The hydrothermal reactions of Zn(SO4)·5H2O, V2O5 and 2,4,6-tri(4-pyridyl)-1,3,5-triazine (tpytrz) yield [Zn(tpytrz)2V2O6] (1) at pH 6.5 and [Zn3(tpytrz)3(H2O)2V 6O18]·6H2O (2·6H2O) at pH 3.5. Substitution of Cu(II) as the secondary metal in the reaction of Cu(SO4)·5H2O, V2O5 and tpytrz yields [Cu3(tpytrz)2(H2O)2V 8O23]·3H2O (3·3H2O). The structure of 1 consists of a bimetallic oxide layer, decorated on both surfaces by monodentate tpytrz groups. The structure of 2 is three-dimensional and constructed from a 3-D bimetallic oxide framework with the organic subunit entrained within larger channels in the oxide scaffolding. While the structure of 3 is grossly similar to that of 2, the different coordination preferences of Zn(II) and Cu(II) are manifested in the detailed structural features. Thus, while the vanadate substructure of 2 is one-dimensional, that of 3 is two-dimensional. Similarly, 2 exhibits both tetrahedral and octahedral secondary metal sites, while 3 possesses only '4 + 2' axially distorted Cu(II) sites.
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