3,3-Bis[(4-meth-oxy-phen-yl)sulfan-yl]-1-methyl-piperidin-2-one.

The piperidone ring in the title compound, C(20)H(23)NO(3)S(2), has a distorted half-chair conformation with the central methyl-ene atom of the propyl fragment lying 0.696 (1) Å out of the plane defined by the other five atoms (r.m.s. deviation = 0.071 Å). One of the S-bound phenyl rings is almost perpendicular to the mean plane through the piperidone ring, whereas the other is splayed [dihedral angles = 71.95 (6) and 38.42 (6)°]. In the crystal, C-H⋯O and C-H⋯π inter-actions lead 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: Caracelli et al. (2012 ▶); Zukerman-Schpector et al. (2010 ▶, 2011 ▶). For ring conformational analysis, see: Cremer & Pople (1975 ▶). For the synthesis, see: Hashmat & McDermott, (2002 ▶); Zoretic & Soja (1976 ▶).

Experimental

Crystal data

C20H23NO3S2

M = 389.53

Monoclinic,

a = 8.5802 (1) Å

b = 9.4744 (1) Å

c = 23.3732 (2) Å

β = 91.018 (1)°

V = 1899.76 (3) Å3

Z = 4

Cu Kα radiation

μ = 2.70 mm−1

T = 100 K

0.30 × 0.25 × 0.20 mm

Data collection

Agilent SuperNova Dual (Cu at zero) Atlas detector diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ▶) T min = 0.498, T max = 0.614

7011 measured reflections

3763 independent reflections

3484 reflections with I > 2σ(I)

R int = 0.016

Refinement

R[F 2 > 2σ(F 2)] = 0.029

wR(F 2) = 0.076

S = 1.06

3763 reflections

238 parameters

H-atom parameters constrained

Δρmax = 0.25 e Å−3

Δρmin = −0.35 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 (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/S1600536812025202/su2445sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812025202/su2445Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812025202/su2445Isup3.cml

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

C20H23NO3S2	F(000) = 824
Mr = 389.53	Dx = 1.362 Mg m−3
Monoclinic, P21/n	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2yn	Cell parameters from 4644 reflections
a = 8.5802 (1) Å	θ = 3.8–74.3°
b = 9.4744 (1) Å	µ = 2.70 mm−1
c = 23.3732 (2) Å	T = 100 K
β = 91.018 (1)°	Prism, colourless
V = 1899.76 (3) Å3	0.30 × 0.25 × 0.20 mm
Z = 4

Agilent SuperNova Dual (Cu at zero) Atlas detector diffractometer	3763 independent reflections
Radiation source: fine-focus sealed tube	3484 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.016
Detector resolution: 10.4041 pixels mm-1	θmax = 74.5°, θmin = 3.8°
ω scans	h = −9→10
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −7→11
Tmin = 0.498, Tmax = 0.614	l = −28→28
7011 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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.076	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.0385P)2 + 0.7353P] where P = (Fo2 + 2Fc2)/3
3763 reflections	(Δ/σ)max < 0.001
238 parameters	Δρmax = 0.25 e Å−3
0 restraints	Δρmin = −0.35 e Å−3

Experimental. Spectroscopic data for compound (I):IR (cm-1): ν(C=O) 1662. NMR (CDCl3, p.p.m.): δ 1.86–1.90 (2H, multiplet), 1.93–1.95 (2H, multiplet), 2.89 (3H, singlet), 3.12–3.14 (2H, triplet, J = 6.0 Hz), 3.82 (6H, singlet) 6.84–6.87 (4H, multiplet, Aryl-H), 7.53–7.55 (4H, multiplet, Aryl-H).

