−0.3 (3)C14—C15—C16—C170.6 (3)
C3—C2—C7—O1−179.24 (18)C15—C16—C17—O4−177.1 (2)
C1—C2—C7—O1−0.1 (2)C15—C16—C17—C182.3 (3)
C3—C2—C7—C60.4 (3)O4—C17—C18—C19176.5 (2)
C1—C2—C7—C6179.5 (2)C16—C17—C18—C19−2.9 (3)
C2—C1—C8—O11.1 (3)C17—C18—C19—C140.7 (3)
S—C1—C8—O1−173.51 (15)C15—C14—C19—C182.1 (3)
C2—C1—C8—C9−179.1 (2)C4—C14—C19—C18−175.23 (19)
S—C1—C8—C96.3 (4)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O4—H4···O3i0.81 (3)2.02 (3)2.829 (3)171 (3)
C13—H13B···O4ii0.962.573.325 (3)135

Symmetry codes: (i) −x+1/2, y−1/2, −z+3/2; (ii) x−1/2, −y+3/2, z−1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BT5043).

References

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  • Bruker (2001). SAINT and SMART Bruker AXS Inc., Madison, Wisconsin, USA.
  • Choi, H. D., Kang, B. W., Seo, P. J., Son, B. W. & Lee, U. (2006). Acta Cryst. E62, o5121–o5122.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Howlett, D. R., Perry, A. E., Godfrey, F., Swatton, J. E., Jennings, K. H., Spitzfaden, C., Wadsworth, H., Wood, S. J. & Markwell, R. E. (1999). Biochem. J 340, 283–289. [PubMed]
  • Reuss, S. H. von & König, W. A. (2004). Phytochemistry, 65, 3113–3118. [PubMed]
  • Sheldrick, G. M. (2000). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Twyman, L. J. & Allsop, D. (1999). Tetrahedron Lett 40, 9383–9384.

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