Crystal structure of a novel bismuth phthalocyanine-bismuth iodide complex

Abstract

A new phthalocyaninato complex of bismuth with formula [(BiPc) 4(Bi 4I 16)] was obtained in the reaction of bismuth with 1,2-dicyanobenzene in iodine vapour. The crystal and molecular structure of the complex was determined by single crystal X-ray diffraction. The unit cell consists of four discrete (BiPc) + cations and (Bi 4I 16) 4− anions. The (Bi 4I 16) 4− complex anion is formed by four edge-sharing BiI 6 octahedra. The arrangement of molecules in the crystalline structure of the complex is mainly determined by ionic attraction between the (BiPc) + and (Bi 4I 16) 4− moieties, i.e. each (Bi 4I 16) 4− complex anion is encapsulated between four (BiPc) + cations. The structure is additionally stabilised by a set of distinct acceptor-donor intermolecular forces. The exceptionally short covalent BiN isoindole bonds are a pronounced feature of the (BiPc) + cations. To our knowledge the [(BiPc) 4(Bi 4I 16)] compound is the only example of a metallophthalocyaninato complex in which the metal atoms are not exclusively incorporated into macrocyclic Pc molecules, but occupy independent sites in the common crystalline lattice.