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

The piperidone ring in the title compound, C(18)H(17)Cl(2)NOS(2), has a distorted half-chair conformation. The S-bound benzene rings are approximately perpendicular to and splayed out of the mean plane through the piperidone ring [dihedral angles = 71.86 (13) and 46.94 (11)°]. In the crystal, C-H⋯O inter-actions link the mol-ecules into [010] supra-molecular chains with a helical topology. C-H⋯Cl and C-H⋯π inter-actions are also present.

Related literature

For background to β-thiocarbonyl compounds, see: Vinhato (2007 ▶); Olivato et al. (2009 ▶). For related structures, see: Zukerman-Schpector et al. (2006 ▶, 2008 ▶). For ring conformational analysis, see: Cremer & Pople (1975 ▶). For further synthetic details, see: Hashmat & McDermott (2002 ▶); Zoretic & Soja (1976 ▶).

Experimental

Crystal data

C18H17Cl2NOS2

M = 398.37

Monoclinic,

a = 8.0313 (2) Å

b = 9.7460 (2) Å

c = 24.2623 (7) Å

β = 94.0767 (12)°

V = 1894.28 (8) Å3

Z = 4

Mo Kα radiation

μ = 0.57 mm−1

T = 290 K

0.33 × 0.30 × 0.29 mm

Data collection

Nonius KappaCCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.82, T max = 0.85

12888 measured reflections

3288 independent reflections

2778 reflections with I > 2σ(I)

R int = 0.049

Refinement

R[F 2 > 2σ(F 2)] = 0.043

wR(F 2) = 0.121

S = 1.05

3288 reflections

218 parameters

H-atom parameters constrained

Δρmax = 0.37 e Å−3

Δρmin = −0.38 e Å−3

Data collection: COLLECT (Nonius, 1999 ▶); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO (Otwinowski & Minor, 1997 ▶) and SCALEPACK; program(s) used to solve structure: SIR97 (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: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810024347/hb5512sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810024347/hb5512Isup2.hkl

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

C18H17Cl2NOS2	F(000) = 824
Mr = 398.37	Dx = 1.397 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 10679 reflections
a = 8.0313 (2) Å	θ = 2.9–27.5°
b = 9.7460 (2) Å	µ = 0.57 mm−1
c = 24.2623 (7) Å	T = 290 K
β = 94.0767 (12)°	Irregular, colourless
V = 1894.28 (8) Å3	0.33 × 0.30 × 0.29 mm
Z = 4

Nonius KappaCCD diffractometer	3288 independent reflections
Radiation source: sealed tube	2778 reflections with I > 2σ(I)
graphite	Rint = 0.049
CCD rotation images scans	θmax = 25.0°, θmin = 3.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→8
Tmin = 0.82, Tmax = 0.85	k = −11→11
12888 measured reflections	l = −28→26

