Li3CeBi2 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 Li(2)Li6Ce2Bi6 cuboctahedra, corners with three equivalent Ce(1)Li2Bi6 octahedra, corners with three equivalent Li(1)Li3Bi4 tetrahedra, edges with three equivalent Ce(1)Li2Bi6 octahedra, edges with six equivalent Li(1)Li3Bi4 tetrahedra, faces with three equivalent Li(2)Li6Ce2Bi6 cuboctahedra, faces with three equivalent Ce(1)Li2Bi6 octahedra, and faces with three equivalent Li(1)Li3Bi4 tetrahedra. The corner-sharing octahedral tilt angles are 20°. In the second Li site, Li(2) is bonded to six equivalent Li(1), two equivalent Ce(1), and six equivalent Bi(1) atoms to form distorted LiLi6Ce2Bi6 cuboctahedra that share corners with two equivalent Li(2)Li6Ce2Bi6 cuboctahedra, corners with twelve equivalent Ce(1)Li2Bi6 octahedra, corners with six equivalent Li(1)Li3Bi4 tetrahedra, faces with six equivalent Li(2)Li6Ce2Bi6 cuboctahedra, faces with two equivalent Ce(1)Li2Bi6 octahedra, and faces with six equivalent Li(1)Li3Bi4 tetrahedra. The corner-sharing octahedral tilt angles are 49°. Ce(1) is bonded to two equivalent Li(2) and six equivalent Bi(1) atoms to form CeLi2Bi6 octahedra that share corners with twelve equivalent Li(2)Li6Ce2Bi6 cuboctahedra, corners with two equivalent Ce(1)Li2Bi6 octahedra, corners with six equivalent Li(1)Li3Bi4 tetrahedra, edges with six equivalent Ce(1)Li2Bi6 octahedra, edges with six equivalent Li(1)Li3Bi4 tetrahedra, faces with two equivalent Li(2)Li6Ce2Bi6 cuboctahedra, 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 Ce(1) atoms.
Li3CeBi2 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 Li(2)Li6Ce2Bi6 cuboctahedra, corners with three equivalent Ce(1)Li2Bi6 octahedra, corners with three equivalent Li(1)Li3Bi4 tetrahedra, edges with three equivalent Ce(1)Li2Bi6 octahedra, edges with six equivalent Li(1)Li3Bi4 tetrahedra, faces with three equivalent Li(2)Li6Ce2Bi6 cuboctahedra, faces with three equivalent Ce(1)Li2Bi6 octahedra, and faces with three equivalent Li(1)Li3Bi4 tetrahedra. The corner-sharing octahedral tilt angles are 20°. All Li(1)-Li(2) bond lengths are 2.94 Å. There are three shorter (2.83 Å) and one longer (2.94 Å) Li(1)-Bi(1) bond length. In the second Li site, Li(2) is bonded to six equivalent Li(1), two equivalent Ce(1), and six equivalent Bi(1) atoms to form distorted LiLi6Ce2Bi6 cuboctahedra that share corners with two equivalent Li(2)Li6Ce2Bi6 cuboctahedra, corners with twelve equivalent Ce(1)Li2Bi6 octahedra, corners with six equivalent Li(1)Li3Bi4 tetrahedra, faces with six equivalent Li(2)Li6Ce2Bi6 cuboctahedra, faces with two equivalent Ce(1)Li2Bi6 octahedra, and faces with six equivalent Li(1)Li3Bi4 tetrahedra. The corner-sharing octahedral tilt angles are 49°. Both Li(2)-Ce(1) bond lengths are 3.76 Å. All Li(2)-Bi(1) bond lengths are 3.29 Å. Ce(1) is bonded to two equivalent Li(2) and six equivalent Bi(1) atoms to form CeLi2Bi6 octahedra that share corners with twelve equivalent Li(2)Li6Ce2Bi6 cuboctahedra, corners with two equivalent Ce(1)Li2Bi6 octahedra, corners with six equivalent Li(1)Li3Bi4 tetrahedra, edges with six equivalent Ce(1)Li2Bi6 octahedra, edges with six equivalent Li(1)Li3Bi4 tetrahedra, faces with two equivalent Li(2)Li6Ce2Bi6 cuboctahedra, and faces with six equivalent Li(1)Li3Bi4 tetrahedra. The corner-sharing octahedra are not tilted. All Ce(1)-Bi(1) bond lengths are 3.33 Å. Bi(1) is bonded in a 10-coordinate geometry to three equivalent Li(2), four equivalent Li(1), and three equivalent Ce(1) atoms.