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The title mol­ecule, C12H14OS2, has approximate Cs symmetry. The di­thia­ne ring adopts a chair conformation with the acetyl substituent in an axial orientation. Weak intermolecular C-H...O hydrogen bonds link mol­ecules into a chain along the y axis.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100014785/qa0403sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100014785/qa0403Isup2.hkl
Contains datablock I

CCDC reference: 156203

Comment top

1-(1,3-Dithian-2-yl)-2-phenylethanone, (I), was first synthesized by Tolstikov et al. (1989). In the course of our studies of synthetic tropane analogues (Tavasli, 1999), this compound was obtained by a different route and its structure is presented here.

The dithiane ring adopts the chair conformation with the phenylacetyl substituent in an axial orientation. The carbonyl group is directed towards the dithiane S atoms and the CC has an almost ideally staggered orientation between the C2—S bonds; the S1—C2—C7—O and S3—C2—C7—O torsion angles are −71.5 (1) and 58.7 (1)°, respectively. The molecule has an approximate (local) Cs symmetry. A survey of the April 2000 release of the Cambridge Structural Database (Allen & Kennard, 1993) revealed 31 structures with a dithiane ring monosubstituted at the 2-position, all of which displayed a chair conformation of the ring. The substituent was axial in ten compounds, equatorial in 20 and in one, namely bis(1,3-dithian-2-yl)methanol, both orientations were observed simultaneously (Bulman-Page et al., 1987). It is noteworthy that an electronegative atom bonded to the α-atom of the side chain usually favours the axial orientation, as in (I). The gas-phase electron diffraction study of unsubstituted dithiane (Adams & Bartell, 1977) also revealed the chair conformation and the bond lengths [average C—S 1.812 (3) and C—C 1.533 (2) Å] very close to those observed in (I) [average C—S 1.817 (5) and C—C 1.519 (2) Å]. The torsion angles in the gas phase, S—C—S—C 61.4, C—S—C—C 58.3 and S—C—C—C 64.1°, differ slightly from those in (I), averaging 53.1, 56.9 and 68.0°, respectively, obviously due to steric repulsion between the ring and the substituent.

Molecules related by the b-glide plane, i.e. the symmetry operation (3/2 − x, 1/2 + y, z), form a very weak hydrogen bond C2—H···O [C—H 0.95 (2), C···O 3.220 (2), H···O(2) 2.39 Å; angles C—H—O 146 (2) and H—O—C 136 (1)°].

Experimental top

A 1.6 M solution of n-butyllithium (0.5 g, 7.3 mmol) in hexane was added dropwise at 213 K to a solution of 1,3-dithiane (0.8 g, 7 mmol) in THF (25 ml) and stirred for 2.5 h at 253 K. N-Methyl-N-methoxyphenylacetamide was prepared according to Sibous & Tipping (1993) and added to the mixture at 213 K (1.5 g, 8.4 mmol, in 5 ml of THF). The reaction was stirred for 18 h at 213 K to room temperature, then quenched with water. Organic products were extracted into CH2Cl2, washed with HCl, saturated NaHCO3 and water, dried over MgSO4, concentrated in vacuo and purified over alumina, giving (I) as a white solid. X-ray quality crystals were obtained from ethyl acetate/petrol (3:7).

Refinement top

Refined C—H distances are in the range 0.92 (2)–0.98 (2) Å.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SMART; data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXTL (Bruker, 1997); program(s) used to refine structure: SHELXTL; software used to prepare material for publication: SHELXTL.

