Synthesis, Crystal Structure, and Magnetic Properties of Li3Mg2OsO6, a Geometrically Frustrated Osmium(V) Oxide with an Ordered Rock Salt Structure: Comparison with Isostructural Li3Mg2RuO6

The novel osmium-based oxide Li3Mg2OsO6 was synthesized in polycrystalline form by reducing Li5OsO6 by osmium metal and osmium­(IV) oxide in the presence of stoichiometric amounts of magnesium oxide. The crystal structure was refined using powder X-ray diffraction data in the orthorhombic Fddd space group with a = 5.88982(5) Å, b = 8.46873(6) Å, and c = 17.6825(2) Å. This compound is isostructural and isoelectronic with the ruthenium-based system Li3Mg2RuO6. The magnetic ion sublattice Os5+ (S = 3/2) consists of chains of interconnected corner- and edge-shared triangles, which brings about the potential for geometric magnetic frustration. The Curie–Weiss law holds over the range 80–300 K with C = 1.42(3) emu·K/mol [μeff = 3.37(2) μB] and θC = −105.8(2) K. Below 80 K, there are three anomalies at 75, 30, and 8 K. Those at 75 and 30 K are suggestive of short-range antiferromagnetic correlations, while that at 8 K is a somewhat sharper maximum showing a zero-field-cooled/field-cooled divergence suggestive of perhaps spin freezing. The absence of magnetic Bragg peaks at 3.9 K in the neutron diffraction pattern supports this characterization, as does the absence of a sharp peak in the heat capacity, which instead shows only a very broad maximum at ∼12 K. A frustration index of f = 106/8 = 13 indicates a high degree of frustration. The magnetic properties of the osmium phase differ markedly from those of the isostructural ruthenium material, which shows long-range antiferromagnetic order below 17 K, f = 6, and no unusual features at higher temperatures. Estimates of the magnetic exchange interactions at the level of spin-dimer analysis for both the ruthenium and osmium materials support a more frustrated picture for the latter. Errors in the calculation and assignment of the exchange pathways in the previous report on Li3Mg2RuO6 are identified and corrected.