A Novel Host/Guest System with a Nanometer Large Cavity for Anions and Cations: [2NH 4+, 2Cl− ⊂ V14O22(OH)4(H2O)2‐(C6H5PO3)8]6−

A polytopic host for several cations and anions or cation/anion aggregates was previously unknown. The anion of the title (structure depicted on the right) is a host/guest system in which the "host"-the shell-consists of electrophilic and nucleophilic components. The cation/anion aggregate (NH4)2Cl2, a section of the NH4Cl ion lattice, is incorporated as "guest".