1-Methyl-3,3-bis-[(4-methyl-phen-yl)sulfan-yl]piperidin-2-one.

The piperidone ring in the title compound, C(20)H(23)NOS(2), 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 inter-actions leads to the formation of supra-molecular 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 = 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

Δρmax = 0.68 e Å−3

Δρmin = −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 ▶).

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

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

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

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

C20H23NOS2	F(000) = 760
Mr = 357.53	Dx = 1.284 Mg m−3
Monoclinic, P21/n	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2yn	Cell parameters from 8545 reflections
a = 7.8943 (1) Å	θ = 3.7–74.2°
b = 9.8078 (2) Å	µ = 2.65 mm−1
c = 23.9145 (4) Å	T = 100 K
β = 92.803 (1)°	Block, colourless
V = 1849.38 (5) Å3	0.25 × 0.20 × 0.15 mm
Z = 4

Agilent SuperNova Dual Cu at zero diffractometer with an Atlas detector	3719 independent reflections
Radiation source: fine-focus sealed tube	3465 reflections with I > 2σ(I)
graphite	Rint = 0.042
Detector resolution: 10.4041 pixels mm-1	θmax = 74.4°, θmin = 3.7°
ω scans	h = −7→9
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	k = −11→12
Tmin = 0.558, Tmax = 0.692	l = −29→29
14169 measured reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.107	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.0608P)2 + 0.7727P] where P = (Fo2 + 2Fc2)/3
3719 reflections	(Δ/σ)max < 0.001
220 parameters	Δρmax = 0.68 e Å−3
0 restraints	Δρmin = −0.31 e Å−3

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	0.56118 (5)	0.85032 (4)	0.742407 (16)	0.02168 (13)
S2	0.59643 (5)	0.63592 (4)	0.658865 (16)	0.02231 (13)
N1	0.15516 (17)	0.80815 (15)	0.66875 (6)	0.0232 (3)
O1	0.38510 (15)	0.88872 (12)	0.62753 (5)	0.0266 (3)
C1	0.0471 (2)	0.8882 (2)	0.62973 (8)	0.0307 (4)
H1A	0.0871	0.8783	0.5918	0.046*
H1B	0.0517	0.9844	0.6407	0.046*
H1C	−0.0701	0.8554	0.6305	0.046*
C2	0.0687 (2)	0.73621 (18)	0.71307 (7)	0.0265 (3)
H2A	0.0091	0.6556	0.6968	0.032*
H2B	−0.0174	0.7973	0.7284	0.032*
C3	0.1907 (2)	0.69027 (17)	0.76010 (7)	0.0229 (3)
H3A	0.1333	0.6258	0.7848	0.028*
H3B	0.2293	0.7698	0.7828	0.028*
C4	0.3418 (2)	0.62117 (16)	0.73509 (6)	0.0201 (3)
H4A	0.3021	0.5441	0.7112	0.024*
H4B	0.4182	0.5844	0.7655	0.024*
C5	0.43854 (18)	0.72223 (16)	0.70031 (6)	0.0193 (3)
C6	0.32331 (19)	0.81387 (16)	0.66234 (6)	0.0204 (3)
C7	0.62175 (19)	0.76581 (16)	0.80585 (6)	0.0194 (3)
C8	0.5588 (2)	0.81362 (17)	0.85544 (7)	0.0240 (3)
H8	0.4773	0.8849	0.8546	0.029*
C9	0.6155 (2)	0.75683 (18)	0.90622 (7)	0.0259 (4)
H9	0.5729	0.7907	0.9400	0.031*
C10	0.7334 (2)	0.65141 (17)	0.90856 (7)	0.0241 (3)
C11	0.7935 (2)	0.60218 (16)	0.85848 (7)	0.0220 (3)
H11	0.8727	0.5292	0.8592	0.026*
C12	0.73859 (19)	0.65906 (16)	0.80755 (6)	0.0197 (3)
H12	0.7808	0.6251	0.7737	0.024*
C13	0.7979 (3)	0.5920 (2)	0.96396 (7)	0.0344 (4)
H13	0.7035	0.5831	0.9889	0.052*
H13B	0.8844	0.6524	0.9812	0.052*
H13C	0.8474	0.5020	0.9577	0.052*
C14	0.46802 (19)	0.53540 (17)	0.61152 (6)	0.0220 (3)
C15	0.4551 (2)	0.39502 (18)	0.61902 (7)	0.0242 (3)
H15	0.5083	0.3533	0.6512	0.029*
C16	0.3648 (2)	0.31557 (19)	0.57978 (7)	0.0273 (4)
H16	0.3568	0.2199	0.5854	0.033*
C17	0.2859 (2)	0.37422 (19)	0.53241 (7)	0.0276 (4)
C18	0.2970 (2)	0.5147 (2)	0.52567 (7)	0.0318 (4)
H18	0.2420	0.5563	0.4938	0.038*
C19	0.3866 (2)	0.59541 (19)	0.56450 (7)	0.0288 (4)
H19	0.3926	0.6912	0.5591	0.035*
C20	0.1961 (2)	0.2880 (2)	0.48744 (8)	0.0356 (4)
H20A	0.0953	0.3364	0.4724	0.053*
H20B	0.1621	0.2010	0.5036	0.053*
H20C	0.2730	0.2709	0.4572	0.053*