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
C1	0.65880 (15)	0.88587 (14)	0.83750 (5)	0.0156 (3)
C2	0.55775 (15)	0.79082 (13)	0.79859 (5)	0.0149 (3)
C3	0.64992 (16)	0.68485 (14)	0.76382 (6)	0.0171 (3)
H3A	0.6783	0.6030	0.7882	0.021*
H3B	0.5846	0.6503	0.7314	0.021*
C4	0.79668 (16)	0.75248 (15)	0.74115 (6)	0.0201 (3)
H4A	0.8519	0.6850	0.7163	0.024*
H4B	0.7693	0.8368	0.7181	0.024*
C5	0.90077 (17)	0.79433 (16)	0.79111 (6)	0.0234 (3)
H5A	0.9456	0.7084	0.8090	0.028*
H5B	0.9880	0.8526	0.7771	0.028*
C6	0.90807 (18)	0.95375 (17)	0.87618 (7)	0.0280 (3)
H6A	0.8835	0.9215	0.9148	0.042*
H6B	0.8841	1.0545	0.8726	0.042*
H6C	1.0191	0.9385	0.8692	0.042*
C7	0.39879 (16)	0.82787 (14)	0.69129 (5)	0.0164 (3)
C8	0.48089 (16)	0.85797 (15)	0.64178 (6)	0.0197 (3)
H8	0.5623	0.9259	0.6429	0.024*
C9	0.44427 (17)	0.78940 (15)	0.59104 (6)	0.0205 (3)
H9	0.5007	0.8103	0.5575	0.025*
C10	0.32476 (16)	0.68970 (14)	0.58905 (5)	0.0166 (3)
C11	0.24152 (15)	0.65820 (14)	0.63809 (6)	0.0161 (3)
H11	0.1602	0.5902	0.6369	0.019*
C12	0.27956 (15)	0.72801 (14)	0.68886 (6)	0.0169 (3)
H12	0.2232	0.7072	0.7225	0.020*
C13	0.52232 (15)	0.59131 (14)	0.88711 (6)	0.0167 (3)
C14	0.52403 (16)	0.44562 (15)	0.87749 (6)	0.0192 (3)
H14	0.4702	0.4078	0.8451	0.023*
C15	0.60328 (16)	0.35581 (15)	0.91466 (6)	0.0208 (3)
H15	0.6035	0.2570	0.9078	0.025*
C16	0.68264 (15)	0.41136 (15)	0.96214 (6)	0.0181 (3)
C17	0.68445 (16)	0.55632 (15)	0.97184 (6)	0.0185 (3)
H17	0.7409	0.5942	1.0036	0.022*
C18	0.60273 (16)	0.64528 (15)	0.93459 (6)	0.0184 (3)
H18	0.6018	0.7440	0.9416	0.022*
C19	0.18049 (18)	0.52401 (17)	0.53274 (6)	0.0269 (3)
H19A	0.1766	0.4858	0.4938	0.040*
H19B	0.0803	0.5681	0.5414	0.040*
H19C	0.2015	0.4475	0.5600	0.040*
C20	0.84281 (17)	0.36600 (17)	1.04494 (6)	0.0247 (3)
H20A	0.8842	0.2863	1.0672	0.037*
H20B	0.7759	0.4237	1.0692	0.037*
H20C	0.9294	0.4236	1.0312	0.037*
N	0.81502 (13)	0.87439 (12)	0.83427 (5)	0.0190 (2)
O1	0.59763 (11)	0.96898 (10)	0.87087 (4)	0.0203 (2)
O2	0.30155 (12)	0.62711 (11)	0.53720 (4)	0.0226 (2)
O3	0.75382 (12)	0.31405 (11)	0.99716 (4)	0.0225 (2)
S1	0.44547 (4)	0.92077 (3)	0.755059 (13)	0.01775 (9)
S2	0.40881 (4)	0.70322 (4)	0.841568 (14)	0.01771 (9)

