LiPrS2 is Caswellsilverite-like structured and crystallizes in the triclinic P1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one S(1), one S(2), two equivalent S(3), and two equivalent S(4) atoms to form LiS6 octahedra that share corners with two equivalent Pr(2)S6 octahedra, corners with four equivalent Li(1)S6 octahedra, edges with four equivalent Li(2)S6 octahedra, edges with four equivalent Pr(1)S6 octahedra, and edges with four equivalent Pr(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 1-2°. In the second Li site, Li(2) is bonded to one S(3), one S(4), two equivalent S(1), and two equivalent S(2) atoms to form LiS6 octahedra that share corners with two equivalent Pr(1)S6 octahedra, corners with four equivalent Li(2)S6 octahedra, edges with four equivalent Li(1)S6 octahedra, edges with four equivalent Pr(1)S6 octahedra, and edges with four equivalent Pr(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 1-2°. There are two inequivalent Pr sites. In the first Pr site, Pr(1) is bonded to one S(3), one S(4), two equivalent S(1), and two equivalent S(2) atoms to form PrS6 octahedra that share corners with two equivalent Li(2)S6 octahedra, corners with four equivalent Pr(1)S6 octahedra, edges with four equivalent Li(1)S6 octahedra, edges with four equivalent Li(2)S6 octahedra, and edges with four equivalent Pr(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 1-2°. In the second Pr site, Pr(2) is bonded to one S(1), one S(2), two equivalent S(3), and two equivalent S(4) atoms to form PrS6 octahedra that share corners with two equivalent Li(1)S6 octahedra, corners with four equivalent Pr(2)S6 octahedra, edges with four equivalent Li(1)S6 octahedra, edges with four equivalent Li(2)S6 octahedra, and edges with four equivalent Pr(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 1-3°. There are four inequivalent S sites. In the first S site, S(1) is bonded to one Li(1), two equivalent Li(2), one Pr(2), and two equivalent Pr(1) atoms to form a mixture of edge and corner-sharing SLi3Pr3 octahedra. The corner-sharing octahedral tilt angles range from 1-2°. In the second S site, S(2) is bonded to one Li(1), two equivalent Li(2), one Pr(2), and two equivalent Pr(1) atoms to form a mixture of edge and corner-sharing SLi3Pr3 octahedra. The corner-sharing octahedral tilt angles range from 1-2°. In the third S site, S(3) is bonded to one Li(2), two equivalent Li(1), one Pr(1), and two equivalent Pr(2) atoms to form a mixture of edge and corner-sharing SLi3Pr3 octahedra. The corner-sharing octahedral tilt angles range from 1-2°. In the fourth S site, S(4) is bonded to one Li(2), two equivalent Li(1), one Pr(1), and two equivalent Pr(2) atoms to form a mixture of edge and corner-sharing SLi3Pr3 octahedra. The corner-sharing octahedral tilt angles range from 1-3°.
LiPrS2 is Caswellsilverite-like structured and crystallizes in the triclinic P1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one S(1), one S(2), two equivalent S(3), and two equivalent S(4) atoms to form LiS6 octahedra that share corners with two equivalent Pr(2)S6 octahedra, corners with four equivalent Li(1)S6 octahedra, edges with four equivalent Li(2)S6 octahedra, edges with four equivalent Pr(1)S6 octahedra, and edges with four equivalent Pr(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 1-2°. The Li(1)-S(1) bond length is 2.95 Å. The Li(1)-S(2) bond length is 2.82 Å. There is one shorter (2.79 Å) and one longer (2.89 Å) Li(1)-S(3) bond length. There is one shorter (2.79 Å) and one longer (2.89 Å) Li(1)-S(4) bond length. In the second Li site, Li(2) is bonded to one S(3), one S(4), two equivalent S(1), and two equivalent S(2) atoms to form LiS6 octahedra that share corners with two equivalent Pr(1)S6 octahedra, corners with four equivalent Li(2)S6 octahedra, edges with four equivalent Li(1)S6 octahedra, edges with four equivalent Pr(1)S6 octahedra, and edges with four equivalent Pr(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 1-2°. The Li(2)-S(3) bond length is 2.82 Å. The Li(2)-S(4) bond length is 2.85 Å. There is one shorter (2.81 Å) and one longer (2.87 Å) Li(2)-S(1) bond length. There is one shorter (2.79 Å) and one longer (2.89 Å) Li(2)-S(2) bond length. There are two inequivalent Pr sites. In the first Pr site, Pr(1) is bonded to one S(3), one S(4), two equivalent S(1), and two equivalent S(2) atoms to form PrS6 octahedra that share corners with two equivalent Li(2)S6 octahedra, corners with four equivalent Pr(1)S6 octahedra, edges with four equivalent Li(1)S6 octahedra, edges with four equivalent Li(2)S6 octahedra, and edges with four equivalent Pr(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 1-2°. The Pr(1)-S(3) bond length is 2.95 Å. The Pr(1)-S(4) bond length is 2.86 Å. There is one shorter (2.83 Å) and one longer (2.85 Å) Pr(1)-S(1) bond length. Both Pr(1)-S(2) bond lengths are 2.84 Å. In the second Pr site, Pr(2) is bonded to one S(1), one S(2), two equivalent S(3), and two equivalent S(4) atoms to form PrS6 octahedra that share corners with two equivalent Li(1)S6 octahedra, corners with four equivalent Pr(2)S6 octahedra, edges with four equivalent Li(1)S6 octahedra, edges with four equivalent Li(2)S6 octahedra, and edges with four equivalent Pr(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 1-3°. The Pr(2)-S(1) bond length is 2.75 Å. The Pr(2)-S(2) bond length is 2.95 Å. Both Pr(2)-S(3) bond lengths are 2.84 Å. There is one shorter (2.83 Å) and one longer (2.85 Å) Pr(2)-S(4) bond length. There are four inequivalent S sites. In the first S site, S(1) is bonded to one Li(1), two equivalent Li(2), one Pr(2), and two equivalent Pr(1) atoms to form a mixture of edge and corner-sharing SLi3Pr3 octahedra. The corner-sharing octahedral tilt angles range from 1-2°. In the second S site, S(2) is bonded to one Li(1), two equivalent Li(2), one Pr(2), and two equivalent Pr(1) atoms to form a mixture of edge and corner-sharing SLi3Pr3 octahedra. The corner-sharing octahedral tilt angles range from 1-2°. In the third S site, S(3) is bonded to one Li(2), two equivalent Li(1), one Pr(1), and two equivalent Pr(2) atoms to form a mixture of edge and corner-sharing SLi3Pr3 octahedra. The corner-sharing octahedral tilt angles range from 1-2°. In the fourth S site, S(4) is bonded to one Li(2), two equivalent Li(1), one Pr(1), and two equivalent Pr(2) atoms to form a mixture of edge and corner-sharing SLi3Pr3 octahedra. The corner-sharing octahedral tilt angles range from 1-3°.