Cation–Cation Interaction in Np(V) Perchlorates and Their Electronic Absorption Spectra

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Four new Np(V) perchlorate complexes of the composition [NpO 2 (H 2 O) 4 ]ClO 4 (orthorhombic) ( 1 ), [(NpO 2 ) 2 (ClO 4 )(H 2 O) 4 ]ClO 4 ·H 2 O ( 3 ), [(NpO 2 )(UO 2 )(H 2 O) 8 ](ClO 4 ) 3 ( 4 ), and [(NpO 2 ) 2 Cl(H 2 O) 4 ]ClO 4 ·2H 2 O ( 5 ) have been synthesized and structurally characterized. The structure of previously known monoclinic modification of NpO 2 ClO 4 ·4H 2 O ( 2 ) has been determined at 100 K. The coordination environment of Np and U atoms in compounds 1 – 5 is pentagonal bipyramids. A cation–cation (CC) interaction was found in structures 1 – 5, in which the NpO 2 + ion manifests itself as a monodentate ( 1, 2 ) or bidentate ( 3 – 5 ) ligand. CC bonds play a fundamental role in the crystal structures of compounds 1, 2, and 4 . They are the main structure-forming bonds that form the crystal package as a whole. The spectra of all compounds in the visible-near-IR range were measured.