	U11	U22	U33	U12	U13	U23
C1	0.0190 (6)	0.0141 (6)	0.0138 (6)	−0.0017 (5)	0.0000 (5)	0.0019 (5)
C2	0.0174 (6)	0.0146 (6)	0.0127 (6)	−0.0002 (5)	0.0004 (5)	0.0012 (5)
C3	0.0229 (7)	0.0139 (6)	0.0146 (6)	0.0017 (5)	0.0006 (5)	−0.0001 (5)
C4	0.0243 (7)	0.0181 (7)	0.0181 (7)	0.0040 (6)	0.0066 (5)	0.0011 (5)
C5	0.0194 (7)	0.0217 (7)	0.0292 (8)	0.0019 (6)	0.0043 (6)	−0.0015 (6)
C6	0.0228 (7)	0.0278 (8)	0.0330 (8)	−0.0062 (6)	−0.0067 (6)	−0.0042 (7)
C7	0.0195 (6)	0.0153 (6)	0.0142 (6)	0.0019 (5)	−0.0028 (5)	0.0010 (5)
C8	0.0218 (7)	0.0185 (7)	0.0188 (7)	−0.0047 (5)	−0.0028 (5)	0.0046 (5)
C9	0.0229 (7)	0.0249 (7)	0.0136 (6)	−0.0032 (6)	0.0013 (5)	0.0053 (5)
C10	0.0189 (6)	0.0169 (6)	0.0139 (6)	0.0023 (5)	−0.0025 (5)	0.0014 (5)
C11	0.0148 (6)	0.0164 (6)	0.0170 (6)	0.0006 (5)	−0.0014 (5)	0.0018 (5)
C12	0.0164 (6)	0.0192 (7)	0.0151 (6)	0.0022 (5)	0.0013 (5)	0.0023 (5)
C13	0.0170 (6)	0.0192 (6)	0.0141 (6)	−0.0030 (5)	0.0028 (5)	0.0022 (5)
C14	0.0214 (7)	0.0215 (7)	0.0149 (6)	−0.0061 (6)	0.0018 (5)	−0.0002 (5)
C15	0.0236 (7)	0.0176 (7)	0.0213 (7)	−0.0041 (5)	0.0051 (5)	0.0002 (5)
C16	0.0162 (6)	0.0218 (7)	0.0165 (6)	−0.0004 (5)	0.0044 (5)	0.0048 (5)
C17	0.0198 (6)	0.0221 (7)	0.0136 (6)	−0.0032 (5)	0.0013 (5)	−0.0002 (5)
C18	0.0216 (7)	0.0180 (7)	0.0157 (6)	−0.0024 (5)	0.0029 (5)	−0.0007 (5)
C19	0.0302 (8)	0.0282 (8)	0.0223 (7)	−0.0073 (7)	−0.0015 (6)	−0.0068 (6)
C20	0.0228 (7)	0.0324 (8)	0.0187 (7)	−0.0002 (6)	0.0004 (5)	0.0074 (6)
N	0.0175 (6)	0.0182 (6)	0.0212 (6)	−0.0028 (5)	−0.0003 (4)	−0.0020 (5)
O1	0.0235 (5)	0.0196 (5)	0.0178 (5)	0.0006 (4)	−0.0007 (4)	−0.0053 (4)
O2	0.0264 (5)	0.0271 (5)	0.0143 (5)	−0.0055 (4)	−0.0002 (4)	−0.0029 (4)
O3	0.0241 (5)	0.0221 (5)	0.0213 (5)	0.0003 (4)	−0.0003 (4)	0.0063 (4)
S1	0.02349 (18)	0.01403 (16)	0.01560 (16)	0.00191 (12)	−0.00321 (12)	−0.00080 (11)
S2	0.01626 (16)	0.02082 (17)	0.01604 (16)	−0.00271 (12)	0.00022 (12)	0.00262 (12)

