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The ternary silicides Mg 5 Pd 10 Si 16  and Mg 5 Pt 10 Si 16  have been prepared by reaction of magnesium with the binary platinum-metal silicides in sealed tantalum containers (Pt-compound: 1200°C, 3 d, up 20 °/h, down 5 °/h; Pd-compound: 1000°C, 2 d, up and down 50 °/h). In the case of the Pd-compound contact with the tantalum had to be avoided by using a boron nitride crucible. The isotypic compounds crystallize in the cubic space group F4̄3m with 4 formula units per unit cell. The crystal structures were determined from single crystal data, lattice constants from Guinier patterns. The following data were obtained: a = 1258.81(8) pm for Mg 5 Pd 10 Si 16  and a = 1256.94(9) pm for Mg 5 Pt 10 Si 16 . Short distances in the three-dimensional platinum-metal silicon network indicate strong, covalent Pd(Pt)-Si-bonding (d(Pd-Si) = 240.2 to 256.1 pm; d(Pt-Si) = 237.1 to 258.5 pm). In addition, homonuclear bonding seems to be important, resulting in the formation of Si 4 -tetrahedra (d(Si-Si) = 250.4 pm (Mg 5 Pd 10 Si 16 ) and 255 pm (Mg 5 Pt 10 Si 16 )), empty Si 12- polyhedra with the shape of truncated tetrahedra (d(Si- Si): 234.5 and 248.2 pm (Mg 5 Pd 10 Si 16 ); 236 and 248.2 pm (Mg 5 Pt 10 Si 16 )), and Mg-centered Pd(Pt)10-clusters with the shape of adamantane (d(Pd-Pd) = 282.3 pm; d(Pt-Pt) = 284.5 pm). Furthermore, Mg 4 -tetrahedra with Mg-Mg-distances of 360 pm are formed. The structure may be described by an expanded cubic “close” packing of MgPd(Pt) 10 -units in which the Si 4 -tetrahedra occupy the octahedral holes while the Si 12 -polyhedra and the Mg 4 -tetrahedra reside in one half of the tetrahedral holes each.

zeitschrift für naturforschung b

Mg 5 Pd 10 Si 16  und Mg 5 Pt 10 Si 16 , Magnesium-Platinmetall-Silicide mit Tetraedern und gekappten Tetraedern aus Silicium-Atomen / Mg 5 Pd 10 Si 16  and Mg 5 Pt 10 Si 16 , Magnesium Platinum Metal Silicides with Si 4  Tetrahedra and Si 12  Truncated Tetrahedra