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In a systematic synthetic, crystallographic and bond theoretical study, the stability ranges as well as the distribution of the isoelectronic late  d -block elements Zn, Cd and Hg ( M ) in the polyanions of the YCd 6 -type phases (Ca/Sr)Cd 6  have been investigated. Starting from Ca(Cd/Hg) 6 , 12−30% of the  M  atoms can be substituted by Zn, which gradually occupies the center of the empty cubes. In all ternary compounds, smaller/less electronegative Zn/Cd atoms occupy the disordered tetrahedra explaining the lack of the YCd 6 -type for pure mercurides. Along the section SrCd 6 -SrHg 6 , the ordered Eu 4 Cd 25 -type is formed (Sr 4 Cd 16.1 Hg 8.9 :  cF 1392,  Fd 3̅,  a =3191.93(5) pm,  R 1=0.0404). Besides, two new complex cubic Ca phases appear at increased Zn proportion: Ca 2 Zn 5.1 Cd 5.8 , which exhibits a nearly complete site preference of Zn and Cd, crystallizes in the rare cubic Mg 2 Zn 11 -type structure ( cP 39− δ ,  Pm 3̅,  a =918.1(1) pm,  R 1=0.0349). In the Ca–Hg system, an increased Zn proportion yielded the new compound CaZn 1.31 Hg 3.69  ( cF 480,  F 4̅3 m ,  a =2145.43(9) pm,  R 1=0.0572), with a complex cubic structure closely related to Ba 20 Hg 103 . All structures, which are commonly described using nested polyhedra around high-symmetric sites, are alternatively described in accordance with the calculated electron densities and charge distribution: building blocks are face-sharing [ M  4 ] tetrahedra (star polyhedra such as TS, IS, OS), each with a cage-critical point in its center, and [ M  8 ] cubes (deformed TS), which are either empty, distorted or filled. The  M  element distribution in the anion is determined by size criteria and the difference in electronegativity, which induces a preferred formation of heteroatomic polar bonds.

Complex cubic metallides AM ~6 ( A =Ca, Sr; M =Zn, Cd, Hg). Synthesis, crystal chemistry and chemical bonding