Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100014785/qa0403sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100014785/qa0403Isup2.hkl |
CCDC reference: 156203
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).
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.
C12H14OS2 | Dx = 1.334 Mg m−3 |
Mr = 238.35 | Melting point: 89–91° C cf. Tolstikov et al. (1989) reported 79–81° C K |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
a = 11.735 (1) Å | Cell parameters from 411 reflections |
b = 9.775 (1) Å | θ = 10–20° |
c = 20.695 (2) Å | µ = 0.42 mm−1 |
V = 2373.9 (4) Å3 | T = 150 K |
Z = 8 | Block, colourless |
F(000) = 1008 | 0.40 × 0.33 × 0.22 mm |
SMART 1K CCD area-detector diffractometer | 2846 independent reflections |
Radiation source: fine-focus sealed tube | 2533 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.025 |
ω scans | θmax = 28.0°, θmin = 2.0° |
Absorption correction: integration XPREP/SHELXTL (Bruker, 1997); R(int)=0.029 before correction | h = −16→14 |
Tmin = 0.878, Tmax = 0.927 | k = −13→12 |
10906 measured reflections | l = −28→14 |
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)] = 0.030 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.080 | All 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 parameters | Δρmax = 0.27 e Å−3 |
0 restraints | Δρmin = −0.26 e Å−3 |
C12H14OS2 | V = 2373.9 (4) Å3 |
Mr = 238.35 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 11.735 (1) Å | µ = 0.42 mm−1 |
b = 9.775 (1) Å | T = 150 K |
c = 20.695 (2) Å | 0.40 × 0.33 × 0.22 mm |
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 = 0.927 | Rint = 0.025 |
10906 measured reflections |
R[F2 > 2σ(F2)] = 0.030 | 0 restraints |
wR(F2) = 0.080 | All H-atom parameters refined |
S = 1.09 | Δρmax = 0.27 e Å−3 |
2804 reflections | Δρmin = −0.26 e Å−3 |
192 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
S1 | 0.48994 (3) | 0.59505 (3) | 0.65416 (2) | 0.02444 (10) | |
C2 | 0.64252 (11) | 0.61342 (13) | 0.66530 (7) | 0.0212 (3) | |
H2 | 0.6608 (14) | 0.6993 (17) | 0.6470 (7) | 0.025 (4)* | |
S3 | 0.68889 (3) | 0.62686 (4) | 0.74854 (2) | 0.02725 (10) | |
C4 | 0.62280 (14) | 0.4769 (2) | 0.78525 (7) | 0.0293 (3) | |
H41 | 0.6595 (15) | 0.3953 (19) | 0.7685 (9) | 0.033 (5)* | |
H42 | 0.6423 (16) | 0.4865 (19) | 0.8299 (9) | 0.040 (5)* | |
C5 | 0.49440 (14) | 0.4710 (2) | 0.77603 (7) | 0.0289 (3) | |
H51 | 0.4605 (16) | 0.552 (2) | 0.7917 (8) | 0.035 (5)* | |
H52 | 0.4676 (17) | 0.394 (2) | 0.8015 (9) | 0.041 (5)* | |
C6 | 0.46002 (13) | 0.4495 (2) | 0.70603 (7) | 0.0269 (3) | |
H61 | 0.4962 (15) | 0.3682 (18) | 0.6874 (9) | 0.031 (4)* | |
H62 | 0.3778 (17) | 0.439 (2) | 0.7010 (9) | 0.040 (5)* | |
C7 | 0.70525 (11) | 0.50212 (14) | 0.62758 (7) | 0.0226 (3) | |
C8 | 0.76882 (14) | 0.55363 (15) | 0.56895 (7) | 0.0268 (3) | |
H81 | 0.8248 (18) | 0.618 (2) | 0.5861 (10) | 0.052 (6)* | |
