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accessMethylene bis(dithiobenzoate)
aDepartment of Chemical Engineering, Tatung University, Taipei 104, Taiwan, bDepartment of Chemistry, Chung-Yuan Christian University, Chung-Li 320, Taiwan, and cDepartment of Chemistry, National Normal Taiwan University, Taipei 106, Taiwan
*Correspondence e-mail: yhlo@ttu.edu.tw
In the title compound, C15H12S4, two phenyldithiocarboxylate units are linked through a methylene C atom on a twofold rotation axis. The central S—CH2—S angle of 116.9 (5)° is significantly larger than the ideal tetrahedral value. The dihedral angle formed by the two phenyl rings is 68.2 (1)°. The refined of 0.2 (3) does not permit unambiguous determination of the absolute structure.
Related literature
For related structures, see: Shrivastav et al. (2002![[Shrivastav, A., Singh, N. K. & Srivastava, G. (2002). Bioorg. Med. Chem. 10, 2693-2704.]](../../../../../../logos/arrows/e_arr.gif "Shrivastav, A., Singh, N. K. & Srivastava, G. (2002). Bioorg. Med. Chem. 10, 2693-2704.")
); Gonzalez-Castro et al. (2000); Quintanilla et al. (2005).
![[Scheme 1]](bi2313scheme1.gif)
Experimental
Crystal data
|
Data collection: COLLECT (Nonius, 1999); cell DENZO and SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.
Supporting information
contains datablocks I, global. DOI: 10.1107/S1600536808037379/bi2313sup1.cif
Structure factors: contains datablock I. DOI: 10.1107/S1600536808037379/bi2313Isup2.hkl
The title compound was obtained unexpectedly during studies on the reactivity of {Ru(Tp)(PPh3)[S2CC6H5]} with CH3CN in dichloromethane. To a solution of {Ru(Tp)(PPh3)[S2CC6H5]} (2.00 g, 2.73 mmol) in CH2Cl2 (20 ml), an excess of CH3CN (2 ml) was added. The resulting yellow solution was heated to reflux for 3 h and the yellow precipitate obtained was filtered and washed with methanol and water to remove excess reagents. The compound was then dried under vacuum to give 0.83 g (91% yield). Crystals for X-ray structure analysis were obtained by recrystallization of the crude product from dichloromethane–hexane.
Elemental analysis calculated: C, 56.21; H, 3.77%; found: C, 56.19; H, 3.69%. 1H NMR (CDCl3,303 K, ppm): δ 7.98–7.35 (m, 10H, Ph), 5.31 (s, 2H, CH2). MS (m/z): 320.5 (M+).
H atoms were placed in idealized positions and constrained to ride on their parent atoms, with C—H = 0.95–0.96 Å and Uiso(H) = 1.2Ueq(C). The refined of 0.2 (3) does not permit unambiguous determination of the absolute structure.
Data collection: COLLECT (Nonius, 1999); cell DENZO and SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./bi2313fig1thm.gif) | Fig. 1. Molecular structure of the title compound showing displacement ellipsoids at the 50% probability level for non-H atoms. Non-labelled atoms are related to labelled atoms by the symmetry code 1-x, 2-y, z. |
| C15H12S4 | F(000) = 332 |
| Mr = 320.49 | Dx = 1.470 Mg m−3 |
| Orthorhombic, P21212 | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: P 2 2ab | Cell parameters from 5256 reflections |
| a = 11.5800 (3) Å | θ = 2.0–25.4° |
| b = 14.6440 (11) Å | µ = 0.64 mm−1 |
| c = 4.2710 (7) Å | T = 200 K |
| V = 724.27 (13) Å3 | Plate, yellow |
| Z = 2 | 0.11 × 0.08 × 0.02 mm |
| Nonius KappaCCD diffractometer | 1317 independent reflections |
| Radiation source: fine-focus sealed tube | 931 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.096 |
| ϕ scans | θmax = 25.5°, θmin = 2.2° |
