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Four new stibocanes substituted with cyclic dithiophosphate ligands O(CH2CH2S)2SbS2P(OCH2)2CEt2 (1), O(CH2CH2S)2SbS2P(OCH2)2C(Me)Pr (2), S(CH2CH2S)2SbS2P(OCH2)2CEt2 (3) and S(CH2CH2S)2SbS2P(OCH2)2C(Me)Pr (4) were prepared from the corresponding chloro oxa- and thia-stibocanes and the sodium salt of the dithiophosphoric acids 5,5-diethyl-(2-mercapto-2-thiono-1,3,2-dioxaphosphinane) and 5-methyl-5-propyl-(2-mercapto-2-thiono-1,3,2-dioxaphosphinane) in ethanol. The compounds obtained were characterized by IR, EI-MS and multinuclear NMR (1H, 13C, 31P) spectroscopies. The single-crystal structures of 1 and 2 were determined which show the presence of three types of secondary bonding: i.e. strong Sb- - -O transannular interactions of 2.607(4) and 2.600(4) A, respectively, anisobidentate coordination of the ligand (exocyclic chelation) average Sb- - -S distance 3.355 A and intermolecular interactions that lead to supramolecular associations. The coordination geometry around antimony atom in both 1 and 2 can be described as Ψ tricapped trigonal bipyramidal AB4CD2E. The eight membered ring presents a boat-chair conformation in both compounds and the 1,3,2-dioxaphosphinane ring has the chair conformation, with the stibocane in the axial position. |
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