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access5,6-Dihydro-2H-1,3-dithiolo[4,5-b][1,4]dioxine-2-thione
aDepartment of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan, People's Republic of China, and bDepartment of Chemical Engineering, Ningbo University of Technology, Cuibai Road 89, Ningbo, People's Republic of China
*Correspondence e-mail: xunwenxiao@gmail.com
The title molecule, C5H4O2S3, consists of a planar [mean deviation = 0.020 (1) Å] 1,3-dithiole-2-thione unit with an ethylenedioxy group in the 4,5-positions. The dioxine ring is in a twist-chair conformation.
Related literature
For related structures, see: Kanchanadevi et al. (2010![[Kanchanadevi, J., Dhayalan, V., Mohanakrishnan, A. K., Anbalagan, G., Chakkaravarthi, G. & Manivannan, V. (2010). Acta Cryst. E66, o3264-o3265.]](../../../../../../logos/arrows/e_arr.gif "Kanchanadevi, J., Dhayalan, V., Mohanakrishnan, A. K., Anbalagan, G., Chakkaravarthi, G. & Manivannan, V. (2010). Acta Cryst. E66, o3264-o3265.")
); Rizvi et al. (2010); Suzuki et al. (1989); Xu et al. (2009); Sugumar et al. (2008). For the synthesis of the title compound, see: Hartke & Lindenblatt (1990); Suzuki et al. (1989).
![[Scheme 1]](aa2007scheme1.gif)
Experimental
Crystal data
|
Data collection: CrystalClear (Rigaku, 2005); cell CrystalClear; data reduction: CrystalStructure (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
Supporting information
contains datablocks I, global. DOI: 10.1107/S1600536811017417/aa2007sup1.cif
Structure factors: contains datablock I. DOI: 10.1107/S1600536811017417/aa2007Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536811017417/aa2007Isup3.cml
The C5H4S3O2 was prepared according to the literature (Suzuki et al., 1989).Yellow crystals were obtained from slow evaporation of a dichloromethane solution at room temperature.
The H atoms were included at geometrically idealized positions and refined in riding-model approximation with the following constraints: C—H distances were set to 0.98 Å for methylene H-atoms, with Uiso(H) = 1.2(C) Ueq of the carrier atoms.
Data collection: CrystalClear (Rigaku, 2005); cell CrystalClear (Rigaku, 2005); data reduction: CrystalStructure (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./aa2007fig1thm.gif) | Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level. |
![[Figure 2]](./aa2007fig2thm.gif) | Fig. 2. The crystal packing diagram view along the crystallographic b axis. |
| C5H4O2S3 | F(000) = 392 |
| Mr = 192.26 | Dx = 1.773 Mg m−3 |
| Monoclinic, P21/n | Mo Kα radiation, λ = 0.71075 Å |
| Hall symbol: -P 2yn | Cell parameters from 3311 reflections |
| a = 5.4645 (8) Å | θ = 3.0–27.5° |
| b = 13.430 (2) Å | µ = 0.96 mm−1 |
| c = 9.8189 (16) Å | T = 223 K |
| β = 91.294 (3)° | Block, yellow |
| V = 720.41 (19) Å3 | 0.55 × 0.20 × 0.20 mm |
| Z = 4 |
| Rigaku Saturn diffractometer | 1332 independent reflections |
| Radiation source: fine-focus sealed tube | 1199 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.021 |
| Detector resolution: 14.63 pixels mm-1 | θmax = 25.5°, θmin = 3.0° |
| ω scans | h = −6→6 |