H82 | 0.7169 (17) | 0.611 (2) | 0.5444 (10) | 0.045 (5)* | |
C9 | 0.82069 (12) | 0.44404 (13) | 0.52689 (6) | 0.0223 (3) | |
C10 | 0.76505 (14) | 0.3998 (2) | 0.47125 (7) | 0.0305 (3) | |
H10 | 0.6950 (16) | 0.441 (2) | 0.4600 (9) | 0.038 (5)* | |
C11 | 0.8134 (2) | 0.2995 (2) | 0.43202 (8) | 0.0409 (4) | |
H11 | 0.7756 (18) | 0.271 (2) | 0.3957 (10) | 0.057 (6)* | |
C12 | 0.9180 (2) | 0.2429 (2) | 0.44811 (8) | 0.0427 (4) | |
H12 | 0.9480 (18) | 0.177 (2) | 0.4217 (10) | 0.054 (6)* | |
C13 | 0.97398 (15) | 0.2862 (2) | 0.50329 (8) | 0.0360 (4) | |
H13 | 1.0457 (17) | 0.249 (2) | 0.5152 (10) | 0.048 (6)* | |
C14 | 0.92543 (13) | 0.38626 (15) | 0.54254 (7) | 0.0265 (3) | |
H14 | 0.9637 (16) | 0.4174 (18) | 0.5794 (9) | 0.033 (5)* | |
O | 0.70427 (12) | 0.38295 (11) | 0.64389 (6) | 0.0453 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0233 (2) | 0.0226 (2) | 0.0274 (2) | 0.00107 (13) | −0.00350 (13) | 0.00248 (13) |
C2 | 0.0225 (6) | 0.0153 (6) | 0.0258 (6) | 0.0005 (5) | 0.0057 (5) | 0.0013 (5) |
S3 | 0.0254 (2) | 0.0239 (2) | 0.0324 (2) | −0.00146 (13) | −0.00586 (14) | −0.00323 (14) |
C4 | 0.0389 (8) | 0.0263 (7) | 0.0228 (7) | 0.0025 (6) | −0.0038 (6) | 0.0023 (6) |
C5 | 0.0353 (8) | 0.0261 (7) | 0.0254 (7) | −0.0015 (6) | 0.0096 (6) | 0.0013 (6) |
C6 | 0.0254 (7) | 0.0235 (7) | 0.0319 (7) | −0.0061 (5) | 0.0023 (6) | 0.0006 (6) |
C7 | 0.0234 (6) | 0.0190 (6) | 0.0253 (6) | 0.0026 (5) | 0.0055 (5) | 0.0015 (5) |
C8 | 0.0343 (8) | 0.0195 (7) | 0.0267 (7) | 0.0018 (6) | 0.0093 (6) | 0.0021 (5) |
C9 | 0.0281 (7) | 0.0184 (6) | 0.0203 (6) | −0.0014 (5) | 0.0077 (5) | 0.0033 (5) |
C10 | 0.0368 (8) | 0.0296 (8) | 0.0250 (7) | −0.0032 (6) | −0.0005 (6) | 0.0053 (6) |
C11 | 0.0691 (12) | 0.0333 (9) | 0.0204 (7) | −0.0112 (8) | 0.0032 (8) | −0.0026 (6) |
C12 | 0.0704 (13) | 0.0252 (8) | 0.0324 (8) | 0.0029 (8) | 0.0278 (8) | −0.0005 (6) |
C13 | 0.0365 (9) | 0.0286 (8) | 0.0428 (9) | 0.0082 (6) | 0.0176 (7) | 0.0118 (7) |
C14 | 0.0278 (7) | 0.0265 (7) | 0.0252 (7) | −0.0021 (6) | 0.0039 (6) | 0.0044 (6) |
O | 0.0672 (8) | 0.0191 (5) | 0.0497 (7) | 0.0133 (5) | 0.0358 (6) | 0.0092 (5) |
S1—C2 | 1.8143 (14) | C7—C8 | 1.511 (2) |
S1—C6 | 1.8165 (15) | C8—C9 | 1.509 (2) |
C2—C7 | 1.528 (2) | C8—H81 | 0.97 (2) |
C2—S3 | 1.8113 (15) | C8—H82 | 0.97 (2) |
C2—H2 | 0.95 (2) | C9—C14 | 1.391 (2) |
S3—C4 | 1.824 (2) | C9—C10 | 1.393 (2) |
C4—C5 | 1.520 (2) | C10—C11 | 1.393 (2) |
C4—H41 | 0.97 (2) | C10—H10 | 0.95 (2) |
C4—H42 | 0.96 (2) | C11—C12 | 1.387 (3) |
C5—C6 | 1.518 (2) | C11—H11 | 0.92 (2) |
C5—H51 | 0.94 (2) | C12—C13 | 1.384 (3) |
C5—H52 | 0.97 (2) | C12—H12 | 0.92 (2) |
C6—H61 | 0.98 (2) | C13—C14 | 1.393 (2) |
C6—H62 | 0.98 (2) | C13—H13 | 0.95 (2) |
C7—O | 1.213 (2) | C14—H14 | 0.94 (2) |
C2—S1—C6 | 101.14 (7) | O—C7—C2 | 122.49 (12) |
C7—C2—S3 | 113.13 (9) | C8—C7—C2 | 114.26 (11) |
C7—C2—S1 | 109.88 (9) | C9—C8—C7 | 115.22 (12) |
