Hydrothermal assembly of (3,6)-connected networks with classical mineral structures constructed from Anderson-type heteropolymolybdate and metal cations

A series of 3D heteropolymolybdates, (NH4)2{[M(H2O)3]2[TeMo6O24]}·H2O (M=Mn(1), Co(2), Ni(3), Cu(4), and Zn(5)) and [Ln(H2O)4]2[TeMo6O24]·3H2O (Ln=La(6), Ce(7), and Nd(8)), has been isolated from hydrothermal reactions and characterized by elemental analyses, IR spectra, X-ray crystallography and magnetic properties. Single-crystal X-ray diffraction analysis reveals that compounds 1–8 possess unusual (3,6)-connected networks constructed from Anderson-type anions [TeMo6O24]6− and transion metal or rare-earth metal cations. Compounds 1–5 are of highly symmetrical structures with pyrite-like topology in which [TeMo6O24]6− anions act as 6-connected sites and transition metal cations act as 3-connected sites. Compounds 6–8 crystallize in symmetrical space groups lower than that of 1–5 exhibiting rutile-like topology with [TeMo6O24]6− anions acting as 6-connected sites and rare-earth metal cations acting as 3-connected sites. The magnetic properties of 1–4 are also presented.