Tungsten I 5700 Two New Transition-Metal Complexes (TMCs)-Templated Three-DimensionalSupramolecular Networks Based on Tungstovanadophosphates. -The new compounds (IV) and (V) are hydrothermally synthesized and characterized by single crystal XRD, IR, EPR, and XPS. (IV) crystallizes in the monoclinic space group C2/c with Z = 4 and (V) in the monoclinic space group P21/n with Z = 4. Their structures exhibit three-dimensional supramolecular networks and contain the new bicapped α-Keggin tungsten-vanadium cluster anion O 40 (V IV O) 2 ] 7-. (V) contains four different kinds of counterions, [Ni(phen)3] 2+ , [Ni(en)3] 2+ , [Ni(en)2(H2O)2] 2+ , and [Ni(en)2] 2+ . -(LU, Y.-K.; CUI, X.-B.; LIU, Y.-B.; YANG, Q.-F.; SHI, S.-Y.; XU*, J.-Q.; WANG, T.-G.; J. Solid State Chem. 182 (2009) 4, 690-697; State Key Lab. Inorg. Synth. Prep. Chem., Coll. Chem., Jilin Univ., Changchun 130023, Peop. Rep. China; Eng.) -W. Pewestorf 28-019 [PW V I 7 W V 2 V IV 3