S3—C2—S1 | 115.12 (7) | C9—C8—H81 | 113.3 (12) |
C7—C2—H2 | 108.6 (10) | C7—C8—H81 | 104.7 (13) |
S3—C2—H2 | 104.3 (10) | C9—C8—H82 | 111.3 (12) |
S1—C2—H2 | 105.1 (10) | C7—C8—H82 | 107.6 (12) |
C2—S3—C4 | 102.13 (7) | H81—C8—H82 | 103.8 (17) |
C5—C4—S3 | 113.58 (11) | C14—C9—C10 | 118.72 (14) |
C5—C4—H41 | 111.3 (11) | C14—C9—C8 | 120.70 (13) |
S3—C4—H41 | 108.9 (11) | C10—C9—C8 | 120.57 (13) |
C5—C4—H42 | 111.3 (12) | C9—C10—C11 | 120.6 (2) |
S3—C4—H42 | 102.8 (12) | C9—C10—H10 | 118.6 (12) |
H41—C4—H42 | 108.6 (15) | C11—C10—H10 | 120.7 (12) |
C6—C5—C4 | 112.87 (12) | C12—C11—C10 | 120.1 (2) |
C6—C5—H51 | 109.3 (11) | C12—C11—H11 | 120.1 (14) |
C4—C5—H51 | 110.0 (11) | C10—C11—H11 | 119.8 (14) |
C6—C5—H52 | 108.8 (12) | C13—C12—C11 | 119.8 (2) |
C4—C5—H52 | 106.4 (12) | C13—C12—H12 | 121.7 (14) |
H51—C5—H52 | 109.3 (15) | C11—C12—H12 | 118.6 (14) |
C5—C6—S1 | 113.85 (10) | C12—C13—C14 | 120.1 (2) |
C5—C6—H61 | 111.9 (10) | C12—C13—H13 | 121.3 (12) |
S1—C6—H61 | 108.6 (10) | C14—C13—H13 | 118.6 (13) |
C5—C6—H62 | 112.3 (11) | C9—C14—C13 | 120.71 (15) |
S1—C6—H62 | 102.2 (11) | C9—C14—H14 | 118.8 (11) |
H61—C6—H62 | 107.4 (15) | C13—C14—H14 | 120.5 (11) |
O—C7—C8 | 123.25 (13) | ||
S1—C2—C7—C8 | 109.0 (1) | C2—S3—C4—C5 | −55.8 (1) |
C2—C7—C8—C9 | −173.6 (1) | S3—C2—S1—C6 | −53.4 (1) |
C7—C8—C9—C10 | 98.3 (2) | S1—C2—S3—C4 | 52.8 (1) |
S1—C2—C7—O | −71.5 (1) | S1—C6—C5—C4 | −68.8 (1) |
S3—C2—C7—O | 58.7 (1) | S3—C4—C5—C6 | 67.1 (1) |
C2—S1—C6—C5 | 58.0 (1) |
Experimental details
Crystal data | |
Chemical formula | C12H14OS2 |
Mr | 238.35 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 150 |
a, b, c (Å) | 11.735 (1), 9.775 (1), 20.695 (2) |
V (Å3) | 2373.9 (4) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.42 |
Crystal size (mm) | 0.40 × 0.33 × 0.22 |
Data collection | |
Diffractometer | SMART 1K CCD area-detector diffractometer |
Absorption correction | Integration XPREP/SHELXTL (Bruker, 1997); R(int)=0.029 before correction |
Tmin, Tmax | 0.878, 0.927 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10906, 2846, 2533 |
Rint | 0.025 |
(sin θ/λ)max (Å−1) | 0.661 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.080, 1.09 |
No. of reflections | 2804 |
No. of parameters | 192 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.27, −0.26 |
Computer programs: SMART (Siemens, 1996), SMART, SAINT (Siemens, 1996), SHELXTL (Bruker, 1997), SHELXTL.
S1—C2 | 1.8143 (14) | C4—C5 | 1.520 (2) |
S1—C6 | 1.8165 (15) | C5—C6 | 1.518 (2) |
C2—C7 | 1.528 (2) | C7—O | 1.213 (2) |
C2—S3 | 1.8113 (15) | C7—C8 | 1.511 (2) |
S3—C4 | 1.824 (2) | C8—C9 | 1.509 (2) |
C2—S1—C6 | 101.14 (7) | S3—C2—S1 | 115.12 (7) |
C7—C2—S3 | 113.13 (9) | C2—S3—C4 | 102.13 (7) |
C7—C2—S1 | 109.88 (9) |
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 C═C 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)°].