3,3-Bis(4-bromo­phenyl­sulfan­yl)-1-methyl­piperidin-2-one

Julio Zukerman-Schpector; Paulo R Olivato; Carlos R Cerqueira Jr; Bruna Contieri; Seik Weng Ng; Edward R T Tiekink

doi:10.1107/S1600536813006995

. 2013 Mar 20;69(Pt 4):o556. doi: 10.1107/S1600536813006995

3,3-Bis(4-bromophenylsulfanyl)-1-methylpiperidin-2-one

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

PMCID: PMC3629608 PMID: 23634095

Abstract

In the title compound, C₁₈H₁₇Br₂NOS₂, the conformation of the piperidin-2-one ring is based on a half-chair with the methylene C atom diagonally opposite the N atom being 0.649 (3) Å above the plane of the remaining five atoms (r.m.s. deviation = 0.1205 Å). The S atoms occupy axial and bisectional positions, and the dihedral angle between the benzene rings of 59.95 (11)° indicates a splayed disposition. Helical supramolecular chains along the b axis sustained by C—H⋯O interactions is the major feature of the crystal packing. The chains are connected into a three-dimensional architecture by C—H⋯Br and C—H⋯π interactions.

Related literature

For background to the chemistry and structures of β-thio-carbonyl compounds, see: Zukerman-Schpector et al. (2009 ▶); Vinhato (2007 ▶); Vinhato et al. (2011 ▶); Olivato et al. (2012 ▶, 2013 ▶). For the synthesis, see: Olivato et al. (2013 ▶). For ring conformational analysis, see: Cremer & Pople (1975 ▶). graphic file with name e-69-0o556-scheme1.jpg

Experimental

Crystal data

C₁₈H₁₇Br₂NOS₂
M _r = 487.27
Monoclinic,
a = 7.8777 (1) Å
b = 9.6481 (1) Å
c = 24.6757 (3) Å
β = 93.190 (1)°
V = 1872.57 (4) Å³
Z = 4
Cu Kα radiation
μ = 7.61 mm⁻¹
T = 100 K
0.25 × 0.25 × 0.05 mm

Data collection

Agilent SuperNova (Dual, Cu at zero, Atlas) diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ▶) T _min = 0.298, T _max = 1.000
18656 measured reflections
3916 independent reflections
3715 reflections with I > 2σ(I)
R _int = 0.038

Refinement

R[F ² > 2σ(F ²)] = 0.029
wR(F ²) = 0.077
S = 1.10
3916 reflections
218 parameters
H-atom parameters constrained
Δρ_max = 0.71 e Å⁻³
Δρ_min = −1.26 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2011 ▶); 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 for Windows (Farrugia, 2012 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Click here for additional data file.^{(20KB, cif)}

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813006995/hg5299sup1.cif

e-69-0o556-sup1.cif^{(20KB, cif)}

Click here for additional data file.^{(188.1KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813006995/hg5299Isup2.hkl

e-69-0o556-Isup2.hkl^{(188.1KB, hkl)}

Click here for additional data file.^{(6.4KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813006995/hg5299Isup3.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
C9—H9⋯Br2ⁱ	0.95	2.87	3.744 (2)	154
C11—H11⋯O1ⁱⁱ	0.95	2.27	3.195 (3)	163
C1—H1B⋯Cg1ⁱ	0.98	2.86	3.660 (3)	139

Open in a new tab

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

Acknowledgments

We thank the Brazilian agencies FAPESP, CNPq and CAPES (808/2009 to JZ-S) for financial support. CRC and BC thank CNPq for scholarships; PRO and JZ-S thank CNPq for fellowships. We also thank the Ministry of Higher Education (Malaysia) for funding structural studies through the High-Impact Research scheme (UM.C/HIR-MOHE/SC/03).

supplementary crystallographic information

Comment

The title compound (I), Fig. 1, was studied as a part of an on-going investigation of conformational and electronic interactions in β-thio-carbonyl compounds, e.g. N,N-diethyl-2-[(4'-substituted) phenylthio]acetamides, N,N-diethyl-2-[(4'-substituted) phenylsulfonyl]acetamides and 3,3-bis[(4'-substituted phenylsulfany)]-1-methyl-2-piperidinones using spectroscopic, theoretical and X-ray diffraction methods (Vinhato, 2007; Zukerman-Schpector et al., 2009; Vinhato et al., 2011; Olivato et al., 2012; Olivato et al., 2013).

In (I), the conformation of the six-membered piperidin-2-one ring is highly distorted with the best description being one based on a half-chair with the C4 atom lying 0.649 (3) Å above the plane of the remaining five atoms (r.m.s. deviation = 0.1205 Å), with puckering parameters: q₂ = 0.463 (2) Å and q₃ = 0.275 (2) Å, and amplitudes: Q = 0.539 (2) Å, θ = 59.4 (2)° and φ₂ = 214.7 (3)° (Cremer & Pople, 1975). The carbonyl-O1 and methyl-C1 atom occupy equatorial positions with respect to the piperidinyl ring while the S1 and S2 atoms are axial and bisectional, respectively. The dihedral angle between the benzene rings is 59.95 (11)°, indicating a splayed disposition.

The crystal packing features helical supramolecular chains along the b axis sustained by rather strong C—H···O interactions, Fig. 2 and Table 1. These are consolidated into a three-dimensional architecture by C—H···Br and C—H···π interactions, Fig. 3 and Table 1.

Experimental

The preparation of the title compound was recently described (Olivato et al., 2013). Suitable crystals were obtained by vapour diffusion of n-hexane into a chloroform solution at 283 K.; M.pt: 383–385 K.