Structural studies in the ruthenium-dithiocarbamate system. Part II. Crystal structures of two salts of the [Ru2(dtc)5]+ cation, one containing the [Ru2Cl6]2- anion

Colin L. Raston, Allan H. White

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Abstract

The crystal structures of two derivatives of ruthenium di-isopropyldithiocarbamate (dtc) have been determined by X-ray diffraction: viz. (I) [Ru2(dtc)5]Cl,2.5C6H6 and (II) [Ru2(dtc)5]2[Ru2Cl 6],2CHCl3,(C6H12 ?). The structures were solved by the heavy-atom method and refined by least squares to R 0.084 [(I) 5 079 reflections] and 0.12 [(II) 4 714 reflections]. Crystals of both are monoclinic, space groups P21/a (I), P21n (II); for (I) a = 27.13(1), b = 17.25(2), c = 14.53(3) Å, β = 97.82(4)°, Z = 4; for (II) a = 33.83(1), b = 12.527(2), c = 15.825(2) Å, β = 95.72(2)°, Z = 2. Within the [Ru2(dtc)5]+ cation, a strong Ru ⋯ Ru interaction is found, the geometry of the bridging ligands being greatly compressed with a short Ru ⋯ Ru distance [2.789(4) Å]. The bridging dithiocarbamate groups are also unusual: the pπ orbital of one of the sulphur atoms is utilized for bonding so that there is an unusual disparity in the two C ⋯ S distances, the longer of which approximates to the single-bond value. (II) contains the novel [Ru2Cl6]2- centrosymmetric anion; the ruthenium atoms are pseudo-tetrahedral.

Original languageEnglish
Pages (from-to)2410-2418
Number of pages9
JournalJournal of the Chemical Society, Dalton Transactions
Issue number22
DOIs
Publication statusPublished - 1975
Externally publishedYes

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