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.121	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.0558P)2 + 0.758P] where P = (Fo2 + 2Fc2)/3
3288 reflections	(Δ/σ)max < 0.001
218 parameters	Δρmax = 0.37 e Å−3
0 restraints	Δρmin = −0.38 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
C2	0.3322 (3)	0.3195 (2)	0.66893 (9)	0.0514 (5)
C3	0.4451 (2)	0.2265 (2)	0.70636 (9)	0.0490 (5)
C4	0.3506 (3)	0.1218 (2)	0.73838 (9)	0.0527 (5)
H4A	0.3189	0.0448	0.7145	0.063*
H4B	0.4223	0.0876	0.7692	0.063*
C5	0.1959 (3)	0.1856 (3)	0.75971 (10)	0.0629 (6)
H5A	0.1407	0.1199	0.7823	0.075*
H5B	0.2264	0.2650	0.7823	0.075*
C6	0.0808 (3)	0.2277 (3)	0.71127 (11)	0.0697 (7)
H6A	0.0309	0.1464	0.6940	0.084*
H6B	−0.0085	0.2835	0.7243	0.084*
C7	0.6208 (2)	0.2649 (2)	0.81264 (9)	0.0520 (5)
C8	0.7382 (3)	0.1601 (2)	0.81591 (10)	0.0557 (5)
H8	0.7841	0.1296	0.7840	0.067*
C9	0.7876 (3)	0.1008 (2)	0.86615 (11)	0.0632 (6)
H9	0.8659	0.0303	0.8681	0.076*
C10	0.7204 (3)	0.1464 (3)	0.91293 (11)	0.0678 (7)
C11	0.6026 (3)	0.2500 (3)	0.91080 (11)	0.0756 (7)
H11	0.5572	0.2800	0.9429	0.091*
C12	0.5534 (3)	0.3082 (3)	0.86065 (10)	0.0673 (7)
H12	0.4737	0.3776	0.8589	0.081*
C13	0.4783 (3)	0.0506 (2)	0.61552 (9)	0.0572 (5)
C14	0.4608 (3)	−0.0901 (3)	0.61981 (11)	0.0687 (6)
H14	0.5093	−0.1360	0.6505	0.082*
C15	0.3712 (4)	−0.1629 (3)	0.57846 (13)	0.0814 (8)
H15	0.3600	−0.2576	0.5811	0.098*
C16	0.2998 (3)	−0.0938 (4)	0.53379 (12)	0.0798 (8)
C17	0.3157 (4)	0.0450 (4)	0.52858 (12)	0.0869 (9)
H17	0.2660	0.0900	0.4979	0.104*
C18	0.4061 (4)	0.1180 (3)	0.56924 (11)	0.0744 (7)
H18	0.4188	0.2123	0.5657	0.089*
C19	0.0614 (4)	0.3812 (3)	0.62912 (13)	0.0835 (8)
H19A	0.0725	0.4778	0.6362	0.125*
H19B	−0.0530	0.3545	0.6314	0.125*
H19C	0.0954	0.3612	0.5928	0.125*
O1	0.3934 (2)	0.40242 (17)	0.63843 (7)	0.0719 (5)
Cl1	0.78388 (14)	0.07472 (10)	0.97627 (4)	0.1129 (3)
Cl2	0.19021 (13)	−0.18374 (14)	0.48074 (4)	0.1289 (4)
S1	0.56494 (8)	0.35278 (6)	0.75025 (3)	0.0615 (2)
S2	0.60276 (7)	0.14457 (7)	0.66590 (3)	0.0638 (2)
N1	0.1666 (2)	0.3052 (2)	0.67012 (8)	0.0589 (5)

	U11	U22	U33	U12	U13	U23
C2	0.0504 (12)	0.0463 (11)	0.0566 (12)	−0.0034 (9)	−0.0033 (9)	−0.0035 (9)
C3	0.0412 (11)	0.0466 (11)	0.0588 (12)	−0.0035 (8)	−0.0002 (9)	−0.0038 (9)
C4	0.0553 (12)	0.0434 (11)	0.0585 (13)	−0.0066 (9)	−0.0020 (10)	−0.0008 (9)
C5	0.0609 (14)	0.0606 (13)	0.0688 (15)	−0.0116 (11)	0.0150 (11)	−0.0024 (11)
C6	0.0474 (13)	0.0693 (15)	0.0928 (19)	−0.0050 (11)	0.0079 (12)	−0.0031 (13)
C7	0.0425 (11)	0.0500 (11)	0.0621 (12)	−0.0023 (9)	−0.0056 (9)	−0.0108 (10)
C8	0.0446 (11)	0.0576 (12)	0.0646 (14)	0.0018 (9)	0.0013 (10)	−0.0100 (10)
C9	0.0493 (12)	0.0538 (13)	0.0846 (17)	0.0044 (10)	−0.0083 (11)	−0.0089 (12)
C10	0.0654 (15)	0.0707 (15)	0.0645 (15)	−0.0047 (12)	−0.0161 (12)	−0.0043 (12)
C11	0.0682 (16)	0.0962 (19)	0.0615 (15)	0.0109 (14)	−0.0027 (12)	−0.0207 (14)
C12	0.0574 (14)	0.0725 (15)	0.0699 (16)	0.0178 (12)	−0.0097 (11)	−0.0204 (12)
C13	0.0451 (11)	0.0698 (14)	0.0566 (13)	0.0102 (10)	0.0043 (9)	−0.0087 (10)
C14	0.0633 (15)	0.0689 (16)	0.0735 (16)	0.0100 (12)	0.0019 (12)	−0.0054 (12)
C15	0.0790 (19)	0.0766 (17)	0.090 (2)	−0.0058 (14)	0.0131 (15)	−0.0209 (15)
C16	0.0612 (16)	0.109 (2)	0.0690 (17)	−0.0075 (15)	0.0079 (13)	−0.0283 (16)
C17	0.086 (2)	0.112 (2)	0.0606 (16)	0.0151 (17)	−0.0100 (14)	−0.0096 (16)
C18	0.0828 (18)	0.0781 (17)	0.0609 (15)	0.0126 (14)	−0.0043 (13)	−0.0028 (12)
C19	0.0666 (17)	0.0893 (19)	0.0905 (19)	0.0192 (14)	−0.0237 (14)	−0.0028 (15)
O1	0.0693 (11)	0.0663 (10)	0.0790 (11)	−0.0096 (8)	−0.0020 (9)	0.0199 (9)
Cl1	0.1408 (8)	0.1145 (7)	0.0781 (5)	0.0100 (6)	−0.0305 (5)	0.0123 (5)
Cl2	0.1044 (7)	0.1885 (11)	0.0944 (6)	−0.0460 (7)	0.0104 (5)	−0.0639 (7)
S1	0.0640 (4)	0.0479 (3)	0.0702 (4)	−0.0118 (2)	−0.0113 (3)	−0.0013 (2)
S2	0.0407 (3)	0.0814 (4)	0.0688 (4)	0.0036 (3)	−0.0002 (3)	−0.0123 (3)
N1	0.0470 (10)	0.0599 (11)	0.0686 (12)	0.0035 (8)	−0.0055 (8)	−0.0025 (9)

