Synthesis and crystal‐structure analysis of the K2NiF4‐type hydride oxides LiLnEuH2-xO2 (Ln=La, Ce, Pr, Nd, Sm) and LiEu2H3O by neutron and X‐ray diffraction

Abstract

The hydride oxides LiLnEuH2-xO2 (Ln=La, Ce, Pr, Nd and Sm) were synthesized by reaction of the lanthanide sesquioxides with europium monoxide, europium dihydride and lithium hydride under inert conditions at 750 °C as black powders. They crystallize in the tetragonal K2NiF4‐type structure (space group: I4/mmm) with a mixed Ln3+/Eu2+ occupation. The crystal structures of the europium representatives LiLaEuH2-xO2 and LiLaEuD2-xO2 were analyzed by powder neutron diffraction data at short wavelengths (λ=70 pm). Hydrogen (deuterium) and oxygen atoms occupy distinct crystallographic sites with considerable vacancy concentrations on the hydrogen positions (a=363.80(8) pm, c=1323.3(3) pm, c/a=3.637 for LiLaEuH1.26(4)O2 and a=363.43(5) pm, c=1321.6(2) pm, c/a=3.636 for LiLaEuD1.41(2)O2). Moving from the mixed Ln/Eu occupation in LiLnEuH2O2 to Ln=Eu2+, we obtained the mixed‐anionic phase LiEu2H3O, which crystallizes in the same structure type with a=370.04(2) pm, c=1317.32(8) pm and c/a=3.560.