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The structural properties of modulated SrGe 6−   x   ( x ≈0.45) were investigated by means of single-crystal and powder X-ray diffraction combined with quantum chemical calculations. The framework compound SrGe 6−   x   adopts a defect variant of the EuGa 2 Ge 4 -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 EuGa 2 Ge 4 -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 SrGe 6−   x   decomposes exothermally and irreversibly at  T =680(10) K into SrGe 2  and germanium, indicating its metastable nature at ambient pressure.

Modulated vacancy ordering in SrGe 6− x ( x ≈0.45)