C2—O1	1.222 (3)	C10—C11	1.382 (4)
C2—N1	1.340 (3)	C10—Cl1	1.731 (3)
C2—C3	1.533 (3)	C11—C12	1.375 (4)
C3—C4	1.518 (3)	C11—H11	0.9300
C3—S2	1.839 (2)	C12—H12	0.9300
C3—S1	1.851 (2)	C13—C14	1.383 (4)
C4—C5	1.513 (3)	C13—C18	1.391 (3)
C4—H4A	0.9700	C13—S2	1.777 (2)
C4—H4B	0.9700	C14—C15	1.388 (4)
C5—C6	1.500 (3)	C14—H14	0.9300
C5—H5A	0.9700	C15—C16	1.367 (4)
C5—H5B	0.9700	C15—H15	0.9300
C6—N1	1.463 (3)	C16—C17	1.366 (4)
C6—H6A	0.9700	C16—Cl2	1.743 (3)
C6—H6B	0.9700	C17—C18	1.380 (4)
C7—C12	1.385 (3)	C17—H17	0.9300
C7—C8	1.388 (3)	C18—H18	0.9300
C7—S1	1.769 (2)	C19—N1	1.460 (3)
C8—C9	1.381 (3)	C19—H19A	0.9600
C8—H8	0.9300	C19—H19B	0.9600
C9—C10	1.365 (4)	C19—H19C	0.9600
C9—H9	0.9300
O1—C2—N1	121.6 (2)	C9—C10—Cl1	119.9 (2)
O1—C2—C3	120.21 (19)	C11—C10—Cl1	119.0 (2)
N1—C2—C3	118.18 (19)	C12—C11—C10	119.2 (2)
C4—C3—C2	113.84 (17)	C12—C11—H11	120.4
C4—C3—S2	111.66 (14)	C10—C11—H11	120.4
C2—C3—S2	109.95 (14)	C11—C12—C7	120.9 (2)
C4—C3—S1	114.26 (15)	C11—C12—H12	119.5
C2—C3—S1	102.08 (13)	C7—C12—H12	119.5
S2—C3—S1	104.26 (10)	C14—C13—C18	119.3 (2)
C5—C4—C3	110.55 (17)	C14—C13—S2	120.93 (19)
C5—C4—H4A	109.5	C18—C13—S2	119.6 (2)
C3—C4—H4A	109.5	C13—C14—C15	120.2 (3)
C5—C4—H4B	109.5	C13—C14—H14	119.9
C3—C4—H4B	109.5	C15—C14—H14	119.9
H4A—C4—H4B	108.1	C16—C15—C14	119.2 (3)
C6—C5—C4	108.67 (19)	C16—C15—H15	120.4
C6—C5—H5A	110.0	C14—C15—H15	120.4
C4—C5—H5A	110.0	C17—C16—C15	121.6 (3)
C6—C5—H5B	110.0	C17—C16—Cl2	118.4 (3)
C4—C5—H5B	110.0	C15—C16—Cl2	119.9 (3)
H5A—C5—H5B	108.3	C16—C17—C18	119.5 (3)
N1—C6—C5	112.44 (19)	C16—C17—H17	120.2
N1—C6—H6A	109.1	C18—C17—H17	120.2
C5—C6—H6A	109.1	C17—C18—C13	120.1 (3)
N1—C6—H6B	109.1	C17—C18—H18	119.9
C5—C6—H6B	109.1	C13—C18—H18	119.9
H6A—C6—H6B	107.8	N1—C19—H19A	109.5
C12—C7—C8	118.7 (2)	N1—C19—H19B	109.5
C12—C7—S1	118.79 (17)	H19A—C19—H19B	109.5
C8—C7—S1	122.34 (17)	N1—C19—H19C	109.5
