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The crystal structures of three new ternary compounds, NaCd0.92Sn1.08 (I), Na(Cd0.28Sn0.72)2 (II), and Na2CdSn5 (III) synthesized in a sodium-cadmium-tin system were determined by single-crystal X-ray analysis to be the following: (I) LiGeZn-type structure (hexagonal, a = 4.9326(1) Å, c = 10.8508(3) Å, space group P-6m2); (II) CaIn2-type structure (hexagonal, a = 4.8458(2) Å, c = 7.7569(3) Å, P63/mmc); and (III) isotype with tI-Na2ZnSn5 (tetragonal, a = 6.4248(1) Å, c = 22.7993(5) Å, I-42d). Each compound has a three-dimensional framework structure mainly composed of four-fold coordinated Cd and Sn atoms with Na atoms located in the framework space. Elucidation of the electrical properties of the polycrystalline samples indicated that compounds (I) and (II) are polar intermetallics with metallic conductivity, and compound (III) is a semiconducting Zintl compound. These properties were consistent with the electronic structures calculated using the ordered structure models of the compounds.

Synthesis and Characterization of NaCd0.92Sn1.08, Na(Cd0.28Sn0.72)2 and Na2CdSn5 with Three-Dimensional Cd-Sn Frameworks