Crystal growth of novel 3D skeleton uranyl germanium complexes: influence of synthetic conditions on crystal structures

Abstract

Five centrosymmetric uranyl germanate compounds, K₈BrF(UO₂)₃(Ge₂O₇)₂, Rb₆(UO₂)₃(Ge₂O₇)₂·0.5H₂O, Cs₆(UO₂)₂Ge₈O₂₁ and A⁺₂(UO₂)₃(GeO₄)₂ (A⁺ = Rb⁺, Cs⁺), were synthesized in this work. K₈BrF(UO₂)₃(Ge₂O₇)₂ and Rb₆(UO₂)₃(Ge₂O₇)₂·0.5H₂O were obtained under mixed KF–KBr flux and hydrothermal conditions, respectively. Both structures crystallized in the triclinic P space group and have similar anionic frameworks featuring novel hexagon shaped 12-membered channels. The condensation of two different types of SBU [UGe₄] pentamers (A) and (A2) results in the formation of K₈BrF(UO₂)₃(Ge₂O₇)₂ and Rb₆(UO₂)₃(Ge₂O₇)₂·0.5H₂O frameworks. Cs₆(UO₂)₂Ge₈O₂₁ was obtained from a CsF–CsCl high temperature flux, and it also crystallized in the centrosymmetric triclinic P space group. The structure of Cs₆(UO₂)₂Ge₈O₂₁ has a novel oxo-germanate layer composed of germanate tetrahedra and trigonal bipyramids. Two new SBU types, (4²·5²-A2) and (5⁴-A2) [UGe₄] pentamers, were found in the structure of Cs₆(UO₂)₂Ge₈O₂₁. A⁺₂(UO₂)₃(GeO₄)₂ (A⁺ = Rb⁺, Cs⁺) were synthesized by a high temperature/high pressure (HT/HP) technique, and both structures with oval-shaped 12-membered channels crystallized in the centrosymmetric orthorhombic Pnma space group. The extreme conditions led to the formation of [U₂Ge₂] tetramers (E), which consist of 7-coordinated U and 5-coordinated Ge. Different synthetic methods of uranyl germanate compounds resulted in a distinct coordination environment of the uranyl cations and a variety of UO and U−O bond lengths, further affecting the dimensionality and types of uranyl units and SBUs. The Raman and IR spectra of the five new phases were collected and analyzed.