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  • Title: Synthesis and structure determination of seven ternary bismuthides: crystal chemistry of the RELi3Bi2 family (RE = La-Nd, Sm, Gd, and Tb).
    Author: Prakash J, Schäfer MC, Bobev S.
    Journal: Acta Crystallogr C Struct Chem; 2015 Oct; 71(Pt 10):894-9. PubMed ID: 26422218.
    Abstract:
    Zintl phases are renowned for their diverse crystal structures with rich structural chemistry and have recently exhibited some remarkable heat- and charge-transport properties. The ternary bismuthides RELi3Bi2 (RE = La-Nd, Sm, Gd, and Tb) (namely, lanthanum trilithium dibismuthide, LaLi3Bi2, cerium trilithium dibismuthide, CeLi3Bi2, praseodymium trilithium dibismuthide, PrLi3Bi2, neodymium trilithium dibismuthide, NdLi3Bi2, samarium trilithium dibismuthide, SmLi3Bi2, gadolinium trilithium dibismuthide, GdLi3Bi2, and terbium trilithium dibismuthide, TbLi3Bi2) were synthesized by high-temperature reactions of the elements in sealed Nb ampoules. Single-crystal X-ray diffraction analysis shows that all seven compounds are isostructural and crystallize in the LaLi3Sb2 type structure in the trigonal space group P-3m1 (Pearson symbol hP6). The unit-cell volumes decrease monotonically on moving from the La to the Tb compound, owing to the lanthanide contraction. The structure features a rare-earth metal atom and one Li atom in a nearly perfect octahedral coordination by six Bi atoms. The second crystallographically unique Li atom is surrounded by four Bi atoms in a slightly distorted tetrahedral geometry. The atomic arrangements are best described as layered structures consisting of two-dimensional layers of fused LiBi4 tetrahedra and LiBi6 octahedra, separated by rare-earth metal cations. As such, these compounds are expected to be valance-precise semiconductors, whose formulae can be represented as (RE(3+))(Li(1+))3(Bi(3-))2.
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