| Absorption correction: multi-scan (REQAB; Jacobson, 1998) | k = −14→16 |
| Tmin = 0.605, Tmax = 0.826 | l = −11→9 |
| 3605 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)] = 0.031 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.083 | H-atom parameters constrained |
| S = 1.17 | w = 1/[σ2(Fo2) + (0.0486P)2 + 0.013P] where P = (Fo2 + 2Fc2)/3 |
| 1332 reflections | (Δ/σ)max < 0.001 |
| 92 parameters | Δρmax = 0.39 e Å−3 |
| 0 restraints | Δρmin = −0.41 e Å−3 |
| C5H4O2S3 | V = 720.41 (19) Å3 |
| Mr = 192.26 | Z = 4 |
| Monoclinic, P21/n | Mo Kα radiation |
| a = 5.4645 (8) Å | µ = 0.96 mm−1 |
| b = 13.430 (2) Å | T = 223 K |
| c = 9.8189 (16) Å | 0.55 × 0.20 × 0.20 mm |
| β = 91.294 (3)° |
| Rigaku Saturn diffractometer | 1332 independent reflections |
| Absorption correction: multi-scan (REQAB; Jacobson, 1998) | 1199 reflections with I > 2σ(I) |
| Tmin = 0.605, Tmax = 0.826 | Rint = 0.021 |
| 3605 measured reflections |
| R[F2 > 2σ(F2)] = 0.031 | 0 restraints |
| wR(F2) = 0.083 | H-atom parameters constrained |
| S = 1.17 | Δρmax = 0.39 e Å−3 |
| 1332 reflections | Δρmin = −0.41 e Å−3 |
| 92 parameters |
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 | ||
| S1 | 1.15131 (11) | 0.20574 (4) | 1.05803 (6) | 0.0394 (2) | |
| S2 | 0.77835 (10) | 0.36220 (4) | 0.99990 (5) | 0.03292 (19) | |
| S3 | 1.18427 (10) | 0.33798 (4) | 0.81841 (6) | 0.03387 (19) | |
| O1 | 0.6189 (3) | 0.51707 (11) | 0.85167 (16) | 0.0381 (4) | |
| O2 | 1.0238 (3) | 0.49167 (11) | 0.66988 (16) | 0.0367 (4) | |
| C1 | 1.0418 (4) | 0.29782 (14) | 0.9629 (2) | 0.0282 (5) | |
| C2 | 0.7954 (4) | 0.44643 (15) | 0.8651 (2) | 0.0276 (4) | |
| C3 | 0.9812 (4) | 0.43492 (14) | 0.7810 (2) | 0.0280 (5) | |
| C4 | 0.6183 (4) | 0.55689 (18) | 0.7147 (2) | 0.0412 (6) | |
| H4A | 0.5199 | 0.6179 | 0.7115 | 0.049* | |
| H4B | 0.5419 | 0.5086 | 0.6523 | 0.049* | |
| C5 | 0.8699 (5) | 0.57960 (16) | 0.6687 (2) | 0.0413 (6) | |
| H5A | 0.8607 | 0.6069 | 0.5761 | 0.050* | |
| H5B | 0.9437 | 0.6303 | 0.7286 | 0.050* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| S1 | 0.0427 (4) | 0.0365 (3) | 0.0392 (4) | 0.0112 (2) | 0.0020 (3) | 0.0078 (2) |
| S2 | 0.0318 (3) | 0.0340 (3) | 0.0333 (3) | 0.0071 (2) | 0.0086 (2) | 0.0068 (2) |
| S3 | 0.0289 (3) | 0.0393 (3) | 0.0337 (3) | 0.0073 (2) | 0.0071 (2) | 0.0031 (2) |
| O1 | 0.0372 (8) | 0.0368 (8) | 0.0406 (9) | 0.0126 (7) | 0.0095 (7) | 0.0107 (7) |
| O2 | 0.0364 (8) | 0.0400 (9) | 0.0340 (9) | 0.0041 (7) | 0.0079 (7) | 0.0105 (6) |
| C1 | 0.0288 (11) | 0.0264 (11) | 0.0295 (11) | 0.0008 (8) | 0.0001 (9) | −0.0033 (8) |
| C2 | 0.0276 (10) | 0.0260 (10) | 0.0293 (11) | 0.0013 (8) | 0.0010 (8) | 0.0018 (8) |
| C3 | 0.0256 (10) | 0.0289 (10) | 0.0296 (11) | −0.0021 (8) | −0.0003 (9) | 0.0015 (8) |
| C4 | 0.0417 (13) | 0.0424 (12) | 0.0394 (13) | 0.0116 (11) | 0.0019 (10) | 0.0134 (10) |
| C5 | 0.0499 (14) | 0.0354 (12) | 0.0387 (13) | 0.0029 (10) | 0.0026 (11) | 0.0091 (10) |
| S1—C1 | 1.654 (2) | O2—C5 | 1.450 (3) |
| S2—C1 | 1.725 (2) | C2—C3 | 1.332 (3) |
| S2—C2 | 1.746 (2) | C4—C5 | 1.488 (3) |
| S3—C1 | 1.720 (2) | C4—H4A | 0.9800 |
| S3—C3 | 1.744 (2) | C4—H4B | 0.9800 |
