K2NaOsO5.5 and K3NaOs2O9: The first osmium perovskites containing alkali cations at the “A” site

K2NaOsO5.5 and K3NaOs2O9 were obtained from solid-state reactions of potassium superoxide, sodium peroxide and osmium metal at elevated oxygen pressures. K2NaOsO5.5 crystallizes as an oxygen-deficient cubic double perovskite in space group Fm View the MathML source3¯m with a=8.4184(5) Å and contains isolated OsO6 octahedra. K3NaOs2O9 crystallizes hexagonally in P63/mmc with a=5.9998(4) Å and c=14.3053(14) Å. K3NaOs2O9 consists of face sharing Os2O9 pairs of octahedra. According to magnetic measurements K2NaOsO5.5 is diamagnetic, whereas K3NaOs2O9 displays strong antiferromagnetic coupling (TN=140 K), indicating enhanced magnetic interactions within the octahedral pair.