C1—O1	1.2323 (16)	C10—O2	1.3607 (16)
C1—N	1.3483 (17)	C10—C11	1.3936 (18)
C1—C2	1.5368 (18)	C11—C12	1.3922 (18)
C2—C3	1.5220 (18)	C11—H11	0.9500
C2—S2	1.8376 (13)	C12—H12	0.9500
C2—S1	1.8558 (13)	C13—C18	1.3935 (18)
C3—C4	1.5168 (19)	C13—C14	1.3986 (19)
C3—H3A	0.9900	C13—S2	1.7801 (14)
C3—H3B	0.9900	C14—C15	1.386 (2)
C4—C5	1.510 (2)	C14—H14	0.9500
C4—H4A	0.9900	C15—C16	1.395 (2)
C4—H4B	0.9900	C15—H15	0.9500
C5—N	1.4700 (18)	C16—O3	1.3694 (16)
C5—H5A	0.9900	C16—C17	1.392 (2)
C5—H5B	0.9900	C17—C18	1.3923 (19)
C6—N	1.4610 (18)	C17—H17	0.9500
C6—H6A	0.9800	C18—H18	0.9500
C6—H6B	0.9800	C19—O2	1.4283 (18)
C6—H6C	0.9800	C19—H19A	0.9800
C7—C12	1.3939 (19)	C19—H19B	0.9800
C7—C8	1.3947 (19)	C19—H19C	0.9800
C7—S1	1.7708 (13)	C20—O3	1.4290 (17)
C8—C9	1.3835 (19)	C20—H20A	0.9800
C8—H8	0.9500	C20—H20B	0.9800
C9—C10	1.394 (2)	C20—H20C	0.9800
C9—H9	0.9500
O1—C1—N	121.47 (12)	C11—C10—C9	120.33 (12)
O1—C1—C2	120.46 (12)	C12—C11—C10	118.92 (12)
N—C1—C2	118.07 (11)	C12—C11—H11	120.5
C3—C2—C1	114.17 (11)	C10—C11—H11	120.5
C3—C2—S2	111.53 (9)	C11—C12—C7	121.19 (12)
C1—C2—S2	109.37 (9)	C11—C12—H12	119.4
C3—C2—S1	114.48 (9)	C7—C12—H12	119.4
C1—C2—S1	102.57 (8)	C18—C13—C14	118.93 (13)
S2—C2—S1	103.89 (7)	C18—C13—S2	121.03 (11)
C4—C3—C2	110.50 (11)	C14—C13—S2	119.92 (11)
C4—C3—H3A	109.5	C15—C14—C13	120.77 (13)
C2—C3—H3A	109.5	C15—C14—H14	119.6
C4—C3—H3B	109.5	C13—C14—H14	119.6
C2—C3—H3B	109.5	C14—C15—C16	119.63 (13)
H3A—C3—H3B	108.1	C14—C15—H15	120.2
C5—C4—C3	108.91 (11)	C16—C15—H15	120.2
C5—C4—H4A	109.9	O3—C16—C17	124.28 (13)
C3—C4—H4A	109.9	O3—C16—C15	115.33 (12)
C5—C4—H4B	109.9	C17—C16—C15	120.38 (13)
C3—C4—H4B	109.9	C16—C17—C18	119.43 (13)
H4A—C4—H4B	108.3	C16—C17—H17	120.3
N—C5—C4	111.70 (11)	C18—C17—H17	120.3
N—C5—H5A	109.3	C17—C18—C13	120.84 (13)
C4—C5—H5A	109.3	C17—C18—H18	119.6
N—C5—H5B	109.3	C13—C18—H18	119.6
C4—C5—H5B	109.3	O2—C19—H19A	109.5
H5A—C5—H5B	107.9	O2—C19—H19B	109.5
N—C6—H6A	109.5	H19A—C19—H19B	109.5
N—C6—H6B	109.5	O2—C19—H19C	109.5
H6A—C6—H6B	109.5	H19A—C19—H19C	109.5
N—C6—H6C	109.5	H19B—C19—H19C	109.5
H6A—C6—H6C	109.5	O3—C20—H20A	109.5
