2,6-Di­phenylthiapyran-4-one

In the title compound, 2,6-di­phenyl­thia­cyclo­hexan-4-one, C₁₇H₁₆OS, mirror site symmetry is retained by the mol­ecule in the solid state in the absence of C-H...X hydrogen bonds. The crystal structure is stabilized by van der Waals interactions, the shortest S...O and C...O contacts being 3.567 (2) and 3.512 (3) Å, respectively.

S1. Comment

The tendency of molecules to pack as closely as possible, usually, overrides that for retention of molecular symmetry upon crystallization and reduces the symmetry of a molecule in the solid state compared to that observed in the free state (Kitaigorodskii, 1973). Though inversion generally is the symmetry element which is carried over into the crystal, the tendency of molecules to possess mirror or twofold symmetry in the solid state seems to depend on the presence, nature and strength of the intermolecular interactions. An example of this is the crystal structure of 2,6-dibenzoyl-1,4-benzoquinone (Biradha et al., 1997), where interference from numerous C—H···O hydrogen bonds lowers the symmetry of the molecule.

In the present structure, (I), the molecule is bisected by a mirror plane passing through the atoms S1, C4 and O1 of the heterocyclic ring (Fig. 1). There are no C—H···X type interactions whose presence otherwise might have had a considerable influence on the molecular conformation. The absence of C—H···O hydrogen bonds is presumably due to the deficiency of acceptors compared to the donors (phenyl C—H). The crystal structure is stabilized by van der Waals interactions. The shortest S···O and C···O contacts observed are 3.567 (2) Å and 3.512 (3) Å, respectively. The strucutre provides a good example of the retention of mirror symmetry of a molecule in the crystals. \sch

S2. Experimental

The crystals were grown by slow evaporation of a saturated ethanol solution.

Computing details

Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: CAD-4 Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLUTO (Motherwell & Clegg, 1978); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. The molecular structure of (I) with the atom-numbering scheme and 50% probability displacement ellipsoids.

2,6-diphenyl-thiopyran-4-one

Crystal data

C17H16OS	F(000) = 568
Mr = 268.36	Dx = 1.245 Mg m^−3
Orthorhombic, Pnma	Cu Kα radiation, λ = 1.54180 Å
Hall symbol: -P 2ac 2n	Cell parameters from 25 reflections
a = 10.867 (3) Å	θ = 8–16°
b = 24.284 (4) Å	µ = 1.90 mm^−1
c = 5.427 (2) Å	T = 293 K
V = 1432.2 (7) Å^3	Plates, colourless
Z = 4	0.20 × 0.12 × 0.08 mm

Data collection

Enraf-Nonius CAD-4 diffractometer	Rint = 0.007
Radiation source: fine-focus sealed tube	θmax = 71.9°, θmin = 3.6°
Graphite monochromator	h = 0→13
ω–2θ scans	k = −29→11
1585 measured reflections	l = −6→0
1436 independent reflections	2 standard reflections every 200 reflections
1285 reflections with I > 2σ(I)	intensity decay: 1%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.043	Only H-atom displacement parameters refined
wR(F^2) = 0.123	w = 1/[σ^2(Fo^2) + (0.0432P)^2 + 0.1515P] where P = (Fo^2 + 2Fc^2)/3
S = 1.17	(Δ/σ)max < 0.001
1436 reflections	Δρmax = 0.35 e Å^−3
124 parameters	Δρmin = −0.18 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0126 (9)

