Half Antiperovskites. III. Crystallographic and Electronic Structure Effects in Sn2−xInxCo3S2

Half antiperovskites were investigated within the series Sn2−xInxCo3S2 by X‐ray diffraction, thermal analysis, and DFT band structure calculations. The shandite type structure was confirmed from powder and single crystal diffraction for the studied compounds. Co orders like Ni in the previously studied InNi3/2S. SnCo3/2S is metrically pseudo cubic and can easily be deduced from the antiperovskite MgCo3C. The Curie temperature Tc = −97 °C of SnCo3/2S was confirmed by calorimetric data. Its electronic structure indicates a spin 1 2 type IA half metallic ground state. Upon In doping the crystal structure becomes hexagonally distorted towards a higher chex/ahex relation. The Curie temperature rapidly falls below −135 °C for x(In) = 0.4. A metal to semiconductor transition is predicted for ordered InSnCo3S2 from its electronic band structure. For InCo3/2S a non magnetic metallic ground state is found.