rac-3-[(3-Chloro-anilino)(4-chloro-phenyl)meth-yl]thian-4-one.

In the title compound, C(18)H(17)Cl(2)NOS, the thio-pyran-one ring adopts a chair conformation, with the substituent in the axial position. The dihedral angle between the two benzene rings is 89.43 (1)°. In the crystal, mol-ecules form inversion dimers through inter-molecular N-H⋯O hydrogen bonds [graph set R(2) (2)(8)].

Related literature

For the preparation and spectroscopic characterization of a series of related compounds and the crystal structure of 3-[(phenyl­amino)(p-tol­yl)methly]dihydro-2H-thio­pyran-4(3H)-one, see: Abaee et al. (2012 ▶). For the crystal structures of related compounds, see: Guo et al. (2007 ▶); Fun et al. (2009 ▶); Harms et al. (2012 ▶). For patterns in hydrogen bonding, see: Bernstein et al. (1995 ▶). For defining the relative configuration of diastereomers, see: IUPAC (2012 ▶).

Experimental

Crystal data

C18H17Cl2NOS

M = 366.29

Monoclinic,

a = 11.2611 (8) Å

b = 8.6686 (7) Å

c = 18.0976 (12) Å

β = 105.266 (8)°

V = 1704.3 (2) Å3

Z = 4

Mo Kα radiation

μ = 0.51 mm−1

T = 193 K

0.29 × 0.24 × 0.05 mm

Data collection

Stoe IPDS-1 image-plate diffractometer

Absorption correction: integration X-RED32 (Stoe & Cie, 2006 ▶) T min = 0.890, T max = 0.978

15404 measured reflections

3134 independent reflections

1867 reflections with I > 2σ(I)

R int = 0.042

Refinement

R[F 2 > 2σ(F 2)] = 0.024

wR(F 2) = 0.048

S = 0.64

3134 reflections

212 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.17 e Å−3

Δρmin = −0.15 e Å−3

Data collection: EXPOSE (Stoe & Cie, 1994 ▶); cell refinement: CELL (Stoe & Cie, 1994 ▶); data reduction: X-RED32 (Stoe & Cie, 2006 ▶); program(s) used to solve structure: SIR92 (Altomare et al., 1994 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2007 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶), PLATON (Spek, 2009 ▶) and WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812004680/zs2176sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812004680/zs2176Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812004680/zs2176Isup3.cml

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

C18H17Cl2NOS	F(000) = 760
Mr = 366.29	Dx = 1.428 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 8000 reflections
a = 11.2611 (8) Å	θ = 1.9–25°
b = 8.6686 (7) Å	µ = 0.51 mm−1
c = 18.0976 (12) Å	T = 193 K
β = 105.266 (8)°	Plate, colourless
V = 1704.3 (2) Å3	0.29 × 0.24 × 0.05 mm
Z = 4

Stoe IPDS-1 image-plate diffractometer	3134 independent reflections
Radiation source: fine-focus sealed tube	1867 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.042
Detector resolution: 6.67 pixels mm-1	θmax = 25.4°, θmin = 1.9°
ω scans	h = −13→13
Absorption correction: integration X-RED32 (Stoe & Cie, 2006)	k = −10→10
Tmin = 0.890, Tmax = 0.978	l = −21→21
15404 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)] = 0.024	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.048	H atoms treated by a mixture of independent and constrained refinement
S = 0.64	w = 1/[σ2(Fo2) + (0.0127P)2] where P = (Fo2 + 2Fc2)/3
3134 reflections	(Δ/σ)max = 0.001
212 parameters	Δρmax = 0.17 e Å−3
0 restraints	Δρmin = −0.15 e Å−3