1-(1,3-Dithian-2-yl)-2-phenylethanone top
Crystal data top
C12H14OS2Dx = 1.334 Mg m3
Mr = 238.35Melting point: 89–91° C cf. Tolstikov et al. (1989) reported 79–81° C K
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
a = 11.735 (1) ÅCell parameters from 411 reflections
b = 9.775 (1) Åθ = 10–20°
c = 20.695 (2) ŵ = 0.42 mm1
V = 2373.9 (4) Å3T = 150 K
Z = 8Block, colourless
F(000) = 10080.40 × 0.33 × 0.22 mm
Data collection top
SMART 1K CCD area-detector
diffractometer
2846 independent reflections
Radiation source: fine-focus sealed tube2533 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.025
ω scansθmax = 28.0°, θmin = 2.0°
Absorption correction: integration
XPREP/SHELXTL (Bruker, 1997); R(int)=0.029 before correction
h = 1614
Tmin = 0.878, Tmax = 0.927k = 1312
10906 measured reflectionsl = 2814
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.030Hydrogen site location: difference Fourier map
wR(F2) = 0.080All H-atom parameters refined
S = 1.09 w = 1/[σ2(Fo2) + (0.0273P)2 + 1.3282P]
where P = (Fo2 + 2Fc2)/3
2804 reflections(Δ/σ)max = 0.001
192 parametersΔρmax = 0.27 e Å3
0 restraintsΔρmin = 0.26 e Å3
Crystal data top
C12H14OS2V = 2373.9 (4) Å3
Mr = 238.35Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 11.735 (1) ŵ = 0.42 mm1
b = 9.775 (1) ÅT = 150 K
c = 20.695 (2) Å0.40 × 0.33 × 0.22 mm
Data collection top
SMART 1K CCD area-detector
diffractometer
2846 independent reflections
Absorption correction: integration
XPREP/SHELXTL (Bruker, 1997); R(int)=0.029 before correction
2533 reflections with I > 2σ(I)
Tmin = 0.878, Tmax = 0.927Rint = 0.025
10906 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0300 restraints
wR(F2) = 0.080All H-atom parameters refined
S = 1.09Δρmax = 0.27 e Å3
2804 reflectionsΔρmin = 0.26 e Å3
192 parameters
Special details top

Experimental. The data collection nominally covered over a hemisphere of reciprocal space, by a combination of four sets of ω scans; each set at different ϕ and/or 2θ angles and each scan (10 sec exposure) covering 0.3° in ω. Crystal decay was monitored by repeating 50 initial frames at the end of data collection and comparing duplicate reflections. Crystal to detector distance 4.5 cm.

