Novel examples of hybrid organic–inorganic solids based on building blocks

New hybrid organic/inorganic copper oxovanadium compounds of composition [Cu(dpa)2]4V4O12 (1), Cu2(bipy)2V4O12 (2), and Cu2(bipy)2V6O17 (3), which crystallize in the monoclinic 1, 2 and triclinic 3 symmetry, respectively, were obtained by soft hydrothermal routes. The first two structures present isolated [V4O12]4− anionic units, the structure of 3 exhibits the same [V4O12]4− cycles coupled by V2O5 dimeric bridges propagated as an infinite chain along the c-direction 3. For compound 1, the copper(I) centers are bonded to four nitrogen atoms with a distorted tetrahedral geometry. For compounds 2 and 3, the copper(II) centers are square pyramidal with two nitrogen atoms from the neutral diimine ligand and three oxygen atoms from the oxovanadium sub-unit. In all the compounds described herein, the vanadium ions are as V(V), occupying solely tetrahedral sites.