La4[(C2)1-xGex]3, Lanthanum(III) Dicarbide(4-) Germanide(4-) Mixed Crystals: A Continuous Transition between the Cubic Structure Types cI40 (Rb4O6/Pu2C3) and cI28 (Th3P4)

The compounds BaGdAuSe3, BaLaCuTe3, BaYCuTe3, BaYAgTe3, BaLaAgTe3, BaYbCuTe3, BaGdAgTe3, BaNdCuTe3, and BaPrCuTe3 were prepared by the reaction in a BaBr2/KBr flux at 850°C of a rare earth, a coinage-group metal, a chalcogen, and BaSe or BaTe. The unit cells of all of the compounds and the crystal structures of the first four compounds were determined by single-crystal X-ray diffraction methods. With the exception of BaLaCuTe3, which crystallizes with four formula units in the orthorhombic space group Pnma, all of these compounds crystallize with four formula units in the orthorhombic space group Cmcm. BaLaCuTe3, isostructural with beta-BaLaCuSe3 and Eu2CuS3 (i.e., Eu2+Eu3+Cu+(S2-)3), and BaGdAuSe3, BaYCuTe3, and BaYAgTe3, isostructural with KZrCuS3, crystallize in a layered structure in which there are 2infinity[LnMQ2-3] layers separated by Ba2+ ions. Ln atoms are coordinated by six Q atoms at the corners of a distorted octahedron, and M atoms are coordinated by four Q atoms at the corners of a tetrahedron. The layers are formed by the connection of edge-sharing octahedral chains and corner-sharing tetrahedral chains. Ba atoms are coordinated by seven Q atoms in BaLaCuTe3 and by eight Q atoms in BaGdAuSe3, BaYCuTe3, and BaYAgTe3. BaNdAgTe3 shows temperaturedependent paramagnetism. Its magnetic susceptibility follows the Curie–Weiss law. The effective magnetic moment of 3.4(3) mu B is in agreement with the theoretical value of 3.6 mu B for Nd3+.