Li3InBr6 is Ilmenite-like structured and crystallizes in the trigonal P-31c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to six equivalent Br(1) atoms to form distorted LiBr6 octahedra that share corners with three equivalent In(1)Br6 octahedra, corners with six equivalent Li(2)Br6 octahedra, edges with three equivalent Li(1)Br6 octahedra, and  a faceface with one In(1)Br6 octahedra. The corner-sharing octahedral tilt angles range from 42-57°. In the second Li site, Li(2) is bonded to six equivalent Br(1) atoms to form LiBr6 octahedra that share corners with twelve equivalent Li(1)Br6 octahedra and edges with three equivalent In(1)Br6 octahedra. The corner-sharing octahedral tilt angles range from 42-57°. In(1) is bonded to six equivalent Br(1) atoms to form InBr6 octahedra that share corners with six equivalent Li(1)Br6 octahedra, edges with three equivalent Li(2)Br6 octahedra, and faces with two equivalent Li(1)Br6 octahedra. The corner-sharing octahedral tilt angles are 54°. Br(1) is bonded in a rectangular see-saw-like geometry to one Li(2), two equivalent Li(1), and one In(1) atom.
Li3InBr6 is Ilmenite-like structured and crystallizes in the trigonal P-31c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to six equivalent Br(1) atoms to form distorted LiBr6 octahedra that share corners with three equivalent In(1)Br6 octahedra, corners with six equivalent Li(2)Br6 octahedra, edges with three equivalent Li(1)Br6 octahedra, and  a faceface with one In(1)Br6 octahedra. The corner-sharing octahedral tilt angles range from 42-57°. There are three shorter (2.68 Å) and three longer (3.01 Å) Li(1)-Br(1) bond lengths. In the second Li site, Li(2) is bonded to six equivalent Br(1) atoms to form LiBr6 octahedra that share corners with twelve equivalent Li(1)Br6 octahedra and edges with three equivalent In(1)Br6 octahedra. The corner-sharing octahedral tilt angles range from 42-57°. All Li(2)-Br(1) bond lengths are 2.81 Å. In(1) is bonded to six equivalent Br(1) atoms to form InBr6 octahedra that share corners with six equivalent Li(1)Br6 octahedra, edges with three equivalent Li(2)Br6 octahedra, and faces with two equivalent Li(1)Br6 octahedra. The corner-sharing octahedral tilt angles are 54°. All In(1)-Br(1) bond lengths are 2.72 Å. Br(1) is bonded in a rectangular see-saw-like geometry to one Li(2), two equivalent Li(1), and one In(1) atom.