Two polyoxovanadate-based metal-organic polyhedra with undiscovered "near-miss Johnson solid" geometry.

Newfangled frangipani-like [MV5O6(μ3-O)5(SO4)(COO)5] (M = Nb/W) polyanions served as 5-connected molecular building blocks (MBBs) that simultaneously assembled with 4-connected [V5O9Cl] MBBs and tricarboxylate ligands (H3BTC) to form two new polyoxovanadate-based metal-organic polyhedra {[MV5O6(μ3-O)5(SO4)]4[V5O9Cl]4(BTC)12} with undiscovered "near-miss Johnson solid" geometry. Moreover, the variable-temperature magnetic susceptibilities were investigated.