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  • Title: Experimental and theoretical investigations of the novel ternary compound Ca4InGe4.
    Author: You TS, Jung Y, Bobev S.
    Journal: Dalton Trans; 2012 Oct 28; 41(40):12446-51. PubMed ID: 22948181.
    Abstract:
    A new polar intermetallic compound with a novel structure type has been synthesized and characterized by both powder and single-crystal X-ray diffraction. Ca(4)InGe(4) crystallizes in the monoclinic crystal system (space group C2/c, Z = 4, Pearson symbol mS36) with five crystallographically unique atomic positions in the asymmetric unit. The corresponding lattice parameters at 200(2) K are a = 18.452(8) Å, b = 5.819(2) Å, c = 8.339(3) Å, and β = 99.330(6)°. The overall crystal structure can be described as a linear intergrowth of two imaginary fragments--Ca(2)InGe(2) with the Gd(2)AlGe(2) type- and CaGe with the FeB type-structures. Another way to rationalize the bonding is to focus on the polyanionic framework, which in this case is made up of unique nets of "seesaw"-shaped [InGe(4)] units. They are interconnected via Ge-Ge dimers into an open three-dimensional framework with Ca(2+) cations occupying the voids within it. Tight-binding linear muffin-tin orbital (LMTO) calculations provide a rationale for the unique local coordination geometry around In and the two distinct types of Ge-Ge bond distances.
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