Abstract
The germanides Ce3Rh11Ge5, Ce6Rh30Ge19.5, and CeRh3Ge2, which are new ternary Rh-rich phases in the Ce–Rh−Ge system, were prepared by reactions of the elements. Their crystal structures were determined by single-crystal and powder X-ray diffraction methods. Ce3Rh11Ge5 adopts the Gd3Ru4Al12-type structure, which represents the fully stoichiometric version of the defect Sc3Ni11Ge4-type structure, in hexagonal space group P63/mmc with Z = 2 and cell parameters a = 8.6964 (12) Å and c = 9.2209 (12) Å. Ce6Rh30Ge19.5 is a filled derivative of the U6Co30Si19-type structure in hexagonal space group P63/m with Z = 2 and cell parameters a = 22.8480 (11) Å and c = 3.9208 (2) Å. CeRh3Ge2 is derived from a symmetry-lowered distortion of the hexagonal CeCo3B2-type (or substitutionally ordered CaCu5-type) structure, and crystallizes in orthorhombic space group Fmmm with Z = 16 and cell parameters a = 7.392 (6) Å, b = 11.341 (9) Å, and c = 19.66 (2) Å. As expected by their Rh-rich compositions, the three compounds exhibit extensive Rh–Rh bonding, but surprisingly, they also show some short Ge–Ge contacts. Analysis of the electron localization functions and Bader charges reveals that charge transfer takes place from Ce to Rh atoms, indicative of a polar character in the bonding in these intermetallic compounds.
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