Reactions in Anhydrous Liquid Ammonia : Syntheses and Crystal Structures of [M(NH3)8]I2 (M = Eu, Yb) with Bicapped Trigonal-Prismatic Octaammine Lanthanoid(II) Cations

The compounds [M(NH3)8]I2 (M = Eu, Yb) were obtained from reactions in anhydrous liquid ammonia solutions as side products. They were characterized by single-crystal X-ray diffraction and found to be isotypic to the compounds [Ca(NH3)8]X2 (X = Cl, Br, I). The coordination sphere of the lanthanoid(II) cations is not square-antiprismatic but much better described as bicapped trigonal-prismatic. In contrast, quantum-chemical gas-phase calculations show the square-antiprismatic coordination polyhedron (point group S8) to be energetically favored over the bicapped trigonal prism and the latter is not even a true local minimum. Obviously, hydrogen bonding and eventually other weak interactions have an impact on the observed bicapped trigonal-prismatic coordination sphere of the [M(NH3)8]2+ cations in the solid state.Peer reviewe