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Acta Cryst. (2008). E64, o727    [ doi:10.1107/S1600536808007046 ]

2-Methyl-1-(phenylsulfonyl)naphtho[2,1-b]furan

H. D. Choi, P. J. Seo, B. W. Son and U. Lee

Abstract top

The title compound, C19H14O3S, was prepared by the oxidation of 2-methyl-1-(phenylsulfanyl)naphtho[2,1-b]furan with 3-chloroperoxybenzoic acid. The phenyl ring makes a dihedral angle of 87.13 (4)° with the plane of the naphthofuran fragment. The crystal structure is stabilized by [pi]-[pi] interactions between the furan and benzene rings of neighbouring molecules [centroid-centroid distance = 3.850 (2) Å] and weak C-H...[pi] interactions. In addition, there are also intramolecular C-H...O interactions.

Comment top

As a part of our ongoing studies on the synthesis and structure of 2-methylnaphtho[2,1-b]furan derivatives, the crystal structures of 2-methyl-1-(methylsulfinyl)naphtho[2,1-b]furan (Choi et al., 2006) and 2-methyl-1-(phenylsulfinyl)naphtho[2,1-b]furan (Choi et al., 2007) have already been described. Herein we report the molecular and the crystal structure of the title compound, 2-methyl-1-(phenylsulfonyl)naphtho[2,1-b]furan (Fig. 1).

The naphthofuran unit is essentially planar, with a mean deviation equal to 0.040 Å from the least-squares plane defined by thirteen constituent atoms. The crystal packing (Fig. 2) is stabilized by aromatic π—π stacking interactions between the furan and the benzene rings from the adjacent naphthofuran fragments. The Cg1···Cg2i distance is 3.850 (2) Å (Cg1 and Cg2 are the centroids of the O1/C12/C1/C2/C11 furan and the C2/C3/C8/C9/C10/C11 benzene rings, respectively, the symmetry code as in Fig. 2). The crystal packing (Fig. 2) is further stabilized by the C—H···π interactions; in both cases the benzene ring of the naphthofuran unit (Cg3) is involved. There are also intramolecular C—H···O interactions present in the structure.

Related literature top

For the crystal structures of similar 2-methylnaphtho[2,1-b]furan compounds, see: Choi et al. (2006, 2007).

Experimental top

3-Chloroperoxybenzoic acid (77%, 471 mg, 2.10 mmol) was added in small portions to a stirred solution of 2-methyl-1-(phenylsulfanyl)naphtho[2,1-b]furan (290 mg, 1.0 mmol) in dichloromethane (20 ml) at 273 K. After having been stirred for 4 h at room temperature, the mixture was washed with saturated sodium hydrogencarbonate 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 colourless solid [yield 84%, m.p. 431–432 K; Rf = 0.63 (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. The average crystal size was approximately 1.0 × 1.0 × 0.5 mm. The crystals are colourless and soluble in polar solvents.

