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LiIr crystallizes in the hexagonal P-6m2 space group. The structure is three-dimensional. Li is bonded to six equivalent Ir atoms to form a mixture of distorted face, edge, and corner-sharing LiIr6 cuboctahedra. All Li–Ir bond lengths are 2.69 Å. Ir is bonded to six equivalent Li atoms to form a mixture of distorted face, edge, and corner-sharing IrLi6 cuboctahedra.
LiIr3 crystallizes in the orthorhombic Imm2 space group. The structure is three-dimensional. Li is bonded in a 12-coordinate geometry to ten Ir atoms. There are a spread of Li–Ir bond distances ranging from 2.61–2.78 Å. There are two inequivalent Ir sites. In the first Ir site, Ir is bonded in a 12-coordinate geometry to three equivalent Li atoms. In the second Ir site, Ir is bonded in a 12-coordinate geometry to four equivalent Li atoms.