| Absorption correction: multi-scan (SORTAV; Blessing, 1995) | h = −13→13 |
| Tmin = 0.933, Tmax = 0.987 | k = −17→17 |
| 5256 measured reflections | l = −5→4 |
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.056 | H-atom parameters constrained |
| wR(F2) = 0.157 | w = 1/[σ2(Fo2) + (0.0733P)2] where P = (Fo2 + 2Fc2)/3 |
| S = 1.13 | (Δ/σ)max < 0.001 |
| 1317 reflections | Δρmax = 0.37 e Å−3 |
| 87 parameters | Δρmin = −0.46 e Å−3 |
| 0 restraints | Absolute structure: Flack (1983), 505 Friedel pairs |
| Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.2 (3) |
| C15H12S4 | V = 724.27 (13) Å3 |
| Mr = 320.49 | Z = 2 |
| Orthorhombic, P21212 | Mo Kα radiation |
| a = 11.5800 (3) Å | µ = 0.64 mm−1 |
| b = 14.6440 (11) Å | T = 200 K |
| c = 4.2710 (7) Å | 0.11 × 0.08 × 0.02 mm |
| Nonius KappaCCD diffractometer | 1317 independent reflections |
| Absorption correction: multi-scan (SORTAV; Blessing, 1995) | 931 reflections with I > 2σ(I) |
| Tmin = 0.933, Tmax = 0.987 | Rint = 0.096 |
| 5256 measured reflections |
| R[F2 > 2σ(F2)] = 0.056 | H-atom parameters constrained |
| wR(F2) = 0.157 | Δρmax = 0.37 e Å−3 |
| S = 1.13 | Δρmin = −0.46 e Å−3 |
| 1317 reflections | Absolute structure: Flack (1983), 505 Friedel pairs |
| 87 parameters | Absolute structure parameter: 0.2 (3) |
| 0 restraints |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 | 0.47264 (14) | 0.89784 (9) | 0.5726 (3) | 0.0446 (5) | |
| S2 | 0.72612 (15) | 0.92562 (10) | 0.5091 (5) | 0.0613 (6) | |
| C1 | 0.5000 | 1.0000 | 0.792 (2) | 0.049 (2) | |
| H1A | 0.4346 | 1.0109 | 0.9253 | 0.058* | |
| C2 | 0.6098 (5) | 0.8635 (4) | 0.4525 (14) | 0.0437 (15) | |
| C3 | 0.6104 (5) | 0.7734 (4) | 0.2900 (15) | 0.0381 (14) | |
| C4 | 0.7071 (5) | 0.7447 (4) | 0.1238 (15) | 0.0480 (17) | |
| H4A | 0.7733 | 0.7828 | 0.1147 | 0.058* | |
| C5 | 0.7082 (6) | 0.6617 (4) | −0.0279 (16) | 0.0572 (18) | |
| H5A | 0.7749 | 0.6428 | −0.1397 | 0.069* | |
| C6 | 0.6127 (6) | 0.6064 (4) | −0.0173 (15) | 0.0562 (18) | |
| H6A | 0.6136 | 0.5491 | −0.1211 | 0.067* | |
| C7 | 0.5161 (6) | 0.6336 (4) | 0.1422 (16) | 0.0600 (19) | |
| H7A | 0.4503 | 0.5949 | 0.1492 | 0.072* | |
| C8 | 0.5140 (6) | 0.7159 (4) | 0.2913 (15) | 0.0499 (17) | |
| H8A | 0.4459 | 0.7345 | 0.3977 | 0.060* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| S1 | 0.0456 (9) | 0.0410 (8) | 0.0472 (9) | −0.0042 (7) | 0.0029 (7) | 0.0005 (7) |
| S2 | 0.0472 (10) | 0.0568 (9) | 0.0800 (14) | −0.0132 (7) | −0.0145 (9) | 0.0109 (10) |
| C1 | 0.063 (7) | 0.043 (5) | 0.039 (5) | −0.008 (4) | 0.000 | 0.000 |
| C2 | 0.042 (4) | 0.048 (3) | 0.041 (3) | −0.003 (2) | −0.012 (3) | 0.017 (3) |
| C3 | 0.035 (3) | 0.035 (3) | 0.044 (4) | 0.001 (3) | 0.000 (3) | 0.016 (3) |
| C4 | 0.038 (4) | 0.058 (4) | 0.048 (4) | 0.002 (3) | 0.002 (3) | 0.018 (3) |
| C5 | 0.055 (4) | 0.062 (4) | 0.054 (4) | 0.019 (3) | 0.016 (4) | 0.011 (4) |
| C6 | 0.068 (5) | 0.039 (3) | 0.062 (4) | 0.013 (3) | 0.012 (4) | −0.001 (4) |
| C7 | 0.057 (5) | 0.046 (3) | 0.077 (5) | −0.001 (3) | 0.017 (4) | −0.005 (3) |
| C8 | 0.044 (4) | 0.042 (3) | 0.064 (4) | 0.003 (3) | 0.008 (4) | 0.001 (3) |
| S1—C2 | 1.743 (6) | C4—H4A | 0.950 |
| S1—C1 | 1.794 (5) | C5—C6 | 1.370 (9) |
| S2—C2 | 1.643 (6) | C5—H5A | 0.950 |
| C1—S1i | 1.794 (5) | C6—C7 | 1.369 (8) |
| C1—H1A | 0.960 | C6—H6A | 0.950 |
| C2—C3 | 1.491 (8) | C7—C8 | 1.364 (8) |
| C3—C4 | 1.391 (8) | C7—H7A | 0.950 |
