Synthesis and crystal structures of two three-dimensional vanadium polyoxoanion-bridged macrocyclic metal complexes

The reactions of transition metal macrocyclic complexes [ML](ClO4)(2) (L = 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane, M = Ni, Cu) with NH4VO3 under hydrothermal conditions gave two coordination polymers, namely [NiL](2)[V6O17] and [CuL](2)[V6O17]. Single-crystal X-ray diffraction analyses indicated that the central Ni(II)/Cu(II) atom displays a distorted six-coordinate octahedral coordination geometry by coordination with four nitrogen atoms of L, and two oxygen atoms of [VO4] tetrahedrons. Compounds [NiL](2)[V6O17] and [CuL](2)[V6O17] show three-dimensional structures, which are constructed through the connections of dodecanuclear [V12O32](4-) rings with [NiL](2+) in [NiL](2)[V6O17], and [V8O22] (n) (4n-) chains with [CuL](2+) in [CuL](2)[V6O17], respectively, generating one-dimensional channels.