PrLi3Sb2 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 Sb(1) atoms to form distorted LiLi3Sb4 tetrahedra that share corners with three equivalent Li(2)Li6Pr2Sb6 cuboctahedra, corners with three equivalent Pr(1)Li2Sb6 octahedra, corners with three equivalent Li(1)Li3Sb4 tetrahedra, edges with three equivalent Pr(1)Li2Sb6 octahedra, edges with six equivalent Li(1)Li3Sb4 tetrahedra, faces with three equivalent Li(2)Li6Pr2Sb6 cuboctahedra, faces with three equivalent Pr(1)Li2Sb6 octahedra, and faces with three equivalent Li(1)Li3Sb4 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 Pr(1), and six equivalent Sb(1) atoms to form distorted LiLi6Pr2Sb6 cuboctahedra that share corners with two equivalent Li(2)Li6Pr2Sb6 cuboctahedra, corners with twelve equivalent Pr(1)Li2Sb6 octahedra, corners with six equivalent Li(1)Li3Sb4 tetrahedra, faces with six equivalent Li(2)Li6Pr2Sb6 cuboctahedra, faces with two equivalent Pr(1)Li2Sb6 octahedra, and faces with six equivalent Li(1)Li3Sb4 tetrahedra. The corner-sharing octahedral tilt angles are 49°. Pr(1) is bonded to two equivalent Li(2) and six equivalent Sb(1) atoms to form PrLi2Sb6 octahedra that share corners with twelve equivalent Li(2)Li6Pr2Sb6 cuboctahedra, corners with two equivalent Pr(1)Li2Sb6 octahedra, corners with six equivalent Li(1)Li3Sb4 tetrahedra, edges with six equivalent Pr(1)Li2Sb6 octahedra, edges with six equivalent Li(1)Li3Sb4 tetrahedra, faces with two equivalent Li(2)Li6Pr2Sb6 cuboctahedra, and faces with six equivalent Li(1)Li3Sb4 tetrahedra. The corner-sharing octahedra are not tilted. Sb(1) is bonded in a 10-coordinate geometry to three equivalent Li(2), four equivalent Li(1), and three equivalent Pr(1) atoms.
PrLi3Sb2 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 Sb(1) atoms to form distorted LiLi3Sb4 tetrahedra that share corners with three equivalent Li(2)Li6Pr2Sb6 cuboctahedra, corners with three equivalent Pr(1)Li2Sb6 octahedra, corners with three equivalent Li(1)Li3Sb4 tetrahedra, edges with three equivalent Pr(1)Li2Sb6 octahedra, edges with six equivalent Li(1)Li3Sb4 tetrahedra, faces with three equivalent Li(2)Li6Pr2Sb6 cuboctahedra, faces with three equivalent Pr(1)Li2Sb6 octahedra, and faces with three equivalent Li(1)Li3Sb4 tetrahedra. The corner-sharing octahedral tilt angles are 20°. All Li(1)-Li(2) bond lengths are 2.87 Å. There are three shorter (2.76 Å) and one longer (2.87 Å) Li(1)-Sb(1) bond length. In the second Li site, Li(2) is bonded to six equivalent Li(1), two equivalent Pr(1), and six equivalent Sb(1) atoms to form distorted LiLi6Pr2Sb6 cuboctahedra that share corners with two equivalent Li(2)Li6Pr2Sb6 cuboctahedra, corners with twelve equivalent Pr(1)Li2Sb6 octahedra, corners with six equivalent Li(1)Li3Sb4 tetrahedra, faces with six equivalent Li(2)Li6Pr2Sb6 cuboctahedra, faces with two equivalent Pr(1)Li2Sb6 octahedra, and faces with six equivalent Li(1)Li3Sb4 tetrahedra. The corner-sharing octahedral tilt angles are 49°. Both Li(2)-Pr(1) bond lengths are 3.70 Å. All Li(2)-Sb(1) bond lengths are 3.21 Å. Pr(1) is bonded to two equivalent Li(2) and six equivalent Sb(1) atoms to form PrLi2Sb6 octahedra that share corners with twelve equivalent Li(2)Li6Pr2Sb6 cuboctahedra, corners with two equivalent Pr(1)Li2Sb6 octahedra, corners with six equivalent Li(1)Li3Sb4 tetrahedra, edges with six equivalent Pr(1)Li2Sb6 octahedra, edges with six equivalent Li(1)Li3Sb4 tetrahedra, faces with two equivalent Li(2)Li6Pr2Sb6 cuboctahedra, and faces with six equivalent Li(1)Li3Sb4 tetrahedra. The corner-sharing octahedra are not tilted. All Pr(1)-Sb(1) bond lengths are 3.27 Å. Sb(1) is bonded in a 10-coordinate geometry to three equivalent Li(2), four equivalent Li(1), and three equivalent Pr(1) atoms.