LiZr2S4 crystallizes in the monoclinic P2/m space group. Li(1) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form LiS6 octahedra that share corners with six equivalent Zr(1)S6 octahedra, edges with two equivalent Li(1)S6 octahedra, edges with two equivalent Zr(1)S6 octahedra, and edges with four equivalent Zr(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 1-2°. There are two inequivalent Zr sites. In the first Zr site, Zr(1) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form ZrS6 octahedra that share corners with six equivalent Li(1)S6 octahedra, edges with two equivalent Li(1)S6 octahedra, edges with two equivalent Zr(1)S6 octahedra, and edges with four equivalent Zr(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 1-2°. In the second Zr site, Zr(2) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form ZrS6 octahedra that share edges with two equivalent Zr(2)S6 octahedra, edges with four equivalent Li(1)S6 octahedra, and edges with four equivalent Zr(1)S6 octahedra. There are two inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Li(1), one Zr(2), and two equivalent Zr(1) atoms to form a mixture of edge and corner-sharing SLi2Zr3 square pyramids. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to one Li(1), one Zr(1), and two equivalent Zr(2) atoms.
LiZr2S4 crystallizes in the monoclinic P2/m space group. Li(1) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form LiS6 octahedra that share corners with six equivalent Zr(1)S6 octahedra, edges with two equivalent Li(1)S6 octahedra, edges with two equivalent Zr(1)S6 octahedra, and edges with four equivalent Zr(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 1-2°. Both Li(1)-S(2) bond lengths are 2.62 Å. All Li(1)-S(1) bond lengths are 2.63 Å. There are two inequivalent Zr sites. In the first Zr site, Zr(1) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form ZrS6 octahedra that share corners with six equivalent Li(1)S6 octahedra, edges with two equivalent Li(1)S6 octahedra, edges with two equivalent Zr(1)S6 octahedra, and edges with four equivalent Zr(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 1-2°. Both Zr(1)-S(2) bond lengths are 2.58 Å. All Zr(1)-S(1) bond lengths are 2.60 Å. In the second Zr site, Zr(2) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form ZrS6 octahedra that share edges with two equivalent Zr(2)S6 octahedra, edges with four equivalent Li(1)S6 octahedra, and edges with four equivalent Zr(1)S6 octahedra. Both Zr(2)-S(1) bond lengths are 2.59 Å. All Zr(2)-S(2) bond lengths are 2.58 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Li(1), one Zr(2), and two equivalent Zr(1) atoms to form a mixture of edge and corner-sharing SLi2Zr3 square pyramids. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to one Li(1), one Zr(1), and two equivalent Zr(2) atoms.