Electronic Structure of Cesium Butyratouranylate(VI) as Derived from DFT-assisted Powder X‑ray Diffraction Data

Investigation of chemical bonding
and electronic structure of coordination
polymers that do not form high-quality single crystals requires special
techniques. Here, we report the molecular and electronic structure
of the first cesium butyratouranylate, Cs­[UO2(n-C3H7COO)3]­[UO2(n-C3H7COO)­(OH)­(H2O)], as
obtained from DFT-assisted powder X-ray diffraction data because of
the low quality of crystalline sample. The topological analysis of
the charge distribution within the quantum theory of atoms-in-molecules
(QTAIM) space partitioning and the distribution of electron localization
function (ELF) is reported. The constancy of atomic domain of the
uranium­(VI) atom at different coordination numbers (7 and 8) and the
presence of three ELF maxima in equatorial plane of an uranyl cation
attributed to the 6s and 6p electrons were demonstrated for the first
time. Details of methodologies applied for additional verification
of the correctness of powder XRD refinement (Voronoi atomic descriptors
and the Morse restraints) are discussed.