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Acta Crystallogr Sect E Struct Rep Online. 2008 December 1; 64(Pt 12): o2366.
Published online 2008 November 13. doi:  10.1107/S1600536808037379
PMCID: PMC2960133

Methyl­ene bis­(dithio­benzoate)

Abstract

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 Flack parameter of 0.2 (3) does not permit unambiguous determination of the absolute structure.

Related literature

For related structures, see: Shrivastav et al. (2002 [triangle]); Gonzalez-Castro et al. (2000 [triangle]); Quintanilla et al. (2005 [triangle]).

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Object name is e-64-o2366-scheme1.jpg

Experimental

Crystal data

  • C15H12S4
  • M r = 320.49
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-64-o2366-efi1.jpg
  • a = 11.5800 (3) Å
  • b = 14.6440 (11) Å
  • c = 4.2710 (7) Å
  • V = 724.27 (13) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.64 mm−1
  • T = 200 (2) K
  • 0.11 × 0.08 × 0.02 mm

Data collection

  • Nonius KappaCCD diffractometer
  • Absorption correction: multi-scan (SORTAV; Blessing, 1995 [triangle]) T min = 0.933, T max = 0.987
  • 5256 measured reflections
  • 1317 independent reflections
  • 931 reflections with I > 2σ(I)
  • R int = 0.096

Refinement

  • R[F 2 > 2σ(F 2)] = 0.056
  • wR(F 2) = 0.157
  • S = 1.13
  • 1317 reflections
  • 87 parameters
  • H-atom parameters constrained
  • Δρmax = 0.37 e Å−3
  • Δρmin = −0.46 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 505 Friedel pairs
  • Flack parameter: 0.2 (3)

Data collection: COLLECT (Nonius, 1999 [triangle]); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997 [triangle]); data reduction: DENZO (Otwinowski & Minor, 1997 [triangle]) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808037379/bi2313sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808037379/bi2313Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

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).

supplementary crystallographic information

Comment

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.

Experimental

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+).

Refinement

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 Flack parameter of 0.2 (3) does not permit unambiguous determination of the absolute structure.

Figures

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.

Crystal data

C15H12S4F000 = 332
Mr = 320.49Dx = 1.470 Mg m3
Orthorhombic, P21212Mo Kα radiation λ = 0.71073 Å
Hall symbol: P 2 2abCell parameters from 5256 reflections
a = 11.5800 (3) Åθ = 2.0–25.4º
b = 14.6440 (11) ŵ = 0.64 mm1
c = 4.2710 (7) ÅT = 200 (2) K
V = 724.27 (13) Å3Plate, yellow
Z = 20.11 × 0.08 × 0.02 mm

Data collection

Nonius KappaCCD diffractometer1317 independent reflections
Radiation source: fine-focus sealed tube931 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.096
T = 200(2) Kθmax = 25.5º
[var phi] scansθmin = 2.2º
Absorption correction: multi-scan(SORTAV; Blessing, 1995)h = −13→13
Tmin = 0.933, Tmax = 0.987k = −17→17
5256 measured reflectionsl = −5→4

Refinement

Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.056  w = 1/[σ2(Fo2) + (0.0733P)2] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.157(Δ/σ)max < 0.001
S = 1.13Δρmax = 0.37 e Å3
1317 reflectionsΔρmin = −0.46 e Å3
87 parametersExtinction correction: none
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983), 505 Friedel pairs
Secondary atom site location: difference Fourier mapFlack parameter: 0.2 (3)