	U11	U22	U33	U12	U13	U23
S1	0.0222 (2)	0.0165 (2)	0.0259 (2)	−0.00289 (13)	−0.00351 (15)	0.00200 (13)
S2	0.0170 (2)	0.0272 (2)	0.0228 (2)	0.00184 (14)	0.00158 (14)	−0.00095 (14)
N1	0.0186 (6)	0.0239 (7)	0.0269 (7)	0.0039 (5)	−0.0015 (5)	−0.0002 (5)
O1	0.0270 (6)	0.0237 (6)	0.0289 (6)	−0.0027 (5)	−0.0023 (5)	0.0067 (5)
C1	0.0246 (9)	0.0338 (10)	0.0329 (9)	0.0076 (7)	−0.0077 (7)	−0.0009 (7)
C2	0.0188 (8)	0.0266 (9)	0.0342 (9)	−0.0007 (6)	0.0038 (6)	−0.0022 (7)
C3	0.0221 (8)	0.0212 (8)	0.0259 (8)	−0.0039 (6)	0.0055 (6)	−0.0023 (6)
C4	0.0201 (7)	0.0169 (7)	0.0233 (8)	−0.0018 (6)	0.0011 (6)	−0.0005 (6)
C5	0.0174 (7)	0.0184 (7)	0.0221 (7)	−0.0003 (6)	0.0005 (5)	0.0001 (6)
C6	0.0209 (7)	0.0154 (7)	0.0246 (8)	−0.0002 (6)	−0.0018 (6)	−0.0017 (6)
C7	0.0178 (7)	0.0176 (7)	0.0225 (7)	−0.0032 (6)	−0.0016 (5)	−0.0002 (6)
C8	0.0201 (8)	0.0225 (8)	0.0295 (8)	0.0011 (6)	0.0012 (6)	−0.0055 (6)
C9	0.0253 (8)	0.0297 (9)	0.0231 (8)	−0.0047 (7)	0.0043 (6)	−0.0069 (6)
C10	0.0248 (8)	0.0252 (8)	0.0219 (8)	−0.0079 (6)	−0.0012 (6)	−0.0001 (6)
C11	0.0208 (7)	0.0190 (8)	0.0260 (8)	−0.0013 (6)	−0.0013 (6)	0.0001 (6)
C12	0.0180 (7)	0.0190 (8)	0.0221 (7)	−0.0017 (6)	0.0017 (6)	−0.0031 (5)
C13	0.0435 (11)	0.0347 (10)	0.0244 (9)	−0.0040 (8)	−0.0040 (7)	0.0023 (7)
C14	0.0193 (7)	0.0265 (8)	0.0204 (7)	0.0044 (6)	0.0032 (5)	−0.0016 (6)
C15	0.0234 (8)	0.0265 (8)	0.0226 (8)	0.0041 (6)	0.0027 (6)	0.0016 (6)
C16	0.0270 (8)	0.0256 (9)	0.0297 (8)	0.0005 (7)	0.0062 (6)	−0.0023 (7)
C17	0.0216 (8)	0.0363 (10)	0.0251 (8)	0.0026 (7)	0.0029 (6)	−0.0070 (7)
C18	0.0353 (9)	0.0364 (10)	0.0232 (8)	0.0098 (8)	−0.0046 (7)	−0.0013 (7)
C19	0.0346 (9)	0.0267 (9)	0.0250 (8)	0.0059 (7)	−0.0008 (7)	0.0009 (7)
C20	0.0312 (9)	0.0441 (11)	0.0316 (9)	−0.0026 (8)	0.0034 (7)	−0.0116 (8)

