Quaternary arsenides ACdGeAs2 (A = K, Rb) built of ethane-like Ge2As6 units.

Reactions of the elements at high temperature resulted in the quaternary arsenides KCdGeAs2 (650 °C) and RbCdGeAs2 (600 °C). Single-crystal X-ray diffraction analysis reveals that they adopt a new triclinic structure type (space group P1̅, Pearson symbol aP20, Z = 4; a = 8.0040(18) Å, b = 8.4023(19) Å, c = 8.703(2) Å, α = 71.019(3)°, β = 75.257(3)°, γ = 73.746(3)° for KCdGeAs2; a = 8.2692(13) Å, b = 8.4519(13) Å, c = 8.7349(13) Å, α = 71.163(2)°, β = 75.601(2)°, γ = 73.673(2)° for RbCdGeAs2). Two-dimensional anionic layers CdGeAs2 are separated by A(+) cations and are built from ethane-like Ge2As6 units forming infinite chains connected via three- and four-coordinated Cd atoms. Being Zintl phases, these compounds satisfy charge balance and are expected to be semiconducting, as confirmed by band structure calculations on KCdGeAs2, which reveal a band gap of 0.8 eV. KCdGeAs2 is diamagnetic.