Crystal structure of mixed-valent Np(IV)/Np(V) chloride, [Np(NpO2)6(H2O)8(OH)Cl9]·H2O

Abstract

A new mixed-valent Np(IV)/Np(V) chloride, [Np(NpO2)6(H2O)8(OH)Cl9]·H2O, was synthesized, and its crystal structure was determined. The crystals consist of NpO2+ and Np4+ cations, of Cl− and OH− anions, of coordination-bonded water molecules, and of water molecules of crystallization. The Np(V) atom, Np(1), has pentagonal bipyramidal coordination surrounding with O atoms in the apical position and with the equatorial plane formed by three Cl− anions, O atom of the adjacent NpO2+ cation, and O atom of water molecule. The mutual coordination of the neptunyl(V) ions, cation-cation (CC) interaction, links the Np(1) coordination polyhedra via common vertices into rings around sixfold axes, with the Np(V)⋯Np(V) distance in these fragments of 4.276 A. The ring fragments are linked with each other via common equatorial edges of the bipyramids into layers perpendicular to c-axis. The Np(IV) atom, Np(2), has coordination surrounding in the form of tricapped trigonal prism (CN 9) with the tetragonal lateral faces formed by the O atoms of the NpO2+ cations and the capping positions occupied by the O atoms of two water molecules and one hydroxy group. The Np(2) atoms act in CC interactions as coordination center for six NpO2+ ions, with the Np(IV)⋯Np(V) distance of 4.183 A. The Np(2) polyhedra are arranged in the crystal between layers of the Np(1) coordination polyhedra, linking them with each other.