LaLi3Sb2 crystallizes in the trigonal P-3m1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to six equivalent Li(2) and six equivalent Sb(1) atoms to form distorted LiLi6Sb6 cuboctahedra that share corners with twelve equivalent La(1)Sb6 octahedra, corners with six equivalent Li(2)Li3Sb4 tetrahedra, faces with six equivalent Li(1)Li6Sb6 cuboctahedra, faces with two equivalent La(1)Sb6 octahedra, and faces with six equivalent Li(2)Li3Sb4 tetrahedra. The corner-sharing octahedral tilt angles are 48°. In the second Li site, Li(2) is bonded to three equivalent Li(1) and four equivalent Sb(1) atoms to form distorted LiLi3Sb4 tetrahedra that share corners with three equivalent Li(1)Li6Sb6 cuboctahedra, corners with six equivalent La(1)Sb6 octahedra, corners with three equivalent Li(2)Li3Sb4 tetrahedra, edges with three equivalent La(1)Sb6 octahedra, edges with six equivalent Li(2)Li3Sb4 tetrahedra, faces with three equivalent Li(1)Li6Sb6 cuboctahedra, and faces with three equivalent Li(2)Li3Sb4 tetrahedra. The corner-sharing octahedral tilt angles range from 20-54°. La(1) is bonded to six equivalent Sb(1) atoms to form LaSb6 octahedra that share corners with twelve equivalent Li(1)Li6Sb6 cuboctahedra, corners with twelve equivalent Li(2)Li3Sb4 tetrahedra, edges with six equivalent La(1)Sb6 octahedra, edges with six equivalent Li(2)Li3Sb4 tetrahedra, and faces with two equivalent Li(1)Li6Sb6 cuboctahedra. Sb(1) is bonded in a 10-coordinate geometry to three equivalent Li(1), four equivalent Li(2), and three equivalent La(1) atoms.
LaLi3Sb2 crystallizes in the trigonal P-3m1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to six equivalent Li(2) and six equivalent Sb(1) atoms to form distorted LiLi6Sb6 cuboctahedra that share corners with twelve equivalent La(1)Sb6 octahedra, corners with six equivalent Li(2)Li3Sb4 tetrahedra, faces with six equivalent Li(1)Li6Sb6 cuboctahedra, faces with two equivalent La(1)Sb6 octahedra, and faces with six equivalent Li(2)Li3Sb4 tetrahedra. The corner-sharing octahedral tilt angles are 48°. All Li(1)-Li(2) bond lengths are 2.88 Å. All Li(1)-Sb(1) bond lengths are 3.23 Å. In the second Li site, Li(2) is bonded to three equivalent Li(1) and four equivalent Sb(1) atoms to form distorted LiLi3Sb4 tetrahedra that share corners with three equivalent Li(1)Li6Sb6 cuboctahedra, corners with six equivalent La(1)Sb6 octahedra, corners with three equivalent Li(2)Li3Sb4 tetrahedra, edges with three equivalent La(1)Sb6 octahedra, edges with six equivalent Li(2)Li3Sb4 tetrahedra, faces with three equivalent Li(1)Li6Sb6 cuboctahedra, and faces with three equivalent Li(2)Li3Sb4 tetrahedra. The corner-sharing octahedral tilt angles range from 20-54°. There are three shorter (2.78 Å) and one longer (2.87 Å) Li(2)-Sb(1) bond length. La(1) is bonded to six equivalent Sb(1) atoms to form LaSb6 octahedra that share corners with twelve equivalent Li(1)Li6Sb6 cuboctahedra, corners with twelve equivalent Li(2)Li3Sb4 tetrahedra, edges with six equivalent La(1)Sb6 octahedra, edges with six equivalent Li(2)Li3Sb4 tetrahedra, and faces with two equivalent Li(1)Li6Sb6 cuboctahedra. All La(1)-Sb(1) bond lengths are 3.30 Å. Sb(1) is bonded in a 10-coordinate geometry to three equivalent Li(1), four equivalent Li(2), and three equivalent La(1) atoms.