Refinement top

All the H atoms were discernible in the difference Fourier map. Nevertheless, during the refinement the H atoms were positioned into idealized positions and refined using a riding model with the distance constraints: C—H = 0.95 Å for aryl H atoms and 0.98 Å for methyl H atoms, respectively, and with Uiso(H) = 1.2Ueq(C) and 1.5Ueq(C) for aryl and methyl H atoms, respectively.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); 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, showing displacement ellipsoides drawn at the 50% probability level.
[Figure 2] Fig. 2. π—π, C—H···π and intramolecular C—H···O interactions (dotted lines) in the title compound. Cg denotes the ring centroids. [Symmetry code: (i) 1 - x, -y, -z; (ii) 2 - x, 1 - y, -z; (iii) x + 1, y + 1, z.]
2-Methyl-1-(phenylsulfonyl)naphtho[2,1-b]furan top
Crystal data top
C19H14O3SF000 = 672
Mr = 322.36Dx = 1.433 Mg m−3
Monoclinic, P21/nMelting point = 431–432 K
Hall symbol: -P 2ynMo Kα radiation
λ = 0.71073 Å
a = 10.7175 (4) ÅCell parameters from 5468 reflections
b = 7.7972 (3) Åθ = 2.3–28.2º
c = 18.0488 (7) ŵ = 0.23 mm−1
β = 97.797 (1)ºT = 173 (2) K
V = 1494.33 (10) Å3Block, colourless
Z = 40.40 × 0.40 × 0.20 mm
Data collection top
Bruker SMART CCD
diffractometer		3222 independent reflections
Radiation source: fine-focus sealed tube2785 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.023
Detector resolution: 10.0 pixels mm-1θmax = 27.0º
T = 173(2) Kθmin = 2.9º
φ and ω scansh = −13→11
Absorption correction: nonek = −9→9
8784 measured reflectionsl = −23→23
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.036H-atom parameters constrained
wR(F2) = 0.098  w = 1/[σ2(Fo2) + (0.0464P)2 + 0.7406P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max < 0.001
3222 reflectionsΔρmax = 0.33 e Å−3
210 parametersΔρmin = −0.39 e Å−3
54 constraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.015 (2)
Crystal data top
C19H14O3SV = 1494.33 (10) Å3
Mr = 322.36Z = 4
Monoclinic, P21/nMo Kα
a = 10.7175 (4) ŵ = 0.23 mm−1
b = 7.7972 (3) ÅT = 173 (2) K
c = 18.0488 (7) Å0.40 × 0.40 × 0.20 mm
β = 97.797 (1)º
Data collection top
Bruker SMART CCD
diffractometer		3222 independent reflections
Absorption correction: none2785 reflections with I > 2σ(I)
8784 measured reflectionsRint = 0.023
Refinement top
R[F2 > 2σ(F2)] = 0.036210 parameters
wR(F2) = 0.098H-atom parameters constrained
S = 1.05Δρmax = 0.33 e Å−3
3222 reflectionsΔρmin = −0.39 e Å−3
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S0.78568 (4)0.07420 (5)0.11326 (2)0.02579 (13)
O10.44773 (10)0.27156 (15)0.07186 (6)0.0317 (3)
O20.81955 (11)−0.07018 (14)0.07052 (7)0.0327 (3)
O30.78345 (12)0.05031 (17)0.19220 (6)0.0376 (3)
C10.63938 (14)0.1558 (2)0.07427 (8)0.0251 (3)
C20.59348 (14)0.19921 (19)−0.00332 (8)0.0239 (3)
C30.63656 (14)0.18767 (19)−0.07498 (8)0.0246 (3)
C40.74995 (16)0.1091 (2)−0.08857 (9)0.0294 (3)
H40.80310.0575−0.04830.035*
C50.78480 (18)0.1059 (2)−0.15919 (9)0.0360 (4)
H50.86120.0516−0.16710.043*
C60.70826 (19)0.1822 (3)−0.21959 (9)0.0407 (4)
H60.73390.1820−0.26800.049*
C70.59747 (18)0.2564 (2)−0.20867 (9)0.0383 (4)
H70.54600.3066−0.25000.046*
C80.55669 (15)0.2608 (2)−0.13718 (9)0.0297 (4)
C90.43790 (16)0.3342 (2)−0.12790 (10)0.0355 (4)
