Structure and Bonding in CsNa₂Hg₁₈, a New Ternary Amalgam with Strong Coulombic Bonding Contributions

Abstract

The new ternary amalgam CsNa2Hg18 was synthesised from the elements in an unconventional low-temperature procedure. It crystallises in a tetragonal structure type (space group I4/mmm, a = 7.3054(7) and c = 20.046 Å) and combines ionic and metallic bonding contributions. In the crystal structure, Cs and Na atoms are embedded in a Hg scaffold with highly covalent Hg–Hg bonding. The alkali metal atoms are coordinated exclusively by Hg atoms in unusual environments with coordination numbers CN = 24 for Cs and CN = 16 for Na. Polar amalgams are suitable model systems for studying the parameters influencing the ’bad metal behaviour’ in polar intermetallic phases. We present structural studies on the basis of powder and single crystal diffraction data together with measurements of the specific resistivity and DFT calculations of the electronic structure. For CsNa2Hg18, a high specific resistivity can be observed, but the Ioffe–Regel saturation of the resistivity is expressed much less than in other polar amalgams.

Keywords

• ternary amalgams
• alkali metal amalgams
• crystal structure
• polar metallic bonding
• band structure
• specific resistivity