Li3GdBi2 crystallizes in the trigonal P-3m1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 14-coordinate geometry to six equivalent Li(2), two equivalent Gd(1), and six equivalent Bi(1) atoms. In the second Li site, Li(2) is bonded to three equivalent Li(1) and four equivalent Bi(1) atoms to form distorted LiLi3Bi4 tetrahedra that share corners with three equivalent Gd(1)Li2Bi6 octahedra, corners with three equivalent Li(2)Li3Bi4 tetrahedra, edges with three equivalent Gd(1)Li2Bi6 octahedra, edges with six equivalent Li(2)Li3Bi4 tetrahedra, faces with three equivalent Gd(1)Li2Bi6 octahedra, and faces with three equivalent Li(2)Li3Bi4 tetrahedra. The corner-sharing octahedral tilt angles are 19°. Gd(1) is bonded to two equivalent Li(1) and six equivalent Bi(1) atoms to form GdLi2Bi6 octahedra that share corners with two equivalent Gd(1)Li2Bi6 octahedra, corners with six equivalent Li(2)Li3Bi4 tetrahedra, edges with six equivalent Gd(1)Li2Bi6 octahedra, edges with six equivalent Li(2)Li3Bi4 tetrahedra, and faces with six equivalent Li(2)Li3Bi4 tetrahedra. The corner-sharing octahedra are not tilted. Bi(1) is bonded in a 10-coordinate geometry to three equivalent Li(1), four equivalent Li(2), and three equivalent Gd(1) atoms.
Li3GdBi2 crystallizes in the trigonal P-3m1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 14-coordinate geometry to six equivalent Li(2), two equivalent Gd(1), and six equivalent Bi(1) atoms. All Li(1)-Li(2) bond lengths are 2.91 Å. Both Li(1)-Gd(1) bond lengths are 3.67 Å. All Li(1)-Bi(1) bond lengths are 3.26 Å. In the second Li site, Li(2) is bonded to three equivalent Li(1) and four equivalent Bi(1) atoms to form distorted LiLi3Bi4 tetrahedra that share corners with three equivalent Gd(1)Li2Bi6 octahedra, corners with three equivalent Li(2)Li3Bi4 tetrahedra, edges with three equivalent Gd(1)Li2Bi6 octahedra, edges with six equivalent Li(2)Li3Bi4 tetrahedra, faces with three equivalent Gd(1)Li2Bi6 octahedra, and faces with three equivalent Li(2)Li3Bi4 tetrahedra. The corner-sharing octahedral tilt angles are 19°. There are three shorter (2.79 Å) and one longer (2.95 Å) Li(2)-Bi(1) bond length. Gd(1) is bonded to two equivalent Li(1) and six equivalent Bi(1) atoms to form GdLi2Bi6 octahedra that share corners with two equivalent Gd(1)Li2Bi6 octahedra, corners with six equivalent Li(2)Li3Bi4 tetrahedra, edges with six equivalent Gd(1)Li2Bi6 octahedra, edges with six equivalent Li(2)Li3Bi4 tetrahedra, and faces with six equivalent Li(2)Li3Bi4 tetrahedra. The corner-sharing octahedra are not tilted. All Gd(1)-Bi(1) bond lengths are 3.25 Å. Bi(1) is bonded in a 10-coordinate geometry to three equivalent Li(1), four equivalent Li(2), and three equivalent Gd(1) atoms.