H90.38670.3809−0.17020.043*
C100.39621 (15)0.3389 (2)−0.06035 (10)0.0335 (4)
H100.31640.3859−0.05430.040*
C110.47661 (14)0.2710 (2)0.00014 (9)0.0273 (3)
C120.54835 (15)0.2028 (2)0.11655 (9)0.0294 (3)
C130.89432 (14)0.24061 (19)0.10214 (8)0.0247 (3)
C140.87639 (16)0.4045 (2)0.12958 (9)0.0299 (4)
H140.80350.43080.15200.036*
C150.96700 (17)0.5283 (2)0.12344 (9)0.0351 (4)
H150.95500.64170.14030.042*
C161.07529 (17)0.4877 (2)0.09275 (9)0.0367 (4)
H161.13770.57300.08970.044*
C171.09280 (16)0.3244 (2)0.06666 (10)0.0360 (4)
H171.16750.29690.04630.043*
C181.00096 (15)0.2003 (2)0.07027 (9)0.0301 (4)
H181.01120.08860.05100.036*
C190.53353 (18)0.1975 (3)0.19698 (10)0.0414 (4)
H19A0.45970.26510.20540.062*
H19B0.60890.24550.22660.062*
H19C0.52220.07840.21210.062*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S0.0269 (2)0.0252 (2)0.0241 (2)0.00073 (15)−0.00082 (14)0.00240 (14)
O10.0246 (6)0.0341 (6)0.0373 (6)−0.0007 (5)0.0076 (5)0.0014 (5)
O20.0342 (6)0.0231 (6)0.0394 (6)0.0013 (5)0.0005 (5)−0.0007 (5)
O30.0411 (7)0.0446 (7)0.0259 (6)−0.0008 (6)−0.0007 (5)0.0089 (5)
C10.0243 (7)0.0255 (8)0.0250 (7)−0.0014 (6)0.0017 (6)0.0009 (6)
C20.0226 (7)0.0204 (7)0.0276 (8)−0.0032 (6)−0.0001 (6)0.0003 (6)
C30.0267 (7)0.0214 (7)0.0245 (7)−0.0049 (6)−0.0012 (6)−0.0004 (6)
C40.0317 (8)0.0298 (8)0.0261 (8)−0.0004 (6)0.0017 (6)−0.0011 (6)
C50.0386 (9)0.0395 (10)0.0307 (8)−0.0018 (7)0.0074 (7)−0.0055 (7)
C60.0503 (11)0.0482 (11)0.0236 (8)−0.0117 (9)0.0056 (7)−0.0026 (8)
C70.0438 (10)0.0421 (10)0.0262 (8)−0.0096 (8)−0.0061 (7)0.0056 (7)
C80.0308 (8)0.0282 (8)0.0278 (8)−0.0075 (7)−0.0046 (6)0.0032 (6)
C90.0304 (9)0.0335 (9)0.0386 (9)−0.0035 (7)−0.0093 (7)0.0097 (7)
C100.0220 (8)0.0305 (9)0.0463 (10)−0.0009 (6)−0.0017 (7)0.0061 (7)
C110.0240 (8)0.0245 (8)0.0331 (8)−0.0040 (6)0.0030 (6)0.0009 (6)
C120.0271 (8)0.0302 (8)0.0311 (8)−0.0032 (6)0.0043 (6)0.0011 (7)
C130.0249 (7)0.0249 (8)0.0228 (7)0.0008 (6)−0.0024 (6)0.0007 (6)
C140.0316 (8)0.0280 (8)0.0293 (8)0.0053 (6)0.0015 (6)−0.0006 (6)
C150.0471 (10)0.0254 (8)0.0311 (8)−0.0008 (7)−0.0009 (7)−0.0016 (7)
C160.0410 (10)0.0359 (10)0.0318 (8)−0.0107 (8)0.0003 (7)0.0023 (7)
C170.0304 (9)0.0425 (10)0.0355 (9)−0.0028 (7)0.0065 (7)−0.0031 (8)
C180.0290 (8)0.0297 (8)0.0309 (8)0.0021 (6)0.0015 (6)−0.0058 (7)
C190.0415 (10)0.0521 (12)0.0335 (9)−0.0013 (9)0.0154 (8)0.0001 (8)
Geometric parameters (Å, °) top
S—O21.4387 (12)C8—C91.426 (2)
S—O31.4403 (12)C9—C101.355 (2)
S—C11.7492 (15)C9—H90.9500
S—C131.7729 (16)C10—C111.400 (2)
O1—C121.366 (2)C10—H100.9500
O1—C111.3713 (19)C12—C191.482 (2)
C1—C121.367 (2)C13—C181.383 (2)
C1—C21.460 (2)C13—C141.393 (2)
C2—C111.381 (2)C14—C151.384 (2)
C2—C31.434 (2)C14—H140.9500
C3—C41.412 (2)C15—C161.389 (3)
C3—C81.434 (2)C15—H150.9500
C4—C51.376 (2)C16—C171.379 (3)
C4—H40.9500C16—H160.9500
C5—C61.405 (3)C17—C181.388 (2)
C5—H50.9500C17—H170.9500
C6—C71.359 (3)C18—H180.9500
C6—H60.9500C19—H19A0.9800
C7—C81.418 (2)C19—H19B0.9800
C7—H70.9500C19—H19C0.9800
Cg1···Cg2i3.850 (2)
O2—S—O3117.93 (7)C9—C10—C11116.63 (15)
O2—S—C1110.28 (7)C9—C10—H10121.7
O3—S—C1108.10 (7)C11—C10—H10121.7
O2—S—C13107.14 (7)O1—C11—C2111.47 (13)
O3—S—C13107.81 (7)O1—C11—C10122.77 (14)
C1—S—C13104.76 (7)C2—C11—C10125.75 (15)
C12—O1—C11107.16 (12)O1—C12—C1109.97 (14)
