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Reported are the synthesis and crystal structure of Ba7Li11Bi10, a new ternary compound crystallizing in its own type with the monoclinic space group C2/m (a = 18.407(3) Å, b = 5.0258(9) Å, and c = 18.353(3) Å; β = 104.43(1)°; Pearson symbol mS56), and those of the structurally related quaternary phases Ba4(Li1−xGax)7Sb6, Ba4(Li1−xInx)7Sb6, Ba4(Li1−xInx)7Bi6, and Eu4(Li1−xInx)7Bi6 (crystallizing in the Eu4Li7Bi6 structure type with the same monoclinic space group C2/m (a = 18.4045(13)–17.642(4) Å, b = 5.012(4)–4.8297(10) Å, and c = 13.2792(10)–12.850(3) Å, β = 126.80(1)–125.85(1)°; Pearson symbol mS34). All studied compounds are identified among the products of the high-temperature reactions of the corresponding elements. Both types of crystal structures are based on corner- and edge-linked Li-centered Sb4 (or Bi4) tetrahedra, Sb6 (or Bi6) octahedra, and Sb2 or Bi2 dumbbells. Given the similarities between the two structures, it might be proposed that they represent the simplest members of a potentially large homologous series described with the general formulae (BaLi3Sb2)n(Ba3Li4Sb4)m or (BaLi3Bi2)n(Ba3Li4Bi4)m, where the more complicated “7-11-10” phase is the member with n = 2 and m = 1, while the “4-7-6” one is the intergrowth of the two components in an equal ratio. The computed electronic band structures of Ba7Li11Bi10 and idealized Ba4Li7Bi6 (a model for Ba4(Li1−xInx)7Bi6) are also discussed.

Synthesis and Structural Characterization of Ba7Li11Bi10 and AE4(Li,Tr)7Pn6 (AE = Sr, Ba, Eu; Tr = Ga, In; Pn = Sb, Bi)