| C3—C8 | 1.399 (8) | C8—H8A | 0.950 |
| C4—C5 | 1.377 (9) | ||
| C2—S1—C1 | 103.5 (2) | C6—C5—C4 | 119.9 (6) |
| S1—C1—S1i | 116.9 (5) | C6—C5—H5A | 120.1 |
| S1—C1—H1A | 108.0 | C4—C5—H5A | 120.1 |
| S1i—C1—H1A | 108.0 | C7—C6—C5 | 120.3 (6) |
| C3—C2—S2 | 123.6 (4) | C7—C6—H6A | 119.9 |
| C3—C2—S1 | 113.4 (4) | C5—C6—H6A | 119.9 |
| S2—C2—S1 | 123.0 (4) | C8—C7—C6 | 120.2 (7) |
| C4—C3—C8 | 117.5 (6) | C8—C7—H7A | 119.9 |
| C4—C3—C2 | 120.6 (5) | C6—C7—H7A | 119.9 |
| C8—C3—C2 | 121.8 (5) | C7—C8—C3 | 121.1 (6) |
| C5—C4—C3 | 121.0 (6) | C7—C8—H8A | 119.5 |
| C5—C4—H4A | 119.5 | C3—C8—H8A | 119.5 |
| C3—C4—H4A | 119.5 | ||
| C2—S1—C1—S1i | 78.0 (2) | C2—C3—C4—C5 | −179.7 (5) |
| C1—S1—C2—C3 | 174.1 (4) | C3—C4—C5—C6 | 0.3 (9) |
| C1—S1—C2—S2 | −6.7 (5) | C4—C5—C6—C7 | 0.3 (10) |
| S2—C2—C3—C4 | −12.4 (8) | C5—C6—C7—C8 | 0.2 (10) |
| S1—C2—C3—C4 | 166.7 (5) | C6—C7—C8—C3 | −1.3 (10) |
| S2—C2—C3—C8 | 169.3 (5) | C4—C3—C8—C7 | 1.8 (9) |
| S1—C2—C3—C8 | −11.6 (7) | C2—C3—C8—C7 | −179.8 (6) |
| C8—C3—C4—C5 | −1.4 (9) |
| Symmetry code: (i) −x+1, −y+2, z. |
Experimental details
| Crystal data | |
| Chemical formula | C15H12S4 |
| Mr | 320.49 |
| Crystal system, space group | Orthorhombic, P21212 |
| Temperature (K) | 200 |
| a, b, c (Å) | 11.5800 (3), 14.6440 (11), 4.2710 (7) |
| V (Å3) | 724.27 (13) |
| Z | 2 |
| Radiation type | Mo Kα |
| µ (mm−1) | 0.64 |
| Crystal size (mm) | 0.11 × 0.08 × 0.02 |
| Data collection | |
| Diffractometer | Nonius KappaCCD diffractometer |
| Absorption correction | Multi-scan (SORTAV; Blessing, 1995) |
| Tmin, Tmax | 0.933, 0.987 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 5256, 1317, 931 |
| Rint | 0.096 |
| (sin θ/λ)max (Å−1) | 0.606 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.056, 0.157, 1.13 |
| No. of reflections | 1317 |
| No. of parameters | 87 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.37, −0.46 |
| Absolute structure | Flack (1983), 505 Friedel pairs |
| Absolute structure parameter | 0.2 (3) |
Computer programs: COLLECT (Nonius, 1999), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
Acknowledgements
This research was supported by the National Science Council, Taiwan (NSC 97–2113-M-036–001-MY2) and in part by the project of specific research fields in Tatung University, Taiwan (B96-C07-081), and the project of specific research fields in Chung Yuan Christian University, Taiwan (CYCU-97-CR-CH).
References
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| CRYSTALLOGRAPHIC COMMUNICATIONS |
During studies on the reactivity of the RuS2 complex {Ru(Tp)(PPh3)[S2CC6H5]}, (hydridotripyrazol-1-ylborato-κ3N2,N2',N2'')(phenyldithiocarboxylato-κ2S,S')(triphenylphosphine-κP)ruthenium, with CH3CN in dichloromethane, we unexpectedly obtained crystals of the title compound. It consists of two phenyldithiocarboxylate units bridged by a methylene group. The 1H NMR spectrum in CDCl3 shows one singlet at 5.31 ppm, assignable to SCH2S. The EI mass spectrum shows the molecular ion [C15H12S4]+ with the characteristic isotopic distribution patterns. In the crystal, the C2—S2 bond length of 1.643 (6) Å is slightly longer than expected for a C=S double bond (ca 1.61 Å), while the C2—S1 and C1—S1 distances of 1.743 (6) and 1.794 (5) Å, respectively, are clearly single bonds. The S—C—S angle of 116.9 (5)° is larger than the ideal tetrahedral value, probably due to repulsion between the CS2 groups.