Li3PrBi2 crystallizes in the monoclinic C2/m 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 Pr(1)Li2Bi6 octahedra, corners with three equivalent Li(1)Li3Bi4 tetrahedra, edges with three equivalent Pr(1)Li2Bi6 octahedra, edges with six equivalent Li(1)Li3Bi4 tetrahedra, faces with three equivalent Pr(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 in a 14-coordinate geometry to six equivalent Li(1), two equivalent Pr(1), and six equivalent Bi(1) atoms. Pr(1) is bonded to two equivalent Li(2) and six equivalent Bi(1) atoms to form PrLi2Bi6 octahedra that share corners with two equivalent Pr(1)Li2Bi6 octahedra, corners with six equivalent Li(1)Li3Bi4 tetrahedra, edges with six equivalent Pr(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 Pr(1) atoms.
Li3PrBi2 crystallizes in the monoclinic C2/m 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 Pr(1)Li2Bi6 octahedra, corners with three equivalent Li(1)Li3Bi4 tetrahedra, edges with three equivalent Pr(1)Li2Bi6 octahedra, edges with six equivalent Li(1)Li3Bi4 tetrahedra, faces with three equivalent Pr(1)Li2Bi6 octahedra, and faces with three equivalent Li(1)Li3Bi4 tetrahedra. The corner-sharing octahedral tilt angles are 20°. There is one shorter (2.92 Å) and two longer (2.94 Å) Li(1)-Li(2) bond lengths. There are a spread of Li(1)-Bi(1) bond distances ranging from 2.81-2.94 Å. In the second Li site, Li(2) is bonded in a 14-coordinate geometry to six equivalent Li(1), two equivalent Pr(1), and six equivalent Bi(1) atoms. Both Li(2)-Pr(1) bond lengths are 3.76 Å. There are four shorter (3.28 Å) and two longer (3.29 Å) Li(2)-Bi(1) bond lengths. Pr(1) is bonded to two equivalent Li(2) and six equivalent Bi(1) atoms to form PrLi2Bi6 octahedra that share corners with two equivalent Pr(1)Li2Bi6 octahedra, corners with six equivalent Li(1)Li3Bi4 tetrahedra, edges with six equivalent Pr(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. There are four shorter (3.32 Å) and two longer (3.33 Å) Pr(1)-Bi(1) bond lengths. Bi(1) is bonded in a 10-coordinate geometry to three equivalent Li(2), four equivalent Li(1), and three equivalent Pr(1) atoms.