Synthesis and X-ray Crystal Structure of Bis[oxamide dioximato-kappa N-2,N '](oxamide dioxime-kappa N-2,N ')cobalt(III) Perchlorate Hexahydrate

摘要

Co(OAC)(2) reacts with oxamide dioxime (H(2)oxado) in water in the presence of ClO4- ions to produce [Co(Hoxado)(2)(H(2)oxado)]ClO4 center dot 6H(2)O (1), where Hoxado(-) is the anion of H(2)oxado, derived from the deprotonation of one of the two hydroximinic groups, and in which oxidation of Co-II to Co-III (in air) had occurred. 1 is the first example of a salt in which the cation, [Co(H(2)oxado)(3)](3+) is doubly deprotonated to generate the chiral cation, [Co(Hoxado)(2)(H(2)oxado)](+). The central cobalt cation is pseudo-octahedrally coordinated by six nitrogen atoms. In the solid state, the complex cations form centro-symmetric dimers via O-H center dot center dot center dot O bridges. The bulk structure is consolidated by an extended three-dimensional network of O-H center dot center dot center dot O and N-H center dot center dot center dot O bridges that interconnect the ionic constituents and the water molecules.