Alkaline-earth tri-mercurides A IIHg3 (A II=Ca, Sr, Ba): binary intermetallic compounds with a common and a new structure type

Abstract

Abstract The alkaline-earth tri-mercurides AHg3 (A=Ca, Sr, Ba) were yielded from stoichiometric melts of the elements in pure phase (in the case of Sr with Sr11Hg54 as a by-product) and their structures were determined by means of single crystal X-ray data. As reported long ago from powder data, CaHg3 and SrHg3 crystallize in the Ni3Sn-type (P63/mmc, a=662.26(2)/689.39(3), c=501.64(2)/510.38(3) pm, Z=2, R1=0.0233/0.0306 for A=Ca/Sr). The structure consists of a hexagonal close packing of ordered layers AHg3 or a dense packing of anti-cuboctahedra [AHg12] (as cation coordination polyhedra, CCP) and [Hg6] octahedra fused via opposite faces to form columns along c. BaHg3 crystallizes in a unique structure type (P4/ncc, a=1193.04(3), c=958.02(5) pm, Z=12, R1=0.0461). It contains three crystallographically different Hg atoms, which form layers of distorted flat square pyramids. In contrast to the layers of the BaAl4-type, 1 5 ${1 \over 5}$ of the pyramids are missing. Due to the 45 degree rotation of adjacent layers, the connection between the layers is not a ‘apical-to-apical’ one like in BaAl4, but is established by ‘apical-to-basal’ bonds. Compared to the Ca and Sr compound, the CCPs of the two different Ba atoms, which are embedded between the pyramid layers, are increased to 12+4 and 14+2 (for Hg+Ba). For all title compounds and the Li phase LiHg3, which is isotypic to CaHg3, the electronic band structures were calculated within the framework of the FP-LAPW DFT method. Even though the compounds are metals and exhibit only very slight minima of the tDOS at the Fermi level, the electron transfer from the alkali/alkaline-earth element towards mercury is almost complete. Thus, Coulomb interactions and the optimized size and arrangement of the A CCPs, besides the flexible Hg–Hg bonding within the polyanion, determine the structure formation.