2-(4-Methoxy­phenyl­sulfin­yl)cyclo­hexan-1-one

Julio Zukerman-Schpector; Elisângela Vinhato; Carlos R Cerqueira Jr; Alessandro Rodrigues; Paulo R Olivato

doi:10.1107/S1600536809013695

. 2009 Apr 18;65(Pt 5):o1075. doi: 10.1107/S1600536809013695

2-(4-Methoxyphenylsulfinyl)cyclohexan-1-one

Julio Zukerman-Schpector ^a,^*, Elisângela Vinhato ^b, Carlos R Cerqueira Jr ^b, Alessandro Rodrigues ^b, Paulo R Olivato ^b

PMCID: PMC2977754 PMID: 21583890

Abstract

The cyclohexanone ring in the title compound, C₁₃H₁₆O₃S, is in a distorted chair conformation. The intramolecular S⋯O_carbonyl distance is 2.814 (2) Å. Molecules are connected into a two-dimensional array via C—H⋯O contacts involving the carbonyl and sulfinyl O atoms.

Related literature

For related literature, see: Zukerman-Schpector, da Silva et al. (2006 ▶). For structure analysis, see: Cremer & Pople (1975 ▶); Iulek & Zukerman-Schpector (1997 ▶). For details of synthesis, see: Bradscher et al. (1954 ▶); Zukerman-Schpector, Maganhi et al. (2006 ▶); Drabowicz & Mikolajczyk (1978 ▶).

Experimental

Crystal data

C₁₃H₁₆O₃S
M _r = 252.33
Monoclinic,
a = 11.0510 (4) Å
b = 10.0875 (2) Å
c = 11.3672 (5) Å
β = 93.886 (2)°
V = 1264.27 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.25 mm⁻¹
T = 290 K
0.15 × 0.10 × 0.10 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: none
8283 measured reflections
2872 independent reflections
2508 reflections with I > 2σ(I)
R _int = 0.024

Refinement

R[F ² > 2σ(F ²)] = 0.040
wR(F ²) = 0.113
S = 1.06
2872 reflections
155 parameters
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT (Bruker, 2006 ▶); data reduction: SAINT and SADABS (Bruker, 2006 ▶); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶), PARST (Nardelli, 1995 ▶) and MarvinSketch (ChemAxon, 2008 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809013695/tk2419sup1.cif

e-65-o1075-sup1.cif^{(18.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809013695/tk2419Isup2.hkl

e-65-o1075-Isup2.hkl^{(138.1KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯O2ⁱ	0.98	2.47	3.257 (2)	137
C3—H3A⋯O2ⁱ	0.97	2.59	3.323 (2)	133
C11—H11⋯O1ⁱⁱ	0.93	2.59	3.500 (2)	167

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

We thank FAPESP (grant No. 2008/02531-5 to JZ-S), CNPq and CAPES for financial support. Professor R. A. Burrow of the Federal University of Santa Maria is gratefully acknowledged for helping with the collection of intensity data.

supplementary crystallographic information

Comment

The obtained product, which has stereogenic centres at S and C1, was a 3:1 mixture of the [C1(R)S(S)/C1(S)S(R)] and [C1(R)S(R)/C1(S)S(S)] diastereomeric sulfoxides, respectively, as determined from ¹H NMR spectroscopy. From hexane/ethanol fractional crystallization, the pure [C1(R)S(S)/C1(S)S(R)] diastereomer, (I), was obtained. The cyclohexanone ring is in a distorted chair conformation as shown by the ring-puckering parameters (Cremer & Pople, 1975; Iulek & Zukerman-Schpector, 1997) q₂ = 0.143 (2) Å, q₃ = 0.499 (2) Å, Q = 0.519 (2) Å, φ₂ = -130.9 (8)°. The methyl moiety is slightly out of the phenyl plane as shown by the C13-O3-C10-C11 torsion angle of 4.9 (2)°. The molecules are linked via intermolecular C—H···O interactions involving the carbonyl- and sulfinyl-oxygen atoms into a 2-D array (Table 1).

Experimental

The starting 2-(4-methoxyphenylthio)cyclohexanone was prepared from the reaction of 2-chlorocyclohexanone and 4-methoxythiophenol as previously reported (Bradscher et al. 1954). The sulfoxide 2-[(4-methoxybenzene)sulfinyl]cyclohexanone was prepared by oxidation of 2-(4-methoxyphenylthio)cyclohexanone (Zukerman-Schpector, Maganhi et al. 2006; Drabowicz & Mikolajczyk, 1978). A CH₃OH (10 ml) solution of SeO₂ (1.23 g, 11.08 mmol) and hydrogen peroxide (30% H₂O₂ in aqueous solution; 1.25 ml, 11.08 mmol) was added drop-wise, at 273 K, to a solution of 2-(4-methoxyphenylthio)cyclohexanone (2.62 g, 11.08 mmol) in CH₃OH (5 ml). The reaction mixture was stirred at 273 K for 2 h and then at room temperature for 2 h. After completion of the reaction, a saturated aqueous NaCl solution (30 ml) was added, the aqueous layer was extracted with CH₂Cl₂ (3 x 20 ml) and dried over anhydrous Na₂SO₄. After solvent evaporation under reduced pressure, 1.39 g (5.5 mmol, yield 50%; m.p. 363–365 K) of the crude 2-[(4-methoxybenzene)sulfinyl]cyclohexanone (I) was obtained. Colourless crystals of (I) were obtained by vapour diffusion from n-hexane/acetone at 298 K.