Mg5Pd10Si16 und Mg5Pt10Si16, Magnesium-Platinmetall-Silicide mit Tetraedern und gekappten Tetraedern aus Silicium-Atomen / Mg5Pd10Si16 and Mg5Pt10Si16, Magnesium Platinum Metal Silicides with Si4 Tetrahedra and Si12 Truncated Tetrahedra
The ternary silicides Mg5Pd10Si16 and Mg5Pt10Si16 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 Mg5Pd10Si16 and a = 1256.94(9) pm for Mg5Pt10Si16. 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 Si4-tetrahedra (d(Si-Si) = 250.4 pm (Mg5Pd10Si16) and 255 pm (Mg5Pt10Si16)), empty Si12-polyhedra with the shape of truncated tetrahedra (d(Si- Si): 234.5 and 248.2 pm (Mg5Pd10Si16); 236 and 248.2 pm (Mg5Pt10Si16)), 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, Mg4-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 Si4-tetrahedra occupy the octahedral holes while the Si12-polyhedra and the Mg4-tetrahedra reside in one half of the tetrahedral holes each.