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 on F2 for ALL reflections except for 42 with very negative F2. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > 2σ(F2) is used only for calculating _R_factor_gt etc. and is not relevant to the choice of reflections for refinement.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.48994 (3)0.59505 (3)0.65416 (2)0.02444 (10)
C20.64252 (11)0.61342 (13)0.66530 (7)0.0212 (3)
H20.6608 (14)0.6993 (17)0.6470 (7)0.025 (4)*
S30.68889 (3)0.62686 (4)0.74854 (2)0.02725 (10)
C40.62280 (14)0.4769 (2)0.78525 (7)0.0293 (3)
H410.6595 (15)0.3953 (19)0.7685 (9)0.033 (5)*
H420.6423 (16)0.4865 (19)0.8299 (9)0.040 (5)*
C50.49440 (14)0.4710 (2)0.77603 (7)0.0289 (3)
H510.4605 (16)0.552 (2)0.7917 (8)0.035 (5)*
H520.4676 (17)0.394 (2)0.8015 (9)0.041 (5)*
C60.46002 (13)0.4495 (2)0.70603 (7)0.0269 (3)
H610.4962 (15)0.3682 (18)0.6874 (9)0.031 (4)*
H620.3778 (17)0.439 (2)0.7010 (9)0.040 (5)*
C70.70525 (11)0.50212 (14)0.62758 (7)0.0226 (3)
C80.76882 (14)0.55363 (15)0.56895 (7)0.0268 (3)
H810.8248 (18)0.618 (2)0.5861 (10)0.052 (6)*
H820.7169 (17)0.611 (2)0.5444 (10)0.045 (5)*
C90.82069 (12)0.44404 (13)0.52689 (6)0.0223 (3)
C100.76505 (14)0.3998 (2)0.47125 (7)0.0305 (3)
H100.6950 (16)0.441 (2)0.4600 (9)0.038 (5)*
C110.8134 (2)0.2995 (2)0.43202 (8)0.0409 (4)
H110.7756 (18)0.271 (2)0.3957 (10)0.057 (6)*
C120.9180 (2)0.2429 (2)0.44811 (8)0.0427 (4)
H120.9480 (18)0.177 (2)0.4217 (10)0.054 (6)*
C130.97398 (15)0.2862 (2)0.50329 (8)0.0360 (4)
H131.0457 (17)0.249 (2)0.5152 (10)0.048 (6)*
C140.92543 (13)0.38626 (15)0.54254 (7)0.0265 (3)
H140.9637 (16)0.4174 (18)0.5794 (9)0.033 (5)*
O0.70427 (12)0.38295 (11)0.64389 (6)0.0453 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0233 (2)0.0226 (2)0.0274 (2)0.00107 (13)0.00350 (13)0.00248 (13)
C20.0225 (6)0.0153 (6)0.0258 (6)0.0005 (5)0.0057 (5)0.0013 (5)
S30.0254 (2)0.0239 (2)0.0324 (2)0.00146 (13)0.00586 (14)0.00323 (14)
C40.0389 (8)0.0263 (7)0.0228 (7)0.0025 (6)0.0038 (6)0.0023 (6)
C50.0353 (8)0.0261 (7)0.0254 (7)0.0015 (6)0.0096 (6)0.0013 (6)
C60.0254 (7)0.0235 (7)0.0319 (7)0.0061 (5)0.0023 (6)0.0006 (6)
C70.0234 (6)0.0190 (6)0.0253 (6)0.0026 (5)0.0055 (5)0.0015 (5)
C80.0343 (8)0.0195 (7)0.0267 (7)0.0018 (6)0.0093 (6)0.0021 (5)
C90.0281 (7)0.0184 (6)0.0203 (6)0.0014 (5)0.0077 (5)0.0033 (5)
C100.0368 (8)0.0296 (8)0.0250 (7)0.0032 (6)0.0005 (6)0.0053 (6)
C110.0691 (12)0.0333 (9)0.0204 (7)0.0112 (8)0.0032 (8)0.0026 (6)
C120.0704 (13)0.0252 (8)0.0324 (8)0.0029 (8)0.0278 (8)0.0005 (6)
C130.0365 (9)0.0286 (8)0.0428 (9)0.0082 (6)0.0176 (7)0.0118 (7)
C140.0278 (7)0.0265 (7)0.0252 (7)0.0021 (6)0.0039 (6)0.0044 (6)
O0.0672 (8)0.0191 (5)0.0497 (7)0.0133 (5)0.0358 (6)0.0092 (5)
Geometric parameters (Å, º) top
S1—C21.8143 (14)C7—C81.511 (2)
S1—C61.8165 (15)C8—C91.509 (2)
C2—C71.528 (2)C8—H810.97 (2)
C2—S31.8113 (15)C8—H820.97 (2)
C2—H20.95 (2)C9—C141.391 (2)
S3—C41.824 (2)C9—C101.393 (2)
C4—C51.520 (2)C10—C111.393 (2)
C4—H410.97 (2)C10—H100.95 (2)
C4—H420.96 (2)C11—C121.387 (3)
C5—C61.518 (2)C11—H110.92 (2)
C5—H510.94 (2)C12—C131.384 (3)
C5—H520.97 (2)C12—H120.92 (2)
C6—H610.98 (2)C13—C141.393 (2)
C6—H620.98 (2)C13—H130.95 (2)
C7—O1.213 (2)C14—H140.94 (2)
C2—S1—C6101.14 (7)O—C7—C2122.49 (12)
C7—C2—S3113.13 (9)C8—C7—C2114.26 (11)
C7—C2—S1109.88 (9)C9—C8—C7115.22 (12)
S3—C2—S1115.12 (7)C9—C8—H81113.3 (12)
C7—C2—H2108.6 (10)C7—C8—H81104.7 (13)
S3—C2—H2104.3 (10)C9—C8—H82111.3 (12)
S1—C2—H2105.1 (10)C7—C8—H82107.6 (12)
C2—S3—C4102.13 (7)H81—C8—H82103.8 (17)
C5—C4—S3113.58 (11)C14—C9—C10118.72 (14)
C5—C4—H41111.3 (11)C14—C9—C8120.70 (13)
S3—C4—H41108.9 (11)C10—C9—C8120.57 (13)
C5—C4—H42111.3 (12)C9—C10—C11120.6 (2)
S3—C4—H42102.8 (12)C9—C10—H10118.6 (12)
H41—C4—H42108.6 (15)C11—C10—H10120.7 (12)
C6—C5—C4112.87 (12)C12—C11—C10120.1 (2)
C6—C5—H51109.3 (11)C12—C11—H11120.1 (14)
C4—C5—H51110.0 (11)C10—C11—H11119.8 (14)
C6—C5—H52108.8 (12)C13—C12—C11119.8 (2)
C4—C5—H52106.4 (12)C13—C12—H12121.7 (14)
H51—C5—H52109.3 (15)C11—C12—H12118.6 (14)
C5—C6—S1113.85 (10)C12—C13—C14120.1 (2)
C5—C6—H61111.9 (10)C12—C13—H13121.3 (12)
S1—C6—H61108.6 (10)C14—C13—H13118.6 (13)
C5—C6—H62112.3 (11)C9—C14—C13120.71 (15)
S1—C6—H62102.2 (11)C9—C14—H14118.8 (11)
H61—C6—H62107.4 (15)C13—C14—H14120.5 (11)
O—C7—C8123.25 (13)
S1—C2—C7—C8109.0 (1)C2—S3—C4—C555.8 (1)
C2—C7—C8—C9173.6 (1)S3—C2—S1—C653.4 (1)
C7—C8—C9—C1098.3 (2)S1—C2—S3—C452.8 (1)
S1—C2—C7—O71.5 (1)S1—C6—C5—C468.8 (1)
S3—C2—C7—O58.7 (1)S3—C4—C5—C667.1 (1)
C2—S1—C6—C558.0 (1)