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
S1	0.28672 (5)	0.2500	0.77840 (10)	0.0600 (2)
O1	0.0090 (2)	0.2500	0.2052 (3)	0.0999 (7)
C2	0.23937 (14)	0.19352 (7)	0.5821 (3)	0.0639 (4)
C3	0.10133 (15)	0.19750 (8)	0.5219 (4)	0.0730 (5)
C4	0.0661 (2)	0.2500	0.3963 (4)	0.0739 (7)
C7	0.27358 (16)	0.14107 (8)	0.7105 (3)	0.0677 (5)
C8	0.2127 (2)	0.12431 (10)	0.9227 (4)	0.0870 (6)
C9	0.2452 (3)	0.07676 (11)	1.0424 (6)	0.1048 (8)
C10	0.3391 (3)	0.04492 (11)	0.9537 (6)	0.1127 (10)
C11	0.4009 (3)	0.06105 (12)	0.7482 (7)	0.1186 (10)
C12	0.3688 (2)	0.10896 (9)	0.6252 (5)	0.0898 (6)
H3A	0.0779 (18)	0.1652 (8)	0.424 (4)	0.084 (6)*
H2	0.2857 (18)	0.1970 (8)	0.430 (4)	0.076 (6)*
H3B	0.053 (2)	0.1970 (8)	0.684 (4)	0.084 (6)*
H9	0.201 (3)	0.0632 (12)	1.195 (6)	0.131 (11)*
H10	0.359 (3)	0.0125 (13)	1.032 (5)	0.137 (10)*
H12	0.467 (3)	0.0420 (11)	0.689 (5)	0.116 (9)*
H11	0.407 (2)	0.1207 (9)	0.476 (4)	0.099 (7)*
H8	0.145 (3)	0.1461 (10)	0.983 (5)	0.122 (9)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0458 (3)	0.0720 (4)	0.0623 (4)	0.000	−0.0069 (2)	0.000
O1	0.0717 (12)	0.161 (2)	0.0673 (11)	0.000	−0.0206 (9)	0.000
C2	0.0486 (8)	0.0856 (11)	0.0576 (9)	−0.0016 (7)	0.0015 (6)	−0.0090 (8)
C3	0.0505 (9)	0.0963 (13)	0.0721 (10)	−0.0067 (8)	−0.0072 (8)	−0.0109 (9)
C4	0.0414 (10)	0.120 (2)	0.0598 (13)	0.000	−0.0025 (9)	0.000
C7	0.0575 (9)	0.0746 (10)	0.0709 (10)	−0.0046 (7)	−0.0077 (7)	−0.0155 (8)
C8	0.0904 (14)	0.0918 (14)	0.0786 (13)	0.0003 (11)	0.0023 (10)	0.0003 (11)
C9	0.1215 (19)	0.0927 (15)	0.1002 (18)	−0.0073 (15)	−0.0128 (16)	0.0088 (13)
C10	0.136 (2)	0.0730 (13)	0.129 (2)	−0.0033 (14)	−0.034 (2)	0.0031 (14)
C11	0.114 (2)	0.0905 (16)	0.152 (3)	0.0285 (16)	−0.0062 (18)	−0.0200 (17)
C12	0.0759 (12)	0.0894 (13)	0.1042 (16)	0.0069 (10)	0.0018 (12)	−0.0162 (12)

Geometric parameters (Å, º)

S1—C2	1.8114 (17)	C7—C8	1.389 (3)
S1—C2^i	1.8114 (17)	C8—C9	1.371 (3)
O1—C4	1.209 (3)	C8—H8	0.96 (3)
C2—C7	1.499 (2)	C9—C10	1.367 (4)
C2—C3	1.538 (2)	C9—H9	1.01 (3)
C2—H2	0.97 (2)	C10—C11	1.359 (5)
C3—C4	1.496 (2)	C10—H10	0.92 (3)
C3—H3A	0.98 (2)	C11—C12	1.386 (4)
C3—H3B	1.02 (2)	C11—H12	0.91 (3)
C4—C3^i	1.495 (2)	C12—H11	0.95 (2)
C7—C12	1.376 (3)
C2—S1—C2^i	98.43 (12)	C12—C7—C2	120.78 (19)
C7—C2—C3	113.20 (15)	C8—C7—C2	121.09 (18)
C7—C2—S1	107.42 (11)	C9—C8—C7	121.1 (3)
C3—C2—S1	110.74 (12)	C9—C8—H8	119.9 (15)
C7—C2—H2	109.9 (11)	C7—C8—H8	119.0 (15)
C3—C2—H2	108.7 (11)	C10—C9—C8	120.1 (3)
S1—C2—H2	106.6 (11)	C10—C9—H9	117.2 (18)
C4—C3—C2	113.57 (16)	C8—C9—H9	122.6 (18)
C4—C3—H3A	111.6 (11)	C11—C10—C9	119.6 (3)
C2—C3—H3A	108.5 (12)	C11—C10—H10	120.5 (18)
C4—C3—H3B	105.7 (11)	C9—C10—H10	119.9 (19)
C2—C3—H3B	108.4 (12)	C10—C11—C12	120.9 (3)
H3A—C3—H3B	108.9 (15)	C10—C11—H12	122.0 (18)
O1—C4—C3^i	121.52 (10)	C12—C11—H12	117.1 (18)
O1—C4—C3	121.51 (10)	C7—C12—C11	120.2 (3)
C3^i—C4—C3	116.9 (2)	C7—C12—H11	116.3 (15)
C12—C7—C8	118.1 (2)	C11—C12—H11	123.4 (15)

Symmetry code: (i) x, −y+1/2, z.