Synthesis and characterization of Na5M(2+x)Sn(10-x) (x approximately = 0.5, M = Zn, Hg)--a doped tetrahedral...

Two homologous and isostructural compounds Na(5)M(2+x)Sn(10-x) (M = Zn, Hg) were obtained by direct reaction of the elements at high temperature. The crystal structures of these novel phases were determined from single-crystal X-ray diffraction data and represent a new structure type in tin chemistry. They crystallize in the space group Pbcn (No. 60, Z = 4) with a = 12.772(1), b = 10.804(1), and c = 12.777(1) A, V = 1763.1(2) A(3) for Na(5)Zn(2.28)Sn(9.72(2)) (I) and a = 12.958(1), b = 10.984(1), and c = 12.960(1) A, V = 1844.5(2) A(3) for Na(5)Hg(2.39)Sn(9.61(1)) (II). The structures consist of an anionic 3D open framework of tetrahedrally coordinated Sn and M atoms interwoven with a cationic 2D array of interconnected {NaNa(4)} tetrahedra. The framework can be partitioned into fragments of realgar-like units {Sn(8-x)M(x)}(2x-) and twice as many {Sn-M}(2-) dimers. Formally, the compounds are charge-balanced Zintl phases for x = 0.5. As the structure refinements lead to x = 0.28 and 0.39 for I and II, respectively, both structures are electron-rich and expected to be metallic. Theoretical investigations at the density functional theory level reveal a deep minimum at the Fermi level for x = 0.5. According to rigid band analyses, the electronic structure of the phases with the experimentally observed compositions corresponds to heavily doped semiconductors, thereby meeting an important requirement of thermoelectric materials.