C9—C8—C7	120.6 (2)	H19A—C19—H19C	109.5
C9—C8—H8	119.7	H19B—C19—H19C	109.5
C7—C8—H8	119.7	C7—S1—C3	105.06 (10)
C10—C9—C8	119.5 (2)	C13—S2—C3	102.48 (9)
C10—C9—H9	120.3	C2—N1—C19	117.4 (2)
C8—C9—H9	120.3	C2—N1—C6	125.80 (19)
C9—C10—C11	121.1 (2)	C19—N1—C6	116.7 (2)
O1—C2—C3—C4	−175.5 (2)	C14—C15—C16—C17	0.6 (4)
N1—C2—C3—C4	3.4 (3)	C14—C15—C16—Cl2	178.7 (2)
O1—C2—C3—S2	−49.4 (2)	C15—C16—C17—C18	0.0 (5)
N1—C2—C3—S2	129.55 (18)	Cl2—C16—C17—C18	−178.1 (2)
O1—C2—C3—S1	60.9 (2)	C16—C17—C18—C13	−0.9 (4)
N1—C2—C3—S1	−120.22 (18)	C14—C13—C18—C17	1.1 (4)
C2—C3—C4—C5	−40.9 (2)	S2—C13—C18—C17	177.0 (2)
S2—C3—C4—C5	−166.11 (15)	C12—C7—S1—C3	−113.91 (19)
S1—C3—C4—C5	75.9 (2)	C8—C7—S1—C3	70.55 (19)
C3—C4—C5—C6	63.6 (2)	C4—C3—S1—C7	29.71 (18)
C4—C5—C6—N1	−48.4 (3)	C2—C3—S1—C7	153.07 (14)
C12—C7—C8—C9	−0.4 (3)	S2—C3—S1—C7	−92.45 (12)
S1—C7—C8—C9	175.18 (17)	C14—C13—S2—C3	−104.0 (2)
C7—C8—C9—C10	−0.3 (3)	C18—C13—S2—C3	80.2 (2)
C8—C9—C10—C11	0.6 (4)	C4—C3—S2—C13	67.21 (17)
C8—C9—C10—Cl1	−178.95 (18)	C2—C3—S2—C13	−60.15 (16)
C9—C10—C11—C12	−0.3 (4)	S1—C3—S2—C13	−168.93 (11)
Cl1—C10—C11—C12	179.3 (2)	O1—C2—N1—C19	6.9 (3)
C10—C11—C12—C7	−0.3 (4)	C3—C2—N1—C19	−172.0 (2)
C8—C7—C12—C11	0.7 (4)	O1—C2—N1—C6	−168.6 (2)
S1—C7—C12—C11	−175.0 (2)	C3—C2—N1—C6	12.5 (3)
C18—C13—C14—C15	−0.4 (4)	C5—C6—N1—C2	11.0 (3)
S2—C13—C14—C15	−176.2 (2)	C5—C6—N1—C19	−164.5 (2)
C13—C14—C15—C16	−0.5 (4)

Cg1 is the centroid of the C7–C12.

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···O1i	0.93	2.32	3.218 (3)	164
C11—H11···Cl2ii	0.93	2.83	3.708 (3)	157
C19—H19a···Cg1iii	0.96	2.95	3.676 (3)	133

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C7–C12.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9⋯O1i	0.93	2.32	3.218 (3)	164
C11—H11⋯Cl2ii	0.93	2.83	3.708 (3)	157
C19—H19a⋯Cg1iii	0.96	2.95	3.676 (3)	133

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