Hydrothermal Syntheses and Crystal Structures of Two New Heteropolyoxovanadoborates Containing {(VO) 12 O 6 [B 3 O 6 (OH)] 6 (H 2 O)} Cluster

Two new heteropolyoxovanadoborates (H 2 dap) 2 H 6 {(VO) 12 O 6 [B 3 O 6 (OH)] 6 (H 2 O)}·13H 2 O ( 1 , dap = 1,2-diaminopropane) and {[Zn(dien)] 2 [Zn(dien)(H 2 O)] 4 (VO) 12 O 6 [B 3 O 6 (OH)] 6 (H 2 O)} 2 ·15H 2 O ( 2 , dien = diethylenetriamine) have been hydrothermally synthesized and structurally characterized. Both 1 and 2 contain {(VO) 12 O 6 [B 3 O 6 (OH)] 6 (H 2 O)} cluster (denoted on V 12 B 18 ), which is constructed by a puckered B 18 O 36 (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 [V 12 B 18 ] 10− cluster anions with H 2 dap 2+ as counterions, while 2 consists of discrete neutral {[Zn(dien)] 2 [Zn(dien)(H 2 O)] 4 [V 12 B 18 ]} clusters, which are built from two types of zinc(II) complex fragments connecting with V 12 B 18 cluster through two Zn-( μ 3 -O)-B bonds. Interestingly, 2 is the only example of the V 12 B 18 cluster decorated by two types of zinc(II) complex fragments.