Modulated vacancy ordering in SrGe6− x (x≈0.45)

Abstract

Abstract The structural properties of modulated SrGe6− x (x≈0.45) were investigated by means of single-crystal and powder X-ray diffraction combined with quantum chemical calculations. The framework compound SrGe6− x adopts a defect variant of the EuGa2Ge4-type crystal structure. Samples of the binary compound with nominal compositions 0≤x≤0.5 were synthesized at pressures from 5 to 6 GPa and a temperature of typically 1400 K. The product reveals diffraction peaks of the EuGa2Ge4-type subcell plus additional reflections indicating an ordered superstructure. Detailed crystal structure analysis evidences the incommensurate nature of the superstructure and a modulation of the vacancy ordering in the germanium network. The computations have shown that the non-stoichiometric composition of the framework with its local defect organization affects the calculated charge of the strontium anions. Although the chemical composition is close to a charge-balanced situation, temperature-dependent resistivity measurements showed metal-type conductivity. At ambient pressure SrGe6− x decomposes exothermally and irreversibly at T=680(10) K into SrGe2 and germanium, indicating its metastable nature at ambient pressure.