Synthesis and Structure of an Oxovanadium(V)—Organophosphonate Cluster Encapsulating a Chloride Ion: [ClV₇O₁₂(O₃PC₆H₅)₆]²⁻

A hollow sphere, constructed from VO₅ square pyramids and PhPO₃ tetrahedra, which encapsulates a chlorine atom—this is an apt description of the anion in 1 (structure shown on the right). At first glance this anion, with its spheroidal structure, appears similar to known polyoxoanions; however, closer inspection reveals the striking structural similarities to analogous binuclear building blocks and to the layered solid VO(O₃PR), H₂O, which extend beyond purely topological relationships to chemical behavior. (Figure Presented.)