Abstract
Single crystals of Ba 3LiIr 2O 9, Ba 3NaIr 2O 9, and Ba 3.44K 1.56Ir 2O 10 were grown from hydroxide fluxes. Ba 3LiIr 2O 9 and Ba 3NaIr 2O 9 form in the 6H–BaTiO 3 or triple perovskite structure, which is derived from the hexagonal and cubic stacking of [ AO 3] layers. The structure contains face-sharing Ir 2O 9 octahedra pairs, which are connected via corner shared LiO 6 (NaO 6) octahedra. Both compounds crystallize in the space group P6 3/ mmc, Z=2, with a=5.7804(4) and c=14.302(1) and a=5.866(4) and c=14.596(1) for the Li and Na member, respectively. The structure of Ba 3.44K 1.56Ir 2O 10 is derived from the stacking of [ AO 3] and mixed [ A 2O] layers, and is an n=3 member of the [ A n M n−1 O 3 n ][ A 2O] family of hexagonal perovskite related oxides. The structure of Ba 3.44K 1.56Ir 2O 10 consists of (Ba 3Ir 2O 9) slabs separated by [(Ba,K) 2O] layers and is isostructural with Ba 5Ru 2O 10. The (Ba 3Ir 2O 9) slabs contain isolated, face-sharing Ir 2O 9 octahedra pairs. The compound crystallizes in the space group P6 3/ mmc, Z=2, with a=5.91330(1) Å and c=18.1792(7) Å. The magnetic moments determined from the temperature dependence of the magnetic susceptibility are low for all three oxides, which is thought to be due to a combination of spin–orbit coupling and strong exchange interactions within the iridium octahedra pairs.
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