Li3SmBi2 crystallizes in the trigonal P-3m1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to three equivalent Li(2) and four equivalent Bi(1) atoms to form distorted LiLi3Bi4 tetrahedra that share corners with three equivalent Sm(1)Li2Bi6 octahedra, corners with three equivalent Li(1)Li3Bi4 tetrahedra, edges with three equivalent Sm(1)Li2Bi6 octahedra, edges with six equivalent Li(1)Li3Bi4 tetrahedra, faces with three equivalent Sm(1)Li2Bi6 octahedra, and faces with three equivalent Li(1)Li3Bi4 tetrahedra. The corner-sharing octahedral tilt angles are 19°. In the second Li site, Li(2) is bonded in a 14-coordinate geometry to six equivalent Li(1), two equivalent Sm(1), and six equivalent Bi(1) atoms. Sm(1) is bonded to two equivalent Li(2) and six equivalent Bi(1) atoms to form SmLi2Bi6 octahedra that share corners with two equivalent Sm(1)Li2Bi6 octahedra, corners with six equivalent Li(1)Li3Bi4 tetrahedra, edges with six equivalent Sm(1)Li2Bi6 octahedra, edges with six equivalent Li(1)Li3Bi4 tetrahedra, and faces with six equivalent Li(1)Li3Bi4 tetrahedra. The corner-sharing octahedra are not tilted. Bi(1) is bonded in a 10-coordinate geometry to three equivalent Li(2), four equivalent Li(1), and three equivalent Sm(1) atoms.
Li3SmBi2 crystallizes in the trigonal P-3m1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to three equivalent Li(2) and four equivalent Bi(1) atoms to form distorted LiLi3Bi4 tetrahedra that share corners with three equivalent Sm(1)Li2Bi6 octahedra, corners with three equivalent Li(1)Li3Bi4 tetrahedra, edges with three equivalent Sm(1)Li2Bi6 octahedra, edges with six equivalent Li(1)Li3Bi4 tetrahedra, faces with three equivalent Sm(1)Li2Bi6 octahedra, and faces with three equivalent Li(1)Li3Bi4 tetrahedra. The corner-sharing octahedral tilt angles are 19°. All Li(1)-Li(2) bond lengths are 2.91 Å. There are three shorter (2.80 Å) and one longer (2.94 Å) Li(1)-Bi(1) bond length. In the second Li site, Li(2) is bonded in a 14-coordinate geometry to six equivalent Li(1), two equivalent Sm(1), and six equivalent Bi(1) atoms. Both Li(2)-Sm(1) bond lengths are 3.71 Å. All Li(2)-Bi(1) bond lengths are 3.27 Å. Sm(1) is bonded to two equivalent Li(2) and six equivalent Bi(1) atoms to form SmLi2Bi6 octahedra that share corners with two equivalent Sm(1)Li2Bi6 octahedra, corners with six equivalent Li(1)Li3Bi4 tetrahedra, edges with six equivalent Sm(1)Li2Bi6 octahedra, edges with six equivalent Li(1)Li3Bi4 tetrahedra, and faces with six equivalent Li(1)Li3Bi4 tetrahedra. The corner-sharing octahedra are not tilted. All Sm(1)-Bi(1) bond lengths are 3.28 Å. Bi(1) is bonded in a 10-coordinate geometry to three equivalent Li(2), four equivalent Li(1), and three equivalent Sm(1) atoms.