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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	0.31042 (19)	0.2357 (2)	0.53806 (11)	0.0272 (5)
H2A	0.3860	0.2956	0.5399	0.033*
H2B	0.2797	0.1939	0.4856	0.033*
C3	0.21227 (18)	0.3451 (2)	0.55471 (10)	0.0238 (5)
H3	0.1946	0.4265	0.5141	0.029*
C4	0.09371 (19)	0.2559 (2)	0.54853 (11)	0.0260 (5)
C5	0.10024 (19)	0.1153 (2)	0.59821 (11)	0.0282 (5)
H5A	0.0184	0.0653	0.5864	0.034*
H5B	0.1218	0.1472	0.6527	0.034*
C6	0.19574 (19)	−0.0013 (2)	0.58604 (12)	0.0308 (5)
H6A	0.1703	−0.0387	0.5325	0.037*
H6B	0.1970	−0.0910	0.6201	0.037*
C7	0.25464 (16)	0.4273 (2)	0.63362 (10)	0.0213 (4)
H7	0.2599	0.3478	0.6744	0.026*
C9	0.15786 (17)	0.6196 (2)	0.70276 (11)	0.0221 (4)
C10	0.23976 (18)	0.5889 (2)	0.77388 (11)	0.0251 (4)
H10	0.3020	0.5129	0.7783	0.030*
C11	0.2297 (2)	0.6703 (2)	0.83810 (11)	0.0288 (5)
C12	0.1428 (2)	0.7834 (3)	0.83454 (13)	0.0365 (6)
H12	0.1373	0.8374	0.8792	0.044*
C13	0.06325 (19)	0.8161 (3)	0.76353 (13)	0.0353 (5)
H13	0.0032	0.8948	0.7594	0.042*
C14	0.07008 (18)	0.7357 (2)	0.69860 (12)	0.0277 (5)
H14	0.0145	0.7598	0.6507	0.033*
C15	0.38184 (17)	0.4989 (2)	0.64544 (10)	0.0215 (4)
C16	0.48456 (17)	0.4248 (2)	0.69185 (10)	0.0240 (4)
H16	0.4738	0.3333	0.7182	0.029*
C17	0.60194 (19)	0.4826 (2)	0.70002 (11)	0.0266 (5)
H17	0.6714	0.4305	0.7312	0.032*
C18	0.61680 (18)	0.6159 (2)	0.66259 (10)	0.0242 (4)
C19	0.51657 (18)	0.6941 (2)	0.61697 (11)	0.0278 (5)
H19	0.5278	0.7872	0.5919	0.033*
C20	0.39949 (18)	0.6339 (2)	0.60864 (11)	0.0266 (5)
H20	0.3303	0.6861	0.5772	0.032*
N8	0.15854 (16)	0.5356 (2)	0.63804 (10)	0.0260 (4)
O1	−0.00210 (14)	0.29351 (18)	0.50276 (9)	0.0404 (4)
S1	0.34870 (5)	0.07723 (6)	0.60476 (3)	0.02864 (13)
Cl1	0.33192 (6)	0.62648 (7)	0.92643 (3)	0.04561 (17)
Cl2	0.76515 (5)	0.68900 (7)	0.67408 (3)	0.03580 (14)
H8	0.1180 (19)	0.569 (2)	0.5974 (11)	0.027 (6)*

