The title compounds were prepared by reaction of CaSb2, SrSb2, or BaSb3 with the transition metals and antimony in sealed silica tubes. They crystallize with the cubic LaFe4P12‐structure, which was refined from single‐crystal X‐ray data of CaFe4Sb12, SrRu4Sb12, and BaRu4Sb12 to residuals of R = 0.014, 0.016, and 0.014, respectively. The thermal parameters of the alkaline earth ions increase with decreasing ionic size. The SbSb distances are greater in the iron compound than they are in the two ruthenium compounds. This is rationalized to be due to a larger portion of electrons in antibonding SbSb states in the iron compound.
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