Experimental details

Crystal data
Chemical formulaC12H14OS2
Mr238.35
Crystal system, space groupOrthorhombic, Pbca
Temperature (K)150
a, b, c (Å)11.735 (1), 9.775 (1), 20.695 (2)
V3)2373.9 (4)
Z8
Radiation typeMo Kα
µ (mm1)0.42
Crystal size (mm)0.40 × 0.33 × 0.22
Data collection
DiffractometerSMART 1K CCD area-detector
diffractometer
Absorption correctionIntegration
XPREP/SHELXTL (Bruker, 1997); R(int)=0.029 before correction
Tmin, Tmax0.878, 0.927
No. of measured, independent and
observed [I > 2σ(I)] reflections
10906, 2846, 2533
Rint0.025
(sin θ/λ)max1)0.661
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.030, 0.080, 1.09
No. of reflections2804
No. of parameters192
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.27, 0.26

Computer programs: SMART (Siemens, 1996), SMART, SAINT (Siemens, 1996), SHELXTL (Bruker, 1997), SHELXTL.

Selected geometric parameters (Å, º) top
S1—C21.8143 (14)C4—C51.520 (2)
S1—C61.8165 (15)C5—C61.518 (2)
C2—C71.528 (2)C7—O1.213 (2)
C2—S31.8113 (15)C7—C81.511 (2)
S3—C41.824 (2)C8—C91.509 (2)
C2—S1—C6101.14 (7)S3—C2—S1115.12 (7)
C7—C2—S3113.13 (9)C2—S3—C4102.13 (7)
C7—C2—S1109.88 (9)
 

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