	U11	U22	U33	U12	U13	U23
C2	0.0317 (12)	0.0281 (12)	0.0222 (10)	−0.0019 (10)	0.0076 (9)	−0.0037 (9)
C3	0.0298 (11)	0.0228 (11)	0.0172 (10)	0.0003 (9)	0.0031 (9)	0.0016 (8)
C4	0.0279 (12)	0.0285 (12)	0.0185 (10)	0.0027 (9)	0.0009 (9)	−0.0070 (9)
C5	0.0262 (11)	0.0277 (12)	0.0297 (11)	−0.0043 (10)	0.0058 (9)	0.0001 (10)
C6	0.0331 (12)	0.0244 (11)	0.0335 (12)	−0.0026 (10)	0.0061 (10)	−0.0013 (10)
C7	0.0233 (10)	0.0211 (10)	0.0184 (9)	0.0029 (9)	0.0035 (8)	0.0015 (9)
C9	0.0196 (10)	0.0201 (11)	0.0283 (10)	−0.0057 (9)	0.0095 (9)	−0.0017 (9)
C10	0.0255 (11)	0.0216 (11)	0.0307 (11)	−0.0034 (9)	0.0116 (9)	−0.0013 (9)
C11	0.0309 (12)	0.0298 (13)	0.0284 (11)	−0.0103 (10)	0.0125 (10)	−0.0022 (10)
C12	0.0368 (13)	0.0357 (14)	0.0444 (14)	−0.0102 (11)	0.0239 (11)	−0.0131 (11)
C13	0.0263 (12)	0.0308 (13)	0.0533 (14)	0.0015 (11)	0.0186 (11)	−0.0070 (11)
C14	0.0209 (11)	0.0262 (12)	0.0369 (12)	−0.0015 (9)	0.0095 (9)	0.0000 (10)
C15	0.0255 (11)	0.0220 (10)	0.0166 (10)	0.0021 (9)	0.0045 (8)	−0.0024 (9)
C16	0.0281 (11)	0.0220 (11)	0.0199 (9)	0.0000 (10)	0.0026 (8)	0.0017 (9)
C17	0.0262 (11)	0.0270 (12)	0.0243 (10)	0.0033 (10)	0.0026 (9)	−0.0021 (9)
C18	0.0241 (11)	0.0244 (11)	0.0245 (10)	−0.0013 (9)	0.0072 (8)	−0.0060 (9)
C19	0.0314 (12)	0.0210 (11)	0.0319 (11)	0.0001 (10)	0.0101 (10)	0.0048 (10)
C20	0.0240 (11)	0.0234 (11)	0.0312 (11)	0.0061 (9)	0.0053 (9)	0.0052 (10)
N8	0.0254 (10)	0.0282 (11)	0.0222 (9)	0.0053 (8)	0.0025 (8)	−0.0009 (8)
O1	0.0317 (8)	0.0408 (9)	0.0384 (8)	0.0017 (8)	−0.0090 (7)	0.0025 (8)
S1	0.0268 (3)	0.0258 (3)	0.0316 (3)	0.0030 (3)	0.0046 (2)	0.0003 (2)
Cl1	0.0576 (4)	0.0523 (4)	0.0252 (3)	−0.0036 (3)	0.0077 (3)	−0.0042 (3)
Cl2	0.0269 (3)	0.0373 (3)	0.0424 (3)	−0.0062 (3)	0.0076 (2)	−0.0012 (3)