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
S10.47264 (14)0.89784 (9)0.5726 (3)0.0446 (5)
S20.72612 (15)0.92562 (10)0.5091 (5)0.0613 (6)
C10.50001.00000.792 (2)0.049 (2)
H1A0.43461.01090.92530.058*
C20.6098 (5)0.8635 (4)0.4525 (14)0.0437 (15)
C30.6104 (5)0.7734 (4)0.2900 (15)0.0381 (14)
C40.7071 (5)0.7447 (4)0.1238 (15)0.0480 (17)
H4A0.77330.78280.11470.058*
C50.7082 (6)0.6617 (4)−0.0279 (16)0.0572 (18)
H5A0.77490.6428−0.13970.069*
C60.6127 (6)0.6064 (4)−0.0173 (15)0.0562 (18)
H6A0.61360.5491−0.12110.067*
C70.5161 (6)0.6336 (4)0.1422 (16)0.0600 (19)
H7A0.45030.59490.14920.072*
C80.5140 (6)0.7159 (4)0.2913 (15)0.0499 (17)
H8A0.44590.73450.39770.060*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0456 (9)0.0410 (8)0.0472 (9)−0.0042 (7)0.0029 (7)0.0005 (7)
S20.0472 (10)0.0568 (9)0.0800 (14)−0.0132 (7)−0.0145 (9)0.0109 (10)
C10.063 (7)0.043 (5)0.039 (5)−0.008 (4)0.0000.000
C20.042 (4)0.048 (3)0.041 (3)−0.003 (2)−0.012 (3)0.017 (3)
C30.035 (3)0.035 (3)0.044 (4)0.001 (3)0.000 (3)0.016 (3)
C40.038 (4)0.058 (4)0.048 (4)0.002 (3)0.002 (3)0.018 (3)
C50.055 (4)0.062 (4)0.054 (4)0.019 (3)0.016 (4)0.011 (4)
C60.068 (5)0.039 (3)0.062 (4)0.013 (3)0.012 (4)−0.001 (4)
C70.057 (5)0.046 (3)0.077 (5)−0.001 (3)0.017 (4)−0.005 (3)
C80.044 (4)0.042 (3)0.064 (4)0.003 (3)0.008 (4)0.001 (3)

Geometric parameters (Å, °)

S1—C21.743 (6)C4—H4A0.950
S1—C11.794 (5)C5—C61.370 (9)
S2—C21.643 (6)C5—H5A0.950
C1—S1i1.794 (5)C6—C71.369 (8)
C1—H1A0.960C6—H6A0.950
C2—C31.491 (8)C7—C81.364 (8)
C3—C41.391 (8)C7—H7A0.950
C3—C81.399 (8)C8—H8A0.950
C4—C51.377 (9)
C2—S1—C1103.5 (2)C6—C5—C4119.9 (6)
S1—C1—S1i116.9 (5)C6—C5—H5A120.1
S1—C1—H1A108.0C4—C5—H5A120.1
S1i—C1—H1A108.0C7—C6—C5120.3 (6)
C3—C2—S2123.6 (4)C7—C6—H6A119.9
C3—C2—S1113.4 (4)C5—C6—H6A119.9
S2—C2—S1123.0 (4)C8—C7—C6120.2 (7)
C4—C3—C8117.5 (6)C8—C7—H7A119.9
C4—C3—C2120.6 (5)C6—C7—H7A119.9
C8—C3—C2121.8 (5)C7—C8—C3121.1 (6)
C5—C4—C3121.0 (6)C7—C8—H8A119.5
C5—C4—H4A119.5C3—C8—H8A119.5
C3—C4—H4A119.5
C2—S1—C1—S1i78.0 (2)C2—C3—C4—C5−179.7 (5)
C1—S1—C2—C3174.1 (4)C3—C4—C5—C60.3 (9)
C1—S1—C2—S2−6.7 (5)C4—C5—C6—C70.3 (10)
S2—C2—C3—C4−12.4 (8)C5—C6—C7—C80.2 (10)
S1—C2—C3—C4166.7 (5)C6—C7—C8—C3−1.3 (10)
S2—C2—C3—C8169.3 (5)C4—C3—C8—C71.8 (9)
S1—C2—C3—C8−11.6 (7)C2—C3—C8—C7−179.8 (6)
C8—C3—C4—C5−1.4 (9)

Symmetry codes: (i) −x+1, −y+2, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BI2313).

References

  • Blessing, R. H. (1995). Acta Cryst. A51, 33–38. [PubMed]
  • Flack, H. D. (1983). Acta Cryst. A39, 876–881.
  • Gonzalez-Castro, A., Gutierrez-Perez, R., Penieres-Carrillo, G., Diaz-Torres, E., Toscano, R. A., Moya-Cabrera, M., Cabrera-Ortiz, C. & Alvarez-Toledano, C. (2000). Heteroatom. Chem.11, 120–128.
  • Nonius (1999). COLLECT Nonius BV, Delft, The Netherlands.
  • Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press.
  • Quintanilla, M. G., Guerra, E., Dotor, J., Maresova, J., Barba, F. & Martin, A. (2005). Phosphorus Sulfur Silicon Relat. Elem 180, 1691–1699.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Shrivastav, A., Singh, N. K. & Srivastava, G. (2002). Bioorg. Med. Chem.10, 2693–2704. [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography