Synthesis and structures of two thiocyanato-lanthanoid cages

The cages [ La2(NCS)5(NCMe)6 2O] MeCN and [ Eu2(NCS)5(NCMe)5 2O] MeCN have been prepared by redox transmetallation between the lanthanoid metals and mercuric thiocyanate in acetonitrile. The structure of the former has a core of four La atoms bonded to a central oxygen atom. Two La atoms are nine coordinate being bonded to oxygen, four terminal MeCN ligands and four N-bridged thiocyanato ligands, whereas the other two are eight coordinate being bonded to oxygen, the four bridging thiocyanato ligands, two terminal acetonitrile molecules, and a terminal N-bonded thiocyanate ion. In the Eu complex, there is a similar core of four Ln atoms bound to a central oxygen atom, but all Eu atoms are eight coordinate, and have four N-bridged thiocyanate ligands. Two have three MeCN ligands, whilst the other two have one terminal NCS- and two acetonitrile ligands.