C12—C1—C2107.47 (14)O1—C12—C19114.10 (14)
C12—C1—S122.78 (12)C1—C12—C19135.93 (16)
C2—C1—S129.59 (11)C18—C13—C14121.17 (15)
C11—C2—C3118.11 (14)C18—C13—S118.24 (12)
C11—C2—C1103.91 (13)C14—C13—S120.44 (12)
C3—C2—C1137.99 (14)C15—C14—C13118.61 (15)
C4—C3—C2125.03 (14)C15—C14—H14120.7
C4—C3—C8118.22 (14)C13—C14—H14120.7
C2—C3—C8116.75 (14)C14—C15—C16120.44 (16)
C5—C4—C3121.14 (15)C14—C15—H15119.8
C5—C4—H4119.4C16—C15—H15119.8
C3—C4—H4119.4C17—C16—C15120.42 (16)
C4—C5—C6120.51 (17)C17—C16—H16119.8
C4—C5—H5119.7C15—C16—H16119.8
C6—C5—H5119.7C16—C17—C18119.82 (16)
C7—C6—C5119.84 (16)C16—C17—H17120.1
C7—C6—H6120.1C18—C17—H17120.1
C5—C6—H6120.1C13—C18—C17119.50 (16)
C6—C7—C8121.71 (16)C13—C18—H18120.2
C6—C7—H7119.1C17—C18—H18120.2
C8—C7—H7119.1C12—C19—H19A109.5
C7—C8—C9120.46 (15)C12—C19—H19B109.5
C7—C8—C3118.54 (16)H19A—C19—H19B109.5
C9—C8—C3120.99 (15)C12—C19—H19C109.5
C10—C9—C8121.70 (15)H19A—C19—H19C109.5
C10—C9—H9119.2H19B—C19—H19C109.5
C8—C9—H9119.2
O2—S—C1—C12136.48 (14)C12—O1—C11—C21.42 (17)
O3—S—C1—C126.22 (17)C12—O1—C11—C10−177.49 (15)
C13—S—C1—C12−108.55 (14)C3—C2—C11—O1179.31 (12)
O2—S—C1—C2−48.68 (16)C1—C2—C11—O1−1.14 (17)
O3—S—C1—C2−178.93 (14)C3—C2—C11—C10−1.8 (2)
C13—S—C1—C266.30 (16)C1—C2—C11—C10177.73 (15)
C12—C1—C2—C110.43 (17)C9—C10—C11—O1178.28 (15)
S—C1—C2—C11−175.02 (12)C9—C10—C11—C2−0.5 (3)
C12—C1—C2—C3179.84 (17)C11—O1—C12—C1−1.10 (18)
S—C1—C2—C34.4 (3)C11—O1—C12—C19178.68 (14)
C11—C2—C3—C4−176.13 (15)C2—C1—C12—O10.41 (18)
C1—C2—C3—C44.5 (3)S—C1—C12—O1176.24 (11)
C11—C2—C3—C83.3 (2)C2—C1—C12—C19−179.31 (19)
C1—C2—C3—C8−176.09 (17)S—C1—C12—C19−3.5 (3)
C2—C3—C4—C5−179.13 (15)O2—S—C13—C18−12.25 (14)
C8—C3—C4—C51.5 (2)O3—S—C13—C18115.62 (13)
C3—C4—C5—C60.5 (3)C1—S—C13—C18−129.41 (12)
C4—C5—C6—C7−1.6 (3)O2—S—C13—C14172.06 (12)
C5—C6—C7—C80.7 (3)O3—S—C13—C14−60.06 (14)
C6—C7—C8—C9−177.78 (17)C1—S—C13—C1454.91 (14)
C6—C7—C8—C31.3 (3)C18—C13—C14—C150.9 (2)
C4—C3—C8—C7−2.3 (2)S—C13—C14—C15176.46 (12)
C2—C3—C8—C7178.25 (14)C13—C14—C15—C16−2.1 (2)
C4—C3—C8—C9176.74 (15)C14—C15—C16—C171.3 (3)
C2—C3—C8—C9−2.7 (2)C15—C16—C17—C180.8 (3)
C7—C8—C9—C10179.50 (16)C14—C13—C18—C171.1 (2)
C3—C8—C9—C100.5 (3)S—C13—C18—C17−174.55 (13)
C8—C9—C10—C111.1 (2)C16—C17—C18—C13−1.9 (3)
Symmetry codes: (i) −x+1, −y, −z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C4—H4···O20.952.353.190 (2)147
C18—H18···O20.952.462.869 (2)106
C19—H19B···O30.982.552.926 (2)103
C19—H19C···Cg3i0.983.033.735 (3)130
C16—H16···Cg3ii0.952.883.761 (3)155
Symmetry codes: (i) −x+1, −y, −z; (ii) −x+2, −y+1, −z.
Table 1
Selected geometric parameters (Å) top
Cg1···Cg2i3.850 (2)
Symmetry codes: (i) −x+1, −y, −z.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C4—H4···O20.952.353.190 (2)147
C18—H18···O20.952.462.869 (2)106
C19—H19B···O30.982.552.926 (2)103
C19—H19C···Cg3i0.983.033.735 (3)130
C16—H16···Cg3ii0.952.883.761 (3)155
Symmetry codes: (i) −x+1, −y, −z; (ii) −x+2, −y+1, −z.
references
References top

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., Son, B. W. & Lee, U. (2007). Acta Cryst. E63, o1731–o1732.

Choi, H. D., Woo, H. M., Seo, P. J., Son, B. W. & Lee, U. (2006). Acta Cryst. E62, o3881–o3882.

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565–?.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.