1-Methyl-3,3-bis-(phenyl-sulfan-yl)piperidin-2-one.

The piperidone ring in the title compound, C(18)H(19)NOS(2), is in a distorted half-chair conformation, distorted towards a twisted boat, with the central methyl-ene C atom of the propyl backbone lying 0.606 (2) Å out of the plane defined by the other five atoms (r.m.s. deviation = 0.1197 Å). One of the S-bound phenyl rings is almost perpendicular to the least-squares plane through the piperidone ring, whereas the other is splayed [dihedral angles = 75.97 (6) and 44.21 (7)°, respectively]. The most prominent feature of the crystal packing is the formation of helical supra-molecular chains along the b axis sustained by C-H⋯O inter-actions. The chains are consolidated into a three-dimensional architecture via C-H⋯π inter-actions whereby one S-bound phenyl ring accepts two C-H⋯π contacts.

Related literature

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

Experimental

Crystal data

C18H19NOS2

M = 329.48

Orthorhombic,

a = 8.2103 (1) Å

b = 9.8329 (1) Å

c = 20.3686 (2) Å

V = 1644.38 (3) Å3

Z = 4

Cu Kα radiation

μ = 2.93 mm−1

T = 100 K

0.35 × 0.30 × 0.25 mm

Data collection

Agilent SuperNova Dual (Cu at zero) diffractometer with an Atlas detector

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ▶) T min = 0.427, T max = 0.585

4452 measured reflections

2769 independent reflections

2728 reflections with I > 2σ(I)

R int = 0.016

Refinement

R[F 2 > 2σ(F 2)] = 0.025

wR(F 2) = 0.067

S = 1.09

2769 reflections

200 parameters

H-atom parameters constrained

Δρmax = 0.19 e Å−3

Δρmin = −0.32 e Å−3

Absolute structure: Flack (1983 ▶), 818 Friedel pairs

Flack parameter: 0.024 (14)

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 ▶), DIAMOND (Brandenburg, 2006 ▶) and MarvinSketch (ChemAxon, 2009 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812021277/hg5220sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812021277/hg5220Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812021277/hg5220Isup3.cml

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

C18H19NOS2	F(000) = 696
Mr = 329.48	Dx = 1.331 Mg m−3
Orthorhombic, P212121	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: P 2ac 2ab	Cell parameters from 3533 reflections
a = 8.2103 (1) Å	θ = 4.5–75.9°
b = 9.8329 (1) Å	µ = 2.93 mm−1
c = 20.3686 (2) Å	T = 100 K
V = 1644.38 (3) Å3	Prism, colourless
Z = 4	0.35 × 0.30 × 0.25 mm

Agilent SuperNova Dual (Cu at zero) diffractometer with an Atlas detector	2769 independent reflections
Radiation source: fine-focus sealed tube	2728 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.016
Detector resolution: 10.4041 pixels mm-1	θmax = 76.2°, θmin = 5.0°
ω scans	h = −8→10
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	k = −11→12
Tmin = 0.427, Tmax = 0.585	l = −25→24
4452 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.025	H-atom parameters constrained
wR(F2) = 0.067	w = 1/[σ2(Fo2) + (0.0401P)2 + 0.3751P] where P = (Fo2 + 2Fc2)/3
S = 1.09	(Δ/σ)max < 0.001
2769 reflections	Δρmax = 0.19 e Å−3
200 parameters	Δρmin = −0.32 e Å−3
0 restraints	Absolute structure: Flack (1983), 818 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.024 (14)

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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.

