1-Methyl-3,3-bis­[(4-methyl­phen­yl)sulfan­yl]piperidin-2-one

Julio Zukerman-Schpector; Paulo R Olivato; Carlos R Cerqueira Jr; Jean M M Santos; Seik Weng Ng; Edward R T Tiekink

doi:10.1107/S1600536811037111

. 2011 Sep 30;67(Pt 10):o2759. doi: 10.1107/S1600536811037111

1-Methyl-3,3-bis[(4-methylphenyl)sulfanyl]piperidin-2-one

Julio Zukerman-Schpector ^a,^*, Paulo R Olivato ^b, Carlos R Cerqueira Jr ^b, Jean M M Santos ^b, Seik Weng Ng ^c,^d, Edward R T Tiekink ^c

PMCID: PMC3201309 PMID: 22065241

Abstract

The piperidone ring in the title compound, C₂₀H₂₃NOS₂, has a half-chair distorted to a twisted-boat conformation [Q _T = 0.5200 (17) Å]. One of the S-bound benzene rings is almost perpendicular to the least-squares plane through the piperidone ring, whereas the other is not [dihedral angles = 75.28 (5) and 46.41 (5) Å, respectively]. In the crystal, the presence of C—H⋯O and C—H⋯π interactions leads to the formation of supramolecular layers in the ab plane.

Related literature

For background to β-thiocarbonyl compounds, see: Vinhato et al. (2011 ▶); Olivato et al. (2009 ▶). For related structures, see: Zukerman-Schpector et al. (2008 ▶, 2010 ▶). For ring conformational analysis, see: Cremer & Pople (1975 ▶). For the synthesis, see: Hashmat & McDermott (2002 ▶); Zoretic & Soja (1976 ▶).

Experimental

Crystal data

C₂₀H₂₃NOS₂
M _r = 357.53
Monoclinic,
a = 7.8943 (1) Å
b = 9.8078 (2) Å
c = 23.9145 (4) Å
β = 92.803 (1)°
V = 1849.38 (5) Å³
Z = 4
Cu Kα radiation
μ = 2.65 mm⁻¹
T = 100 K
0.25 × 0.20 × 0.15 mm

Data collection

Agilent SuperNova Dual Cu at zero diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ▶) T _min = 0.558, T _max = 0.692
14169 measured reflections
3719 independent reflections
3465 reflections with I > 2σ(I)
R _int = 0.042

Refinement

R[F ² > 2σ(F ²)] = 0.039
wR(F ²) = 0.107
S = 1.06
3719 reflections
220 parameters
H-atom parameters constrained
Δρ_max = 0.68 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SIR92 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811037111/hg5094sup1.cif

e-67-o2759-sup1.cif^{(20.7KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811037111/hg5094Isup2.hkl

e-67-o2759-Isup2.hkl^{(178.6KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811037111/hg5094Isup3.cml

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

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

Cg1 is the centroid of the C7–C12 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C11—H11⋯O1ⁱ	0.95	2.37	3.294 (3)	166
C1—H1b⋯Cg1ⁱⁱ	0.98	2.84	3.624 (2)	137
C15—H15⋯Cg1ⁱⁱⁱ	0.95	2.88	3.459 (2)	120

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

Acknowledgments

We thank the Brazilian agencies FAPESP, CNPq (fellowships to JZ-S and PRO) and CAPES (808/2009 to JZ-S) for financial support. The authors also thank the University of Malaya for support of the crystallographic facility.

supplementary crystallographic information

Comment

As part of our on-going research on the conformational and electronic interactions in β-thio-carbonyl and β-bis-thio-carbonyl compounds, e.g. N,N-diethyl-2-[(4'-substituted)phelysulfonyl] acetamides, N-methoxy-N-methyl-2-[(4'-substituted) phenylthio]propanamides, 1-methyl-3-phenylsulfonyl-2-piperidone and 3,3-bis[(4-chlorophenyl)sulfanyl]-1-methyl-2-piperidone, utilizing spectroscopic, theoretical and X-ray diffraction methods (Vinhato, et al. 2011; Olivato et al., 2009; Zukerman-Schpector et al. 2008, 2010), the title compound, (I), was synthesized and its crystal structure determined.

In (I), Fig. 1, the piperidone ring has a distorted half-chair conformation with the C3 atom lying 0.687 (2) Å out of the plane defined by the other five atoms (r.m.s. deviation = 0.0833 Å). The ring puckering parameters are: q₂ = 0.4309 (17) Å, q₃ = 0.2909 (17) Å, QT = 0.5200 (17) Å, φ₂ = 145.6 (2) ° (Cremer & Pople, 1975). The S2-bound benzene ring is orientated to be almost perpendicular to the plane through the piperidone ring [dihedral angle = 75.28 (5) °]. The S1-bond benzene ring is somewhat splayed with respect to the other rings, forming dihedral angles of 46.41 (5) and 59.02 (5) ° with those through the piperidone and S2-bound benzene rings, respectively.

The crystal packing of (I), Table 1, is sustained by C—H···O and C—H···π interactions that lead to the formation of supramolecular layers in the ab plane, Fig. 1. The S1-benzene accepts to C—H···π contacts. Layers stack along the c axis as illustrated in Fig.3.

Experimental

Firstly, 4-methylthiophenol (5.0 g, 40 mmol) was reacted with bromine (1.1 ml, 20 mmol) in dichloromethane (250 ml) on hydrated silica gel support (25 g of SiO₂ and 12 ml of water) to give 4-methylphenyl disulfide (4.1 g, yield = 83%). A white solid was obtained after filtration and evaporation without further purification (Hashmat & McDermott, 2002). 1-Methyl-2-piperidinone (1.9 g, 17 mmol) was added drop-wise to a cooled (195 K) solution of hexamethylphosphoramide (HMPA) (3.1 ml, 17 mmol), diisopropylamine (2.6 ml, 17 mmol) and butyllithium (13.5 ml, 17 mmol) in THF (60 ml). After 20 minutes, 4-methylphenyl disulfide (4.1 g, 17 mmol) dissolved in THF (10 ml) was added drop-wise to the enolate solution (Zoretic & Soja, 1976). After the mixture was stirred for 4 h at 195 K, water (80 ml) was added at room temperature and extraction with chloroform was performed. The organic layer was dried over anhydrous sodium sulfate. After evaporation of solvent, a crude solid was obtained. Purification through flash chromatography with a solution of hexane and ethyl acetate in a 7:3 ratio give the pure product (3.3 g, yield = 56%). Suitable crystals for X-ray analysis were obtained by vapour diffusion of n-hexane into a chloroform solution of (I) held at 283 K; m.p. 392–393 K. IR (cm^-1): ν(C=O) 1662. NMR (CDCl₃, p.p.m.): δ 1.88–1.93 (2H, m), 1.96–1.99 (2H, m), 2.38 (6H, s), 2.93 (3H, s), 3.163.18 (2H, t, J = 6.1 Hz), 7.15–7.17 (4H, d, J = 7.8 Hz,Aryl-H), 7.52–7.54 (4H, m, Aryl-H). Analysis found: C 67.22, H 6.45, N 3.95%. C₂₀H₂₃ONS₂ requires: C 67.19, H 6.48, N 3.92%.