Synthesis,crystal structures and chemical bonding of RE5−xLixGe4 (RE = Nd,Sm and Gd; x≃ 1) with the orthorhombic Gd5Si4 type

The syntheses and single‐crystal and electronic structures of three new ternary lithium rare earth germanides, RE_5−xLi_xGe₄ (RE = Nd, Sm and Gd; x≃ 1), namely tetrasamarium lithium tetragermanide (Sm_3.97Li_1.03Ge₄), tetraneodymium lithium tetragermanide (Nd_3.97Li_1.03Ge₄) and tetragadolinium lithium tetragermanide (Gd_3.96Li_1.03Ge₄), are reported. All three compounds crystallize in the orthorhombic space group Pnma and adopt the Gd₅Si₄ structure type (Pearson code oP36). There are six atoms in the asymmetric unit: Li1 in Wyckoff site 4c, RE1 in 8d, RE2 in 8d, Ge1 in 8d, Ge2 in 4c and Ge3 in 4c. One of the RE sites, i.e. RE2, is statistically occupied by RE and Li atoms, accounting for the small deviation from ideal RE₄LiGe₄ stoichiometry.