	x	y	z	Uiso*/Ueq
S1	0.30204 (5)	1.02555 (4)	0.75801 (2)	0.01619 (10)
S2	0.35543 (5)	0.81897 (4)	0.65673 (2)	0.01664 (10)
N1	−0.07129 (19)	0.98484 (16)	0.66379 (7)	0.0177 (3)
O1	0.15902 (17)	1.07356 (13)	0.62189 (6)	0.0212 (3)
C1	0.0918 (2)	0.99466 (17)	0.66038 (8)	0.0152 (3)
C2	0.1941 (2)	0.90147 (17)	0.70511 (8)	0.0134 (3)
C3	0.0940 (2)	0.79738 (17)	0.74265 (8)	0.0146 (3)
H3A	0.0652	0.7210	0.7132	0.018*
H3B	0.1593	0.7606	0.7794	0.018*
C4	−0.0604 (2)	0.86200 (18)	0.76924 (9)	0.0180 (4)
H4A	−0.1205	0.7955	0.7965	0.022*
H4B	−0.0325	0.9412	0.7970	0.022*
C5	−0.1651 (2)	0.9070 (2)	0.71229 (9)	0.0216 (4)
H5A	−0.2130	0.8260	0.6908	0.026*
H5B	−0.2557	0.9639	0.7289	0.026*
C6	−0.1655 (3)	1.0590 (2)	0.61425 (9)	0.0253 (4)
H6A	−0.1307	1.0306	0.5703	0.038*
H6B	−0.1470	1.1569	0.6194	0.038*
H6C	−0.2816	1.0392	0.6199	0.038*
C7	0.3549 (2)	0.93152 (17)	0.82931 (8)	0.0142 (3)
C8	0.2861 (2)	0.96954 (18)	0.88918 (8)	0.0188 (3)
H8	0.2052	1.0385	0.8906	0.023*
C9	0.3364 (3)	0.90622 (19)	0.94685 (8)	0.0216 (4)
H9	0.2906	0.9328	0.9877	0.026*
C10	0.4531 (2)	0.80460 (19)	0.94479 (9)	0.0203 (4)
H10	0.4880	0.7626	0.9844	0.024*
C11	0.5195 (2)	0.76355 (18)	0.88520 (9)	0.0197 (4)
H11	0.5975	0.6923	0.8839	0.024*
C12	0.4711 (2)	0.82740 (18)	0.82761 (8)	0.0159 (3)
H12	0.5170	0.8003	0.7868	0.019*
C13	0.2397 (2)	0.71592 (18)	0.60188 (8)	0.0152 (3)
C14	0.2444 (2)	0.57523 (19)	0.60717 (8)	0.0184 (4)
H14	0.3047	0.5338	0.6416	0.022*
C15	0.1608 (2)	0.49458 (19)	0.56209 (9)	0.0220 (4)
H15	0.1653	0.3983	0.5655	0.026*
C16	0.0713 (2)	0.5546 (2)	0.51225 (9)	0.0221 (4)
H16	0.0131	0.4998	0.4818	0.027*
C17	0.0671 (3)	0.6953 (2)	0.50700 (9)	0.0261 (4)
H17	0.0059	0.7366	0.4728	0.031*
C18	0.1512 (3)	0.77555 (19)	0.55114 (8)	0.0224 (4)
H18	0.1486	0.8717	0.5469	0.027*

	U11	U22	U33	U12	U13	U23
S1	0.0193 (2)	0.01418 (17)	0.01510 (18)	−0.00298 (17)	−0.00493 (16)	0.00065 (14)
S2	0.01155 (18)	0.0246 (2)	0.01375 (18)	−0.00025 (17)	−0.00070 (15)	−0.00305 (16)
N1	0.0151 (7)	0.0212 (7)	0.0167 (6)	0.0036 (6)	−0.0037 (6)	0.0015 (6)
O1	0.0241 (7)	0.0212 (6)	0.0182 (6)	−0.0059 (6)	−0.0033 (5)	0.0061 (5)
C1	0.0182 (8)	0.0152 (8)	0.0122 (7)	−0.0006 (7)	−0.0022 (6)	−0.0011 (7)
C2	0.0126 (7)	0.0160 (7)	0.0116 (7)	−0.0014 (7)	−0.0022 (6)	0.0003 (6)
C3	0.0162 (8)	0.0145 (7)	0.0132 (7)	−0.0018 (7)	−0.0004 (6)	0.0001 (7)
C4	0.0171 (9)	0.0199 (8)	0.0171 (8)	−0.0015 (7)	0.0029 (7)	−0.0002 (7)
C5	0.0135 (8)	0.0262 (9)	0.0252 (9)	−0.0001 (8)	0.0015 (8)	−0.0002 (7)
C6	0.0243 (10)	0.0303 (9)	0.0213 (8)	0.0088 (9)	−0.0098 (8)	−0.0003 (8)
C7	0.0127 (7)	0.0163 (7)	0.0135 (7)	−0.0029 (7)	−0.0037 (7)	−0.0017 (6)
C8	0.0199 (9)	0.0186 (8)	0.0180 (8)	0.0014 (8)	−0.0014 (7)	−0.0038 (7)
C9	0.0284 (10)	0.0242 (9)	0.0123 (7)	−0.0039 (8)	−0.0003 (7)	−0.0025 (7)
C10	0.0236 (9)	0.0200 (8)	0.0173 (8)	−0.0066 (8)	−0.0079 (7)	0.0022 (7)
C11	0.0151 (8)	0.0170 (8)	0.0270 (9)	−0.0019 (7)	−0.0062 (8)	0.0011 (7)
C12	0.0123 (8)	0.0183 (8)	0.0172 (8)	−0.0015 (7)	0.0000 (6)	−0.0031 (7)
C13	0.0117 (8)	0.0229 (8)	0.0109 (7)	0.0010 (7)	0.0006 (6)	−0.0026 (6)
C14	0.0164 (8)	0.0235 (8)	0.0154 (7)	0.0058 (8)	0.0007 (7)	−0.0013 (7)
C15	0.0226 (9)	0.0221 (9)	0.0213 (8)	0.0008 (8)	0.0015 (8)	−0.0053 (7)
C16	0.0176 (8)	0.0317 (10)	0.0170 (8)	−0.0014 (8)	0.0006 (7)	−0.0088 (7)
C17	0.0266 (10)	0.0351 (10)	0.0167 (8)	0.0049 (9)	−0.0100 (8)	−0.0018 (8)
C18	0.0293 (10)	0.0223 (8)	0.0157 (8)	0.0014 (8)	−0.0045 (8)	0.0006 (7)

S1—C7	1.7755 (17)	C7—C12	1.400 (3)
S1—C2	1.8535 (17)	C8—C9	1.392 (2)
S2—C13	1.7826 (17)	C8—H8	0.9500
S2—C2	1.8396 (18)	C9—C10	1.385 (3)
N1—C1	1.344 (2)	C9—H9	0.9500
N1—C6	1.466 (2)	C10—C11	1.390 (3)
N1—C5	1.468 (2)	C10—H10	0.9500
O1—C1	1.233 (2)	C11—C12	1.389 (2)
C1—C2	1.541 (2)	C11—H11	0.9500
C2—C3	1.519 (2)	C12—H12	0.9500
C3—C4	1.518 (2)	C13—C14	1.388 (3)
C3—H3A	0.9900	C13—C18	1.393 (2)
C3—H3B	0.9900	C14—C15	1.394 (3)
C4—C5	1.511 (3)	C14—H14	0.9500
C4—H4A	0.9900	C15—C16	1.385 (3)
C4—H4B	0.9900	C15—H15	0.9500
C5—H5A	0.9900	C16—C17	1.388 (3)
C5—H5B	0.9900	C16—H16	0.9500
C6—H6A	0.9800	C17—C18	1.381 (3)
C6—H6B	0.9800	C17—H17	0.9500
C6—H6C	0.9800	C18—H18	0.9500
C7—C8	1.395 (2)
C7—S1—C2	104.46 (7)	H6B—C6—H6C	109.5
C13—S2—C2	101.69 (8)	C8—C7—C12	119.57 (16)
C1—N1—C6	117.01 (16)	C8—C7—S1	118.46 (13)
C1—N1—C5	126.51 (15)	C12—C7—S1	121.82 (13)
C6—N1—C5	116.48 (15)	C9—C8—C7	119.86 (17)
O1—C1—N1	121.59 (16)	C9—C8—H8	120.1
O1—C1—C2	120.39 (16)	C7—C8—H8	120.1
N1—C1—C2	118.00 (15)	C10—C9—C8	120.14 (17)
C3—C2—C1	113.80 (14)	C10—C9—H9	119.9
C3—C2—S2	111.23 (11)	C8—C9—H9	119.9
C1—C2—S2	109.75 (11)	C9—C10—C11	120.47 (17)
C3—C2—S1	114.18 (11)	C9—C10—H10	119.8
C1—C2—S1	102.29 (11)	C11—C10—H10	119.8
S2—C2—S1	104.91 (9)	C12—C11—C10	119.60 (17)
C4—C3—C2	110.44 (14)	C12—C11—H11	120.2
C4—C3—H3A	109.6	C10—C11—H11	120.2
C2—C3—H3A	109.6	C11—C12—C7	120.32 (16)
C4—C3—H3B	109.6	C11—C12—H12	119.8
C2—C3—H3B	109.6	C7—C12—H12	119.8
H3A—C3—H3B	108.1	C14—C13—C18	119.44 (16)
C5—C4—C3	108.91 (14)	C14—C13—S2	120.21 (14)
C5—C4—H4A	109.9	C18—C13—S2	120.25 (14)
C3—C4—H4A	109.9	C13—C14—C15	120.15 (17)
C5—C4—H4B	109.9	C13—C14—H14	119.9
C3—C4—H4B	109.9	C15—C14—H14	119.9
H4A—C4—H4B	108.3	C16—C15—C14	120.10 (18)
N1—C5—C4	111.75 (15)	C16—C15—H15	120.0
