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Single crystals of the Np(V) and Pu(V) benzoate complexes with 2,2′-bipyridine were prepared. According to X-ray diffraction analysis data, they are isostructural neutral dimers with the [AnO 2 (C 10 H 8 N 2 )(OOCC 6 H 5 )] 2  (An = Np or Pu) composition. In crystals of these compounds the AnO 2  +  are linked to each other in pairs, acting simultaneously as ligands and coordinating centers. Due to the cation-cationic interaction the dimeric An 2 O 4  2+  cations are formed with the very short An…An distance equal to 3.4281(5) and 3.4088(14)Å for Np and Pu, respectively. The [NpO 2 (C 10 H 8 N 2 )(OOCC 6 H 5 )] 2  complex is a new representative of compounds containing a very rare system of cation–cation bonds in the structure. The cation–cation bonds and the Pu 2 O 4  2+  dimeric cations in the [PuO 2 (C 10 H 8 N 2 )(OOCC 6 H 5 )] 2  structure have been found for the first time.

radiochimica acta

Cation–cation interaction in crystal structures of Np(V) and Pu(V) benzoate complexes with 2,2′-bipyridine, [NpO 2 (C 10 H 8 N 2 )(OOCC 6 H 5 )] 2  and [PuO 2 (C 10 H 8 N 2 )(OOCC 6 H 5 )] 2