C2—C3	1.545 (3)	C10—C11	1.389 (3)
C2—S1	1.804 (2)	C10—H10	0.9500
C2—H2A	0.9900	C11—C12	1.375 (3)
C2—H2B	0.9900	C11—Cl1	1.748 (2)
C3—C4	1.521 (3)	C12—C13	1.388 (3)
C3—C7	1.555 (2)	C12—H12	0.9500
C3—H3	1.0000	C13—C14	1.385 (3)
C4—O1	1.219 (2)	C13—H13	0.9500
C4—C5	1.505 (3)	C14—H14	0.9500
C5—C6	1.533 (3)	C15—C20	1.386 (3)
C5—H5A	0.9900	C15—C16	1.395 (3)
C5—H5B	0.9900	C16—C17	1.385 (3)
C6—S1	1.799 (2)	C16—H16	0.9500
C6—H6A	0.9900	C17—C18	1.372 (3)
C6—H6B	0.9900	C17—H17	0.9500
C7—N8	1.451 (2)	C18—C19	1.388 (3)
C7—C15	1.524 (3)	C18—Cl2	1.747 (2)
C7—H7	1.0000	C19—C20	1.389 (3)
C9—N8	1.381 (2)	C19—H19	0.9500
C9—C10	1.397 (3)	C20—H20	0.9500
C9—C14	1.399 (3)	N8—H8	0.81 (2)
C3—C2—S1	113.20 (13)	C11—C10—H10	120.2
C3—C2—H2A	108.9	C9—C10—H10	120.2
S1—C2—H2A	108.9	C12—C11—C10	122.5 (2)
C3—C2—H2B	108.9	C12—C11—Cl1	119.15 (16)
S1—C2—H2B	108.9	C10—C11—Cl1	118.39 (17)
H2A—C2—H2B	107.8	C11—C12—C13	117.82 (19)
C4—C3—C2	109.45 (16)	C11—C12—H12	121.1
C4—C3—C7	110.60 (15)	C13—C12—H12	121.1
C2—C3—C7	113.47 (15)	C14—C13—C12	121.1 (2)
C4—C3—H3	107.7	C14—C13—H13	119.5
C2—C3—H3	107.7	C12—C13—H13	119.5
C7—C3—H3	107.7	C13—C14—C9	120.82 (19)
O1—C4—C5	121.19 (19)	C13—C14—H14	119.6
O1—C4—C3	121.12 (19)	C9—C14—H14	119.6
C5—C4—C3	117.63 (17)	C20—C15—C16	118.50 (18)
C4—C5—C6	111.94 (16)	C20—C15—C7	121.65 (17)
C4—C5—H5A	109.2	C16—C15—C7	119.80 (17)
C6—C5—H5A	109.2	C17—C16—C15	120.98 (19)
C4—C5—H5B	109.2	C17—C16—H16	119.5
C6—C5—H5B	109.2	C15—C16—H16	119.5
H5A—C5—H5B	107.9	C18—C17—C16	119.29 (19)
C5—C6—S1	113.37 (15)	C18—C17—H17	120.4
C5—C6—H6A	108.9	C16—C17—H17	120.4
S1—C6—H6A	108.9	C17—C18—C19	121.32 (19)
C5—C6—H6B	108.9	C17—C18—Cl2	118.95 (16)
S1—C6—H6B	108.9	C19—C18—Cl2	119.73 (16)
H6A—C6—H6B	107.7	C18—C19—C20	118.74 (19)
N8—C7—C15	114.59 (17)	C18—C19—H19	120.6
N8—C7—C3	107.13 (14)	C20—C19—H19	120.6
C15—C7—C3	111.44 (14)	C15—C20—C19	121.15 (19)
N8—C7—H7	107.8	C15—C20—H20	119.4
C15—C7—H7	107.8	C19—C20—H20	119.4
C3—C7—H7	107.8	C9—N8—C7	123.97 (17)
N8—C9—C10	122.09 (18)	C9—N8—H8	116.9 (15)
N8—C9—C14	119.70 (18)	C7—N8—H8	115.6 (14)
C10—C9—C14	118.17 (18)	C6—S1—C2	96.53 (10)
C11—C10—C9	119.63 (19)
S1—C2—C3—C4	−61.14 (18)	C10—C9—C14—C13	−1.2 (3)
S1—C2—C3—C7	62.93 (19)	N8—C7—C15—C20	−46.3 (2)
C2—C3—C4—O1	−120.6 (2)	C3—C7—C15—C20	75.5 (2)
C7—C3—C4—O1	113.7 (2)	N8—C7—C15—C16	136.32 (18)
C2—C3—C4—C5	56.6 (2)	C3—C7—C15—C16	−101.83 (19)
C7—C3—C4—C5	−69.1 (2)	C20—C15—C16—C17	−1.2 (3)
O1—C4—C5—C6	121.5 (2)	C7—C15—C16—C17	176.23 (17)
C3—C4—C5—C6	−55.7 (2)	C15—C16—C17—C18	0.8 (3)
C4—C5—C6—S1	58.2 (2)	C16—C17—C18—C19	0.3 (3)
C4—C3—C7—N8	−61.7 (2)	C16—C17—C18—Cl2	179.32 (15)
C2—C3—C7—N8	174.84 (16)	C17—C18—C19—C20	−0.9 (3)
C4—C3—C7—C15	172.20 (16)	Cl2—C18—C19—C20	180.00 (15)
C2—C3—C7—C15	48.8 (2)	C16—C15—C20—C19	0.5 (3)
N8—C9—C10—C11	−175.75 (18)	C7—C15—C20—C19	−176.88 (18)
C14—C9—C10—C11	1.9 (3)	C18—C19—C20—C15	0.5 (3)
C9—C10—C11—C12	−1.3 (3)	C10—C9—N8—C7	−10.8 (3)
C9—C10—C11—Cl1	178.88 (15)	C14—C9—N8—C7	171.62 (18)
C10—C11—C12—C13	−0.2 (3)	C15—C7—N8—C9	−62.2 (2)
Cl1—C11—C12—C13	179.69 (16)	C3—C7—N8—C9	173.59 (17)
C11—C12—C13—C14	0.9 (3)	C5—C6—S1—C2	−56.47 (16)
C12—C13—C14—C9	−0.3 (3)	C3—C2—S1—C6	58.68 (16)
N8—C9—C14—C13	176.54 (18)

D—H···A	D—H	H···A	D···A	D—H···A
N8—H8···O1i	0.81 (2)	2.27 (2)	3.070 (2)	168 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N8—H8⋯O1i	0.81 (2)	2.27 (2)	3.070 (2)	168 (2)

Symmetry code: (i) .