Hydrothermal Syntheses and Crystal Structures of Two New Heteropolyoxovanadoborates Containing {(VO)₁₂O₆[B₃O₆(OH)]₆(H₂O)} Cluster

Two new heteropolyoxovanadoborates (H(2)dap)(2)H-6{(VO)(12)O-6[B3O6(OH)](6)(H2O)}center dot 13H(2)O (1, dap = 1,2-diaminopropane) and {[Zn(dien)](2)[Zn(dien)(H2O)](4)(VO)(12)O-6[B3O6(OH)](6)(H2O)}(2)center dot 15H(2)O (2, dien = diethylenetriamine) have been hydrothermally synthesized and structurally characterized. Both 1 and 2 contain {(VO)(12)O-6[B3O6(OH)](6)(H2O)} cluster (denoted on V12B18), which is constructed by a puckered B18O36(OH)(6) ring sandwiched between two triangles of six alternating cis and trans edge-sharing vanadium atoms, and a central water molecule. 1 consists of discrete [V12B18](10-) cluster anions with H(2)dap(2+) as counterions, while 2 consists of discrete neutral {[Zn(dien)](2)[Zn(dien)(H2O)](4)[V12B18]} clusters, which are built from two types of zinc(II) complex fragments connecting with V12B18 cluster through two Zn-(mu (3)-O)-B bonds. Interestingly, 2 is the only example of the V12B18 cluster decorated by two types of zinc(II) complex fragments.