| O1—C2 | 1.357 (2) | C5—H5A | 0.9800 |
| O1—C4 | 1.447 (3) | C5—H5B | 0.9800 |
| O2—C3 | 1.356 (2) | ||
| C1—S2—C2 | 96.07 (10) | O1—C4—C5 | 112.07 (18) |
| C1—S3—C3 | 96.32 (9) | O1—C4—H4A | 109.2 |
| C2—O1—C4 | 109.56 (15) | C5—C4—H4A | 109.2 |
| C3—O2—C5 | 110.75 (15) | O1—C4—H4B | 109.2 |
| S1—C1—S3 | 122.39 (12) | C5—C4—H4B | 109.2 |
| S1—C1—S2 | 123.28 (13) | H4A—C4—H4B | 107.9 |
| S3—C1—S2 | 114.33 (12) | O2—C5—C4 | 111.73 (18) |
| C3—C2—O1 | 124.84 (18) | O2—C5—H5A | 109.3 |
| C3—C2—S2 | 116.70 (16) | C4—C5—H5A | 109.3 |
| O1—C2—S2 | 118.45 (14) | O2—C5—H5B | 109.3 |
| C2—C3—O2 | 125.52 (18) | C4—C5—H5B | 109.3 |
| C2—C3—S3 | 116.52 (16) | H5A—C5—H5B | 107.9 |
| O2—C3—S3 | 117.97 (14) | ||
| C3—S3—C1—S1 | −177.35 (13) | O1—C2—C3—S3 | −179.51 (15) |
| C3—S3—C1—S2 | 2.19 (13) | S2—C2—C3—S3 | −0.7 (2) |
| C2—S2—C1—S1 | 177.05 (14) | C5—O2—C3—C2 | 11.6 (3) |
| C2—S2—C1—S3 | −2.48 (13) | C5—O2—C3—S3 | −168.64 (15) |
| C4—O1—C2—C3 | 17.2 (3) | C1—S3—C3—C2 | −0.90 (19) |
| C4—O1—C2—S2 | −161.53 (15) | C1—S3—C3—O2 | 179.31 (15) |
| C1—S2—C2—C3 | 1.93 (18) | C2—O1—C4—C5 | −45.5 (3) |
| C1—S2—C2—O1 | −179.19 (16) | C3—O2—C5—C4 | −39.8 (2) |
| O1—C2—C3—O2 | 0.3 (3) | O1—C4—C5—O2 | 59.5 (3) |
| S2—C2—C3—O2 | 179.05 (15) |
Experimental details
| Crystal data | |
| Chemical formula | C5H4O2S3 |
| Mr | 192.26 |
| Crystal system, space group | Monoclinic, P21/n |
| Temperature (K) | 223 |
| a, b, c (Å) | 5.4645 (8), 13.430 (2), 9.8189 (16) |
| β (°) | 91.294 (3) |
| V (Å3) | 720.41 (19) |
| Z | 4 |
| Radiation type | Mo Kα |
| µ (mm−1) | 0.96 |
| Crystal size (mm) | 0.55 × 0.20 × 0.20 |
| Data collection | |
| Diffractometer | Rigaku Saturn diffractometer |
| Absorption correction | Multi-scan (REQAB; Jacobson, 1998) |
| Tmin, Tmax | 0.605, 0.826 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 3605, 1332, 1199 |
| Rint | 0.021 |
| (sin θ/λ)max (Å−1) | 0.605 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.031, 0.083, 1.17 |
| No. of reflections | 1332 |
| No. of parameters | 92 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.39, −0.41 |
Computer programs: CrystalClear (Rigaku, 2005), CrystalStructure (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), SHELXTL (Sheldrick, 2008).
Acknowledgements
This work was supported by the NNS (20902051), the Education Committee of Zhejiang Province (Z200906833), Ningbo Natural Science (2010 A610186) and the Ministry of Education Scientific Research Foundation for Returned Overseas Scholars.
References
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The title compound is a precursor to ethylenedioxotetrathiafulvalene(EDO-TTF). EDO-TTF has attracted much interest due to ultrafast gigantic photo-response in organic salts (EDO-TTF)2PF6.
In the title compound (Fig.1), the five-membered ring and attached S and O atoms are essentially coplanar, mean deviation from the mean plane 0.020 (1) Å. The C—S bond lengths range from 1.728 to 1.748 Å, it is smaller than that typical of C—S bond lengths, 1.82 Å, suggesting a degree of conjugation in the dithiole-2-thione system. The dioxine ring is in a twist-chair conformation.