total of 73 new quaternary rare-earth germanides RE4M2XGe4 (RE = rare-earth metal; M = Mn-Ni; X = Ag, Cd) were prepared through reactions of the elements. The solid solution Nd4Mn2Cd(Ge1-ySiy)(4) was also prepared under the same conditions and found to be complete over the entire range. All of these compounds adopt the monoclinic Ho4Ni2InGe4-type structure (space group C2/m, a = 14.2-16.7 angstrom, b = 4.0-4.6 angstrom, c = 6.8-7.5 angstrom, beta = 106-109 degrees), as revealed by powder X-ray diffraction analysis and single-crystal X-ray diffraction analysis on selected members. The structure determination of Nd-4(Mn0.78(1)Ag0.22(1))(2)Ag0.83(1)Ge4 disclosed disorder of Mn and Ag atoms within the tetrahedral site and Ag deficiencies within the square planar site. Within the solid solution Nd4Mn2Cd(Ge1-ySiy)(4), the end-members and two intermediate members were structurally characterized; as the Si content increases, the Cd sites become less deficient and the individual [Mn(2)Tt(2)] layers contract but become further apart from each other. Electronic band structure calculations confirm that the Ag-Ge or Cd-Ge bonds are the weakest in the structure and thus prone to distortion. Thermal property measurements confirm expectations from machine-learning predictions that these quaternary germanides should exhibit low thermal conductivity, which was found to be <10 W m(-1) for Nd4Mn2AgGe4.
