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cis-Influence and trans-Influence on Bond Distances. Synthesis and Crystal Structures of the Bis(trifluoromethanesulfonates) of Tetrakis(dimethylsulfide)- and Tetrakis(1,4-thioxane)-platinum(II)

Bugarcic, Zivadin; Noren, Bertil; Oskarsson, Åke; Stålhandske, Claes-Ivar LU and Elding, Lars Ivar LU (1991) In Acta Chemica Scandinavica 45(4). p.361-366
Abstract (Swedish)
Crystals of [Pt{(CH3)2S}4](CF3SO3)2, M(r) = 741.76, and [Pt(C4H8OS)4](CF3SO3)2.H2O, M(r) = 927.93, were prepared by dissolution of platinum(II) hydroxide in solutions of trifluoromethanesulfonic acid in dimethyl sulfide and 1,4-thioxane, respectively. The structures were determined from X-ray intensity data (Mo K-alpha, lambda = 0.7107 angstrom) collected at room temperature with a CAD-4 diffractometer. The space group for the dimethylsulfide compound is P2(1)/c with a = 8.5630(8), b = 8.692(1), c = 16.360(3) angstrom, beta = 97.064(9)-degrees, V = 1208.4(2) angstrom 3, Z = 2, D(x) = 2.038 Mg m-3, F(000) = 720 and mu = 6.43 mm-1. The refinements converged to R = 0.025 for 1922 reflections with I > 3 sigma(I). The 1,4-thioxane compound... (More)
Crystals of [Pt{(CH3)2S}4](CF3SO3)2, M(r) = 741.76, and [Pt(C4H8OS)4](CF3SO3)2.H2O, M(r) = 927.93, were prepared by dissolution of platinum(II) hydroxide in solutions of trifluoromethanesulfonic acid in dimethyl sulfide and 1,4-thioxane, respectively. The structures were determined from X-ray intensity data (Mo K-alpha, lambda = 0.7107 angstrom) collected at room temperature with a CAD-4 diffractometer. The space group for the dimethylsulfide compound is P2(1)/c with a = 8.5630(8), b = 8.692(1), c = 16.360(3) angstrom, beta = 97.064(9)-degrees, V = 1208.4(2) angstrom 3, Z = 2, D(x) = 2.038 Mg m-3, F(000) = 720 and mu = 6.43 mm-1. The refinements converged to R = 0.025 for 1922 reflections with I > 3 sigma(I). The 1,4-thioxane compound crystallizes in the space group C2/c with a = 14.438(2), b = 13.016(2), c = 21.696(3) angstrom, beta = 126.32(1)degrees, V = 3285.0(6) angstrom 3, Z = 4, D(x) = 1.876 Mg m-3, F(000) = 1832 and mu = 4.76 mm-1. The refinements converged to R = 0.035 for 2268 reflections with I > 3-sigma(I). The coordination around platinum is square-planar with four sulfur donor ligands in both cases. In the dimethyl sulfide complex the two unique (CH3)2S groups are disordered. The sulfur atoms occupy two different positions with coinciding methyl carbon atoms. The platinum-sulfur distances are between 2.317(3) and 2.321(4) angstrom in the dimethylsulfide and between 2.318(2) and 2.321(2) angstrom in the thioxane complex. Packing forces thus have a negligible influence on these Pt-S distances, and the mean Pt-S distance of 2.319(2) angstrom is a suitable reference distance for calculation of the cis- and trans-influence by other donor atoms on the Pt-S bond in other complexes. (Less)
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organization
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type
Contribution to journal
publication status
published
subject
keywords
cis-influence , trans-influence, Platinum(II), Bond distance, Crystal structure, Synthesis, Dimethyl sulfide, 1,4-thiioxane, trifluoromethanesulfonate
in
Acta Chemica Scandinavica
volume
45
issue
4
pages
361 - 366
publisher
Munksgaard International Publishers
ISSN
0904-213X
DOI
10.3891/acta.chem.scand.45-0361
language
Swedish
LU publication?
yes
id
9a2fdd9b-ec9c-4c8e-9cdb-1da8336c3a63
date added to LUP
2017-01-08 18:48:11
date last changed
2017-05-29 11:37:39
@article{9a2fdd9b-ec9c-4c8e-9cdb-1da8336c3a63,
  abstract     = {Crystals of [Pt{(CH3)2S}4](CF3SO3)2, M(r) = 741.76, and [Pt(C4H8OS)4](CF3SO3)2.H2O, M(r) = 927.93, were prepared by dissolution of platinum(II) hydroxide in solutions of trifluoromethanesulfonic acid in dimethyl sulfide and 1,4-thioxane, respectively. The structures were determined from X-ray intensity data (Mo K-alpha, lambda = 0.7107 angstrom) collected at room temperature with a CAD-4 diffractometer. The space group for the dimethylsulfide compound is P2(1)/c with a = 8.5630(8), b = 8.692(1), c = 16.360(3) angstrom, beta = 97.064(9)-degrees, V = 1208.4(2) angstrom 3, Z = 2, D(x) = 2.038 Mg m-3, F(000) = 720 and mu = 6.43 mm-1. The refinements converged to R = 0.025 for 1922 reflections with I > 3 sigma(I). The 1,4-thioxane compound crystallizes in the space group C2/c with a = 14.438(2), b = 13.016(2), c = 21.696(3) angstrom, beta = 126.32(1)degrees, V = 3285.0(6) angstrom 3, Z = 4, D(x) = 1.876 Mg m-3, F(000) = 1832 and mu = 4.76 mm-1. The refinements converged to R = 0.035 for 2268 reflections with I > 3-sigma(I). The coordination around platinum is square-planar with four sulfur donor ligands in both cases. In the dimethyl sulfide complex the two unique (CH3)2S groups are disordered. The sulfur atoms occupy two different positions with coinciding methyl carbon atoms. The platinum-sulfur distances are between 2.317(3) and 2.321(4) angstrom in the dimethylsulfide and between 2.318(2) and 2.321(2) angstrom in the thioxane complex. Packing forces thus have a negligible influence on these Pt-S distances, and the mean Pt-S distance of 2.319(2) angstrom is a suitable reference distance for calculation of the cis- and trans-influence by other donor atoms on the Pt-S bond in other complexes.},
  author       = {Bugarcic, Zivadin and Noren, Bertil and Oskarsson, Åke and Stålhandske, Claes-Ivar and Elding, Lars Ivar},
  issn         = {0904-213X},
  keyword      = {cis-influence ,trans-influence,Platinum(II),Bond distance,Crystal structure,Synthesis,Dimethyl sulfide,1,4-thiioxane,trifluoromethanesulfonate},
  language     = {swe},
  number       = {4},
  pages        = {361--366},
  publisher    = {Munksgaard International Publishers},
  series       = {Acta Chemica Scandinavica},
  title        = {cis-Influence and trans-Influence on Bond Distances. Synthesis and Crystal Structures of the Bis(trifluoromethanesulfonates) of Tetrakis(dimethylsulfide)- and Tetrakis(1,4-thioxane)-platinum(II)},
  url          = {http://dx.doi.org/10.3891/acta.chem.scand.45-0361},
  volume       = {45},
  year         = {1991},
}