S1—C7	1.7738 (16)	C9—C10	1.390 (3)
S1—C5	1.8531 (16)	C9—H9	0.9500
S2—C14	1.7802 (17)	C10—C11	1.396 (2)
S2—C5	1.8366 (16)	C10—C13	1.513 (2)
N1—C6	1.345 (2)	C11—C12	1.390 (2)
N1—C1	1.462 (2)	C11—H11	0.9500
N1—C2	1.469 (2)	C12—H12	0.9500
O1—C6	1.229 (2)	C13—H13	0.9800
C1—H1A	0.9800	C13—H13B	0.9800
C1—H1B	0.9800	C13—H13C	0.9800
C1—H1C	0.9800	C14—C15	1.393 (2)
C2—C3	1.513 (2)	C14—C19	1.398 (2)
C2—H2A	0.9900	C15—C16	1.390 (2)
C2—H2B	0.9900	C15—H15	0.9500
C3—C4	1.520 (2)	C16—C17	1.390 (2)
C3—H3A	0.9900	C16—H16	0.9500
C3—H3B	0.9900	C17—C18	1.391 (3)
C4—C5	1.523 (2)	C17—C20	1.516 (2)
C4—H4A	0.9900	C18—C19	1.387 (3)
C4—H4B	0.9900	C18—H18	0.9500
C5—C6	1.542 (2)	C19—H19	0.9500
C7—C8	1.389 (2)	C20—H20A	0.9800
C7—C12	1.395 (2)	C20—H20B	0.9800
C8—C9	1.390 (2)	C20—H20C	0.9800
C8—H8	0.9500
C7—S1—C5	105.06 (7)	C9—C8—H8	120.1
C14—S2—C5	102.60 (7)	C8—C9—C10	121.29 (15)
C6—N1—C1	116.97 (14)	C8—C9—H9	119.4
C6—N1—C2	126.74 (14)	C10—C9—H9	119.4
C1—N1—C2	116.19 (14)	C9—C10—C11	118.54 (15)
N1—C1—H1A	109.5	C9—C10—C13	121.17 (16)
N1—C1—H1B	109.5	C11—C10—C13	120.28 (16)
H1A—C1—H1B	109.5	C12—C11—C10	120.56 (16)
N1—C1—H1C	109.5	C12—C11—H11	119.7
H1A—C1—H1C	109.5	C10—C11—H11	119.7
H1B—C1—H1C	109.5	C11—C12—C7	120.31 (15)
N1—C2—C3	112.24 (13)	C11—C12—H12	119.8
N1—C2—H2A	109.2	C7—C12—H12	119.8
C3—C2—H2A	109.2	C10—C13—H13	109.5
N1—C2—H2B	109.2	C10—C13—H13B	109.5
C3—C2—H2B	109.2	H13—C13—H13B	109.5
H2A—C2—H2B	107.9	C10—C13—H13C	109.5
C2—C3—C4	108.87 (13)	H13—C13—H13C	109.5
C2—C3—H3A	109.9	H13B—C13—H13C	109.5
C4—C3—H3A	109.9	C15—C14—C19	119.09 (15)
C2—C3—H3B	109.9	C15—C14—S2	120.57 (12)
C4—C3—H3B	109.9	C19—C14—S2	120.24 (13)
H3A—C3—H3B	108.3	C16—C15—C14	120.38 (15)
C3—C4—C5	110.42 (13)	C16—C15—H15	119.8
C3—C4—H4A	109.6	C14—C15—H15	119.8
C5—C4—H4A	109.6	C15—C16—C17	120.85 (17)
C3—C4—H4B	109.6	C15—C16—H16	119.6
C5—C4—H4B	109.6	C17—C16—H16	119.6
H4A—C4—H4B	108.1	C16—C17—C18	118.45 (16)
C4—C5—C6	113.82 (12)	C16—C17—C20	121.49 (17)
C4—C5—S2	111.49 (11)	C18—C17—C20	120.01 (17)
C6—C5—S2	110.31 (10)	C19—C18—C17	121.37 (16)
C4—C5—S1	114.02 (10)	C19—C18—H18	119.3
C6—C5—S1	101.67 (10)	C17—C18—H18	119.3
S2—C5—S1	104.79 (7)	C18—C19—C14	119.84 (17)
O1—C6—N1	121.93 (14)	C18—C19—H19	120.1
O1—C6—C5	120.32 (14)	C14—C19—H19	120.1
N1—C6—C5	117.75 (13)	C17—C20—H20A	109.5
C8—C7—C12	119.48 (15)	C17—C20—H20B	109.5
C8—C7—S1	118.66 (12)	H20A—C20—H20B	109.5
C12—C7—S1	121.73 (12)	C17—C20—H20C	109.5
C7—C8—C9	119.81 (16)	H20A—C20—H20C	109.5
C7—C8—H8	120.1	H20B—C20—H20C	109.5
C6—N1—C2—C3	12.2 (2)	C5—S1—C7—C12	68.39 (14)
C1—N1—C2—C3	−163.84 (14)	C12—C7—C8—C9	1.4 (2)
N1—C2—C3—C4	−47.35 (18)	S1—C7—C8—C9	−174.50 (12)
C2—C3—C4—C5	63.55 (16)	C7—C8—C9—C10	−0.7 (2)
C3—C4—C5—C6	−43.61 (17)	C8—C9—C10—C11	−0.5 (2)
C3—C4—C5—S2	−169.18 (10)	C8—C9—C10—C13	178.60 (16)
C3—C4—C5—S1	72.41 (14)	C9—C10—C11—C12	1.1 (2)
C14—S2—C5—C4	65.40 (12)	C13—C10—C11—C12	−178.10 (15)
C14—S2—C5—C6	−62.08 (12)	C10—C11—C12—C7	−0.3 (2)
C14—S2—C5—S1	−170.79 (8)	C8—C7—C12—C11	−0.9 (2)
C7—S1—C5—C4	31.05 (13)	S1—C7—C12—C11	174.87 (12)
C7—S1—C5—C6	153.97 (10)	C5—S2—C14—C15	−105.11 (14)
C7—S1—C5—S2	−91.12 (8)	C5—S2—C14—C19	78.55 (14)
C1—N1—C6—O1	4.1 (2)	C19—C14—C15—C16	1.1 (2)
C2—N1—C6—O1	−171.93 (15)	S2—C14—C15—C16	−175.31 (12)
C1—N1—C6—C5	−175.70 (14)	C14—C15—C16—C17	0.0 (2)
C2—N1—C6—C5	8.2 (2)	C15—C16—C17—C18	−1.1 (3)
C4—C5—C6—O1	−171.64 (14)	C15—C16—C17—C20	176.18 (16)
S2—C5—C6—O1	−45.45 (17)	C16—C17—C18—C19	1.1 (3)
S1—C5—C6—O1	65.30 (16)	C20—C17—C18—C19	−176.26 (16)
C4—C5—C6—N1	8.2 (2)	C17—C18—C19—C14	0.0 (3)
S2—C5—C6—N1	134.37 (13)	C15—C14—C19—C18	−1.1 (2)
S1—C5—C6—N1	−114.88 (13)	S2—C14—C19—C18	175.28 (14)
C5—S1—C7—C8	−115.80 (13)

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

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

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