SrZn2Sn2 and Ca2Zn3Sn6 — two new Ae–Zn–Sn polar intermetallic compounds (Ae: alkaline earth metal)

SrZn2Sn2 and Ca2Zn3Sn6, two closely related new polar intermetallic compounds, were obtained by high temperature reactions of the elements. Their crystal structures were determined with single crystal XRD methods, and their electronic structures were analyzed by means of DFT calculations. The Zn–Sn structure part of SrZn2Sn2 comprises (anti-)PbO-like {ZnSn4/4} and {SnZn4/4} layers. Ca2Zn3Sn6 shows similar {ZnSn4/4} layers and {Sn4Zn} slabs constructed of a covalently bonded Sn scaffold capped by Zn atoms. For both phases, the two types of layers are alternatingly stacked and interconnected via Zn–Sn bonds. SrZn2Sn2 adopts the SrPd2Bi2 structure type, and Ca2Zn3Sn6 is isotypic to the R2Zn3Ge6 compounds (R=La, Ce, Pr, Nd). Band structure calculations indicate that both SrZn2Sn2 and Ca2Zn3Sn6 are metallic. Analyses of the chemical bonding with the electron localization function (ELF) show lone pair like basins at Sn atoms and Zn–Sn bonding interactions between the layers for both title phases, and covalent Sn–Sn bonding within the {Sn4Zn} layers of Ca2Zn3Sn6. - Graphical abstract: Crystal structures of the new Ae–Zn–Sn polar intermetallic phases SrZn2Sn2 and Ca2Zn3Sn6. Highlights: ► New polar intermetallic phases SrZn2Sn2 and Ca2Zn3Sn6. ► Obtained by high temperature reactions of the elements. ► Single crystal XRD structure determination and DFT electronic structure calculations. ► Closely related crystal and electronic structures. ► Metallic conductivity coexisting with lone pairs and covalent bonding features.