Ternary plumbides ATPb2 (A = Ca, Sr, Ba, Eu; T = Rh, Pd, Pt) with distorted, lonsdaleite-related substructures of tetrahedrally connected lead atoms

Abstract

Abstract The plumbides CaTPb2 (T = Rh, Pd), EuTPb2 (T = Rh, Pd, Pt), SrTPb2 (T = Rh, Pd, Pt) and BaTPb2 (T = Pd, Pt) were obtained by direct reactions of the elements in sealed tantalum tubes in an induction furnace. The moisture sensitive polycrystalline samples were characterized by X-ray powder diffraction. They crystallize with the orthorhombic MgCuAl2-type structure, space group Cmcm. The structures of CaRhPb2 (a = 433.78(3), b = 1102.06(8), c = 798.43(6) pm, wR = 0.0285, 432 F2 values and 16 variables) and EuPdPb2 (a = 457.24(5), b = 1158.27(13), c = 775.73(8), wR = 0.0464, 464 F2 values and 16 variables) were refined from single crystal X-ray diffractometer data. The characteristic structural motif is the distorted tetrahedral substructure built up by the lead atoms with Pb–Pb distances of 326–327 pm in CaRhPb2 and of 315–345 pm in EuPdPb2. With increasing size of the alkaline earth (Eu) cation, the lead substructure becomes more anisotropic with a shift of the [TPb2] polyanions from three- to two-dimensional, leading to significantly increased moisture sensitivity. Temperature dependent magnetic susceptibility studies reveal Pauli paramagnetism for SrRhPb2, SrPtPb2, BaPdPb2 and BaPtPb2. EuRhPb2 and EuPdPb2 are Curie–Weiss paramagnets with stable divalent europium as is also evident from 151Eu Mössbauer spectra. EuRhPb2 is a ferromagnet with T C = 17.7(2) K, while EuPdPb2 orders antiferromagnetically at T N = 15.9 K. This is in agreement with the full magnetic hyperfine field splitting of the 151Eu Mössbauer spectra at T = 6 K.