Several metal phosphate solids have been prepared from hydrothermal reaction methods that involve vanadium and either alkali metal ions or organic amine templating agents. A variety of magnetic behavior is observed, depending on the structures of the solids that are isolated. Binuclear [(VO)(2)Cl-2(H2O)(2)(PhAsO(3)H)(2)Ph(4)PCl], trinuclear [(C2H5NH3)(2)(VO)(3)H2O(C2H5PO3)(6)], hexanuclear [(C2H5)(4)N-2(VO)(6)(H2O)(2)(C2H5PO3)(6)], 16-atom cluster [V16O2O(OCH2CCH2O)(8)(H2O)(4)] and polymeric [AVOPO(4), A = Na, NH3] materials have been prepared. Some materials exhibit long range antiferromagnetic phase transitions that result from strong lattice interactions between magnetic centers. Ferromagnetic behavior is also observed in [H3N(CH2)(3)NH3(VO)(3)(OH)(2)(H2O)(2)(PO4)(2)] with a ferromagnetic phase transition at T-c = 5K. The magnetic data are interpreted in terms of the molecular and crystallographic data.