1-Methyl-3-phenyl­sulfonyl-2-piperidone

Julio Zukerman-Schpector; Paulo R Olivato; Carlos R Cerqueira Jr; Elisângela Vinhato; Edward R T Tiekink

doi:10.1107/S1600536808009288

. 2008 Apr 16;64(Pt 5):o835–o836. doi: 10.1107/S1600536808009288

1-Methyl-3-phenylsulfonyl-2-piperidone

Julio Zukerman-Schpector ^a,^*, Paulo R Olivato ^b, Carlos R Cerqueira Jr ^b, Elisângela Vinhato ^b, Edward R T Tiekink ^c

PMCID: PMC2961210 PMID: 21202324

Abstract

The piperidone ring in the title compound, C₁₂H₁₅NO₃S, has a slightly distorted half-chair conformation with the methyl, carbonyl and phenylsulfonyl ring substituents occupying equatorial, equatorial and axial positions, respectively. Molecules are connected into centrosymmetric dimers via C—H⋯O interactions and these associate into layers via C—H⋯O—S contacts. Further C—H⋯O interactions involving both the carbonyl and sulfonyl O atoms consolidate the crystal packing by providing connections between the layers.

Related literature

For related structures, see: Zukerman-Schpector et al. (1999 ▶, 2006 ▶). For related literature, see: Distefano et al. (1991 ▶); Olivato et al. (1992 ▶, 1997 ▶, 2003 ▶, 2004 ▶); Dal Colle et al. (1995 ▶). For ring conformational analysis, see: Cremer & Pople (1975 ▶). For the synthesis, see: Drabowicz et al. (1983 ▶); Zoretic & Soja (1976 ▶).

Experimental

Crystal data

C₁₂H₁₅NO₃S
M _r = 253.32
Monoclinic,
a = 9.0191 (16) Å
b = 10.4920 (18) Å
c = 13.446 (3) Å
β = 107.861 (3)°
V = 1211.1 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 98 (2) K
0.25 × 0.18 × 0.10 mm

Data collection

Rigaku AFC12κ/SATURN724 diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T _min = 0.945, T _max = 0.974
5193 measured reflections
2729 independent reflections
2549 reflections with I > 2σ(I)
R _int = 0.025

Refinement

R[F ² > 2σ(F ²)] = 0.047
wR(F ²) = 0.118
S = 1.12
2729 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.45 e Å⁻³

Data collection: CrystalClear (Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SIR92 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPII (Johnson, 1976 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808009288/ng2443sup1.cif

e-64-0o835-sup1.cif^{(17.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808009288/ng2443Isup2.hkl

e-64-0o835-Isup2.hkl^{(134KB, 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
C2—H2⋯O1ⁱ	1.00	2.29	3.272 (2)	168
C6—H6B⋯O2ⁱⁱ	0.98	2.55	3.424 (3)	148
C11—H11⋯O3ⁱⁱⁱ	0.95	2.62	3.224 (3)	122
C4—H4A⋯O1^iv	0.99	2.48	3.328 (2)	144

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

Acknowledgments

We thank FAPESP and CNPq for financial support. CRC and EV thank CNPq for doctoral fellowships; PRO and JZ-S thank CNPq for fellowships (Brazil). Support from UTSA, CNPq and FAPESP to allow JZ-S to spend a sabbatical at UTSA is gratefully acknowledged.

supplementary crystallographic information

Comment

The title compound (I), Fig. 1, was studied as a part of an on-going investigation of conformational and electronic aspects of different classes of β-keto-sulfones, i.e.α-phenylsulfonyl -acetones, -acetophenones and -cyclohexanones, utilizing spectroscopic, theoretical and X-ray diffraction methods (Dal Colle et al., 1995; Zukerman-Schpector et al., 1999; 2006).

The piperidone ring has a slightly distorted half-chair conformation with a tendency towards a half-boat conformation: the ring-puckering parameters are q₂ = 0.340 (2) Å, q₃ = 0.332 (2) Å, QT = 0.476 (2) °, φ₂ = -145.0 (3)° (Cremer & Pople, 1975). The ring substituents, i.e. N-methyl, C-carbonyl and C-phenylsulfonyl, occupy equatorial, equatorial and axial positions, respectively.

The crystal packing is dominated by C—H···O interactions, Table 1. Centrosymmetrically related molecules of (I) are connected into dimeric aggregates via C2—H···O1 contacts and these are linked into layers stacked along (1 0 1) via C6—H···O2 contacts. Connections betweem layers are also of the type C—H···O and serve to consolidate the crystal packing.

Experimental

Initially, the 3-phenylsulfanyl-1-methyl-2-piperidone was obtained from the reaction of 1-methyl-2-piperidinone and diphenyl disulfide with LDA in THF as described in the literature (Zoretic and Soja, 1976). The product was oxidized with H₂O₂ and SeO₂ (as catalyst) in methanol (Drabowicz et al. 1983) to give compound (I). After extraction with chloroform and subsequent evaporation, a crude solid was obtained. This product was subjected to flash chromatography with a solution of ethyl acetate and acetone in a 7:3 ratio. Suitable crystals were obtained by vapor diffusion from chloroform/n-hexane at 283 K.; m.p. 414–415 K. IR (cm^-1): ν(C=O) 1652, ν(SO₂)(as) 1307, ν(SO₂)(s) 1148. NMR (CDCl₃, p.p.m.): δ 1.79–2.74 (4H, m), 2.95 (3H, s), 3.30–3.48 (2H, m), 3.97 (1H, triplet, J = 6.1 Hz), 7.53–7.57 (2H, m, aryl-H), 7.62–7.67 (1H, m, aryl-H), 7.92–7.94 (2H, m, aryl-H). Analysis found: C 56.86, H 6.04, N 5.58; C₁₂H₁₅O₃NS requires: C 56.89, H 5.97, N 5.53%.