Hexaeyanochromates(HI) and Hexacyanocobaltates(III) of Copper(II) with Tridentate and Tetradentate N-donor Ligands. Crystal Structure of ({Cu(ept)}3{Co(CN)6}2)·H2O (ept = N-(2-aminoethyl)-1,3-propandiamine)

摘要

The following complexes [{Cu(ept)}3{Cr(CN)6}2]·5H2O, [{Cu(hatce)}3{Cr(CN)6}2]· 15H2O, [{Cu(hatco)}3{Cr(CN)6}2]·14H2O, [{Cu(ept)}3{Co(CN)6}2]·5H2O, [{Cu(hatce)}3{Co(CN)6}2]·18H2O and [{Cu(medpt)}3{Co(CN)6}2]·H2O (ept = N-(2-aminoethyl)-1,3-propandiamine, hatce = 1,3,6,10,12,15-hexaazatricyclo [13.3.1.1~(6,10)]eicosane, hatco = 1,3,6,9,11,14-hexaazatricyclo[12.2.1.1~(6,9)]octadecane and medpt = N,N-bis-(3-aminopropyl)methylamine) have been synthesized by the reactions of Cu(ClO4)2·6H2O or Cu(NO3)2·3H2O and ept or medpt, or [Cu(hatce)](ClO4)2·2H2O and [Cu(hatco)Cl]ClO4·H2O, and K3[Cr(CN)6] or K3[Co(CN)6] in aqueous solution, respectively. All the compounds have been characterized by elemental analyses, IR and UV-Vis spectroscopies and magnetic measurements and the three selected complexes were studied using thermal analysis. The crystal structure of [{Cu(ept)}3{Co(CN)6}2]· H2O has been determined by single-crystal X-ray analysis - the studied compound can be formulated as [{Cu(ept)}6{Co(CN)6}3][Co(CN)6]·2H2O. The copper atom is five-coordinated by two cyanide-nitrogen and three ept-nitrogen atoms, in a distorted square-pyramidal arrangement. The structure of the other complexes with cyanide bridges between hexacoordinated chromium(III) (S = 3/2) or cobalt(III) (S = 0) and penta- or hexacoordinated copper(II) (S = 1/2) is proposed.