Stereochemistry of Neptunium in Oxygen-Containing Compounds

详细

Coordination of Np(III–VII) atoms in the crystal structures of all the oxygen-containing compounds characterized with the R-factor lower than 0.1 was analyzed with the aid of Voronoi–Dirichlet polyhedra (VDPs). Nine types of NpO_n coordination polyhedra (6 ≤ n ≤ 12) are realized. The most characteristic of them are trigonal dodecahedra [Np(IV)], penta- and hexagonal bipyramids [Np(V) and Np(VI)], and octahedra [Np(VII)] based on square NpO₄^– cores. For Np atoms of a fixed oxidation state, the volume of their VDPs in the NpO_n complexes is virtually independent of the coordination number n. The VDP parameters can be used for determining the valence state of the Np atoms, finding compounds with the maximal nonlinearity of the NpO₂⁺ and NpO₂²⁺ dioxocations, and revealing errors in the crystal structure data. Anion–anion interactions involving NpO₄^– and OH^– ions are an important structure-forming factor in Np(VII) compounds. In sublattices consisting of Np atoms only (Np sublattices), the rule of 14 neighbors is fulfilled. Compounds in which binding Np···Np 5f interactions in crystal structures are possible were revealed by analysis of the VDPs of the atoms in the Np sublattices. In such compounds, the metal atoms form bent Np=O–Np bridging fragments and the Np^VO₇ bipyramids are combined in dimers sharing a common axial edge, with the Np atoms of the dimers being also bound via two carboxylate bridges.