N1—C5—H5A	109.3	C14—C15—H15	120.0
C4—C5—H5A	109.3	C15—C16—C17	119.63 (18)
N1—C5—H5B	109.3	C15—C16—H16	120.2
C4—C5—H5B	109.3	C17—C16—H16	120.2
H5A—C5—H5B	107.9	C18—C17—C16	120.46 (19)
N1—C6—H6A	109.5	C18—C17—H17	119.8
N1—C6—H6B	109.5	C16—C17—H17	119.8
H6A—C6—H6B	109.5	C17—C18—C13	120.21 (18)
N1—C6—H6C	109.5	C17—C18—H18	119.9
H6A—C6—H6C	109.5	C13—C18—H18	119.9
C6—N1—C1—O1	7.5 (3)	C3—C4—C5—N1	−48.7 (2)
C5—N1—C1—O1	−172.54 (16)	C2—S1—C7—C8	−115.91 (15)
C6—N1—C1—C2	−171.12 (14)	C2—S1—C7—C12	68.49 (16)
C5—N1—C1—C2	8.9 (3)	C12—C7—C8—C9	1.6 (3)
O1—C1—C2—C3	−172.11 (15)	S1—C7—C8—C9	−174.07 (15)
N1—C1—C2—C3	6.5 (2)	C7—C8—C9—C10	−0.7 (3)
O1—C1—C2—S2	−46.74 (18)	C8—C9—C10—C11	−0.9 (3)
N1—C1—C2—S2	131.88 (15)	C9—C10—C11—C12	1.6 (3)
O1—C1—C2—S1	64.23 (17)	C10—C11—C12—C7	−0.6 (3)
N1—C1—C2—S1	−117.15 (15)	C8—C7—C12—C11	−1.0 (3)
C13—S2—C2—C3	61.95 (12)	S1—C7—C12—C11	174.61 (13)
C13—S2—C2—C1	−64.87 (12)	C2—S2—C13—C14	−111.92 (15)
C13—S2—C2—S1	−174.12 (8)	C2—S2—C13—C18	71.68 (16)
C7—S1—C2—C3	33.97 (14)	C18—C13—C14—C15	−0.1 (3)
C7—S1—C2—C1	157.38 (11)	S2—C13—C14—C15	−176.56 (14)
C7—S1—C2—S2	−88.05 (9)	C13—C14—C15—C16	−0.7 (3)
C1—C2—C3—C4	−42.33 (18)	C14—C15—C16—C17	0.8 (3)
S2—C2—C3—C4	−166.90 (11)	C15—C16—C17—C18	−0.1 (3)
S1—C2—C3—C4	74.61 (16)	C16—C17—C18—C13	−0.7 (3)
C2—C3—C4—C5	63.97 (18)	C14—C13—C18—C17	0.8 (3)
C1—N1—C5—C4	13.1 (3)	S2—C13—C18—C17	177.28 (16)
C6—N1—C5—C4	−166.90 (15)

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11···O1i	0.95	2.32	3.237 (3)	163
C6—H6b···Cg1ii	0.98	2.95	3.606 (2)	125
C14—H14···Cg1iii	0.95	2.96	3.544 (2)	121

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	2.32	3.237 (3)	163
C6—H6b⋯Cg1ii	0.98	2.95	3.606 (2)	125
C14—H14⋯Cg1iii	0.95	2.96	3.544 (2)	121

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