Mixed cations and structural complexity in (Eu(1-x)Ca(x))(4)In(3)Ge(4) and (Eu(1-x)Ca(x))(3)In(2)Ge(3)--the first two members of the homologous series A(2[n+m])In(2n+m)Ge(2[n+m]) (n, m = 1, 2, ...infinity; A = Ca, Sr, Ba, Eu, or Yb).

Reported are the synthesis and the structural characterization of two members of a new homologous series of polar intermetallic compounds, which exist only with mixed alkaline-earth and rare-earth metal cations. Crystals of (Eu(1-x)Ca(x))(4)In(3)Ge(4) (0.35(1) <or= x <or= 0.70(1)) and (Eu(1-x)Ca(x))(3)In(2)Ge(3) (0.78(1) <or= x <or= 0.90(1)) have been grown using a molten In metal flux and structurally characterized by single-crystal X-ray diffraction. (Eu(1-x)Ca(x))(4)In(3)Ge(4) adopts the monoclinic Mg(5)Si(6)-type structure (space group C2/m, Z = 2, Pearson symbol mS22) with lattice parameters a = 16.874(1)-17.024(2) A, b = 4.496(3)-4.556(1) A, c = 7.473(4)-7.540(1) A, and beta = 107.306(10)-105.631(3) degrees . (Eu(1-x)Ca(x))(3)In(2)Ge(3) crystallizes with a novel orthorhombic structure (space group Pnma, Z = 4, Pearson symbol oP32) with lattice parameters in the ranges a = 7.382(2)-7.4010(9) A, b = 4.452(1)-4.4640(6) A, and c = 23.684(6)-23.734(3) A, depending on the Eu/Ca ratio. The polyanionic substructures in both cases are related and are based on InGe(4) edge-shared tetrahedra, Ge(2) dimers, and bridging In atoms in a nearly square-planar environment. The (Eu(1-x)Ca(x))(4)In(3)Ge(4) structure can be viewed as a 1:1 intergrowth of Mo(2)FeB(2)-like and TiNiSi-like fragments, whereas (Eu(1-x)Ca(x))(3)In(2)Ge(3) can be rationalized as a 2:1 intergrowth of the same structural motifs. Both phases exhibit fairly wide homogeneity ranges and exist only with mixed cations. The experimental results have been complemented by linear muffin-tin orbital tight-binding band structure calculations, as well as an analysis of the observed cationic site preferences.