Structural Role of Isonicotinic Acid in U(VI), Np(VI), and Pu(VI) Complexes with TcO4-, ReO4-, and ClO4- Ions

Inorg Chem. 2017 Oct 16;56(20):12199-12205. doi: 10.1021/acs.inorgchem.7b01611. Epub 2017 Sep 26.

Abstract

A series of new pertechnetate, perrhenate, and perchlorate compounds of hexavalent U, Np, and Pu containing isonicotinic acid were synthesized. Their crystal structures were determined by X-ray diffractometry. In all compounds, actinide atoms are found in pentagonal bipyramidal surroundings. They are coordinated by 2 to 4 isonicotinic acid molecules which exist in zwitterionic form as a result of N atom protonation. If only 2 or 3 isonicotinic acid molecules are present in the surroundings of an actinide (An) atom, TcO4- or ReO4- anions act as monodentate ligands. Otherwise, XO4- play the role of outer sphere anions. Electron and IR spectra of the compounds correlate with their crystal structure.