Synthesis and Structure of 12-Member Ring Crown-Shaped Oxovanadium Borophosphate Polyanions:  [H3NC2H4NH2C2H4NH2C2H4NH3]4H[M(VO)12{O3POB(O)2OPO3}6]·nH2O (M = NH4 +, K+)

Using multiethylenemultiamine to direct the crystallization of inorganic frameworks through multipoint hydrogen bonds, two new oxovanadium borophosphates, denoted VBP-J1 and VBP-J2, have been synthesized by hydrothermal methods as well as under reflux conditions. Powder X-ray diffraction patterns indicate that VBP-J1 and VBP-J2 are structural analogues. Structure determinations show that both VBP-J1, [H3NC2H4NH2C2H4NH2C2H4NH3]4H[NH4(VO)12{O3POB(O)2OPO3}6]·14H2O and VBP-J2, [H3NC2H4NH2C2H4NH2C2H4NH3]4H[K(VO)12{O3POB(O)2OPO3}6]·16H2O crystallize in the orthorhombic space group Pbca with crystal data: a = 21.454(11) Å, b = 16.315(6) Å, c = 29.651(12) Å, α = β = γ = 90°, V = 10378(8) Å3, Z = 4 for VBP-J1 and a = 21.537(2) Å, b = 16.2667(13) Å, c = 29.717(4) Å, α = β = γ = 90°, V = 10410.8(18) Å3, Z = 4 for VBP-J2. VBP-J1 and VBP-J2 are constructed by edge-sharing {V2O10} binuclear unit and {BP2O10} trimer to form interesting 12-member ring crown-shaped clusters with NH4 + and K+ cations encapsulated in the clusters. The ring diameters are 5.873 × 5.412 × 5.561 Å for VBP-J1 and 5.758 × 5.421 × 5.236 Å for VBP-J2. An extended network of multiple hydrogen bonds among anions, cations, and water molecules links the structure in three dimensions.