H6B—C6—H6C	109.5	O3—C20—H20B	109.5
C12—C7—C8	119.09 (12)	H20A—C20—H20B	109.5
C12—C7—S1	121.77 (10)	O3—C20—H20C	109.5
C8—C7—S1	119.12 (10)	H20A—C20—H20C	109.5
C9—C8—C7	120.31 (13)	H20B—C20—H20C	109.5
C9—C8—H8	119.8	C1—N—C6	116.94 (12)
C7—C8—H8	119.8	C1—N—C5	126.17 (12)
C8—C9—C10	120.16 (13)	C6—N—C5	116.84 (12)
C8—C9—H9	119.9	C10—O2—C19	117.24 (11)
C10—C9—H9	119.9	C16—O3—C20	117.50 (11)
O2—C10—C11	124.76 (12)	C7—S1—C2	103.84 (6)
O2—C10—C9	114.89 (12)	C13—S2—C2	102.56 (6)
O1—C1—C2—C3	−174.73 (12)	O3—C16—C17—C18	−177.42 (12)
N—C1—C2—C3	4.69 (17)	C15—C16—C17—C18	1.8 (2)
O1—C1—C2—S2	−48.98 (15)	C16—C17—C18—C13	−1.5 (2)
N—C1—C2—S2	130.43 (11)	C14—C13—C18—C17	0.4 (2)
O1—C1—C2—S1	60.84 (14)	S2—C13—C18—C17	176.48 (10)
N—C1—C2—S1	−119.75 (11)	O1—C1—N—C6	6.26 (19)
C1—C2—C3—C4	−40.74 (15)	C2—C1—N—C6	−173.14 (12)
S2—C2—C3—C4	−165.34 (9)	O1—C1—N—C5	−171.00 (13)
S1—C2—C3—C4	77.07 (12)	C2—C1—N—C5	9.59 (19)
C2—C3—C4—C5	63.62 (14)	C4—C5—N—C1	13.72 (19)
C3—C4—C5—N	−49.55 (15)	C4—C5—N—C6	−163.55 (12)
C12—C7—C8—C9	0.0 (2)	C11—C10—O2—C19	1.48 (19)
S1—C7—C8—C9	−178.44 (11)	C9—C10—O2—C19	179.98 (13)
C7—C8—C9—C10	0.1 (2)	C17—C16—O3—C20	−3.66 (19)
C8—C9—C10—O2	−178.68 (12)	C15—C16—O3—C20	177.13 (12)
C8—C9—C10—C11	−0.1 (2)	C12—C7—S1—C2	77.37 (12)
O2—C10—C11—C12	178.54 (12)	C8—C7—S1—C2	−104.27 (11)
C9—C10—C11—C12	0.1 (2)	C3—C2—S1—C7	30.09 (11)
C10—C11—C12—C7	−0.1 (2)	C1—C2—S1—C7	154.33 (8)
C8—C7—C12—C11	0.1 (2)	S2—C2—S1—C7	−91.77 (7)
S1—C7—C12—C11	178.42 (10)	C18—C13—S2—C2	77.44 (12)
C18—C13—C14—C15	0.5 (2)	C14—C13—S2—C2	−106.48 (11)
S2—C13—C14—C15	−175.69 (10)	C3—C2—S2—C13	61.21 (10)
C13—C14—C15—C16	−0.2 (2)	C1—C2—S2—C13	−66.04 (10)
C14—C15—C16—O3	178.31 (12)	S1—C2—S2—C13	−174.98 (6)
C14—C15—C16—C17	−0.9 (2)

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11···O1i	0.95	2.50	3.4211 (16)	165
C9—H9···O3ii	0.95	2.48	3.3473 (17)	151
C6—H6b···Cg1ii	0.98	2.93	3.5232 (17)	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	2.50	3.4211 (16)	165
C9—H9⋯O3ii	0.95	2.48	3.3473 (17)	151
C6—H6b⋯Cg1ii	0.98	2.93	3.5232 (17)	120

Symmetry codes: (i) ; (ii) .