Li4Zr3O8 crystallizes in the orthorhombic C222 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form LiO6 octahedra that share corners with two equivalent Zr(2)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Zr(1)O6 octahedra, and edges with four equivalent Zr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-10°. In the second Li site, Li(2) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form LiO6 octahedra that share corners with four equivalent Li(3)O6 octahedra, edges with two equivalent Zr(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Zr(2)O6 octahedra. The corner-sharing octahedral tilt angles are 12°. In the third Li site, Li(3) is bonded to two equivalent O(3) and four equivalent O(1) atoms to form LiO6 octahedra that share corners with two equivalent Zr(1)O6 octahedra, corners with four equivalent Li(2)O6 octahedra, edges with two equivalent Zr(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Zr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-12°. There are two inequivalent Zr sites. In the first Zr site, Zr(1) is bonded to two equivalent O(3) and four equivalent O(1) atoms to form ZrO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Zr(2)O6 octahedra. The corner-sharing octahedra are not tilted. In the second Zr site, Zr(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form ZrO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with four equivalent Zr(2)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Zr(1)O6 octahedra, and edges with four equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-10°. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Li(3), one Zr(1), and one Zr(2) atom to form OLi3Zr2 square pyramids that share corners with two equivalent O(2)Li3Zr2 square pyramids, corners with seven equivalent O(1)Li3Zr2 square pyramids, edges with four equivalent O(3)Li3Zr3 octahedra, edges with two equivalent O(1)Li3Zr2 square pyramids, and edges with two equivalent O(2)Li3Zr2 square pyramids. In the second O site, O(2) is bonded to one Li(2), two equivalent Li(1), and two equivalent Zr(2) atoms to form OLi3Zr2 square pyramids that share corners with four equivalent O(3)Li3Zr3 octahedra,  a cornercorner with one O(2)Li3Zr2 square pyramid, corners with four equivalent O(1)Li3Zr2 square pyramids, edges with two equivalent O(3)Li3Zr3 octahedra, edges with two equivalent O(2)Li3Zr2 square pyramids, and edges with four equivalent O(1)Li3Zr2 square pyramids. The corner-sharing octahedral tilt angles range from 2-7°. In the third O site, O(3) is bonded to one Li(3), two equivalent Li(1), one Zr(1), and two equivalent Zr(2) atoms to form OLi3Zr3 octahedra that share corners with two equivalent O(3)Li3Zr3 octahedra, corners with four equivalent O(2)Li3Zr2 square pyramids, edges with two equivalent O(3)Li3Zr3 octahedra, edges with two equivalent O(2)Li3Zr2 square pyramids, and edges with eight equivalent O(1)Li3Zr2 square pyramids. The corner-sharing octahedra are not tilted.
Li4Zr3O8 crystallizes in the orthorhombic C222 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form LiO6 octahedra that share corners with two equivalent Zr(2)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Zr(1)O6 octahedra, and edges with four equivalent Zr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-10°. Both Li(1)-O(1) bond lengths are 2.46 Å. Both Li(1)-O(2) bond lengths are 2.22 Å. Both Li(1)-O(3) bond lengths are 2.16 Å. In the second Li site, Li(2) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form LiO6 octahedra that share corners with four equivalent Li(3)O6 octahedra, edges with two equivalent Zr(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Zr(2)O6 octahedra. The corner-sharing octahedral tilt angles are 12°. Both Li(2)-O(2) bond lengths are 2.10 Å. All Li(2)-O(1) bond lengths are 2.24 Å. In the third Li site, Li(3) is bonded to two equivalent O(3) and four equivalent O(1) atoms to form LiO6 octahedra that share corners with two equivalent Zr(1)O6 octahedra, corners with four equivalent Li(2)O6 octahedra, edges with two equivalent Zr(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Zr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-12°. Both Li(3)-O(3) bond lengths are 2.34 Å. All Li(3)-O(1) bond lengths are 2.16 Å. There are two inequivalent Zr sites. In the first Zr site, Zr(1) is bonded to two equivalent O(3) and four equivalent O(1) atoms to form ZrO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Zr(2)O6 octahedra. The corner-sharing octahedra are not tilted. Both Zr(1)-O(3) bond lengths are 2.18 Å. All Zr(1)-O(1) bond lengths are 2.08 Å. In the second Zr site, Zr(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form ZrO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with four equivalent Zr(2)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Zr(1)O6 octahedra, and edges with four equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-10°. Both Zr(2)-O(1) bond lengths are 2.08 Å. Both Zr(2)-O(2) bond lengths are 2.07 Å. Both Zr(2)-O(3) bond lengths are 2.31 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Li(3), one Zr(1), and one Zr(2) atom to form OLi3Zr2 square pyramids that share corners with two equivalent O(2)Li3Zr2 square pyramids, corners with seven equivalent O(1)Li3Zr2 square pyramids, edges with four equivalent O(3)Li3Zr3 octahedra, edges with two equivalent O(1)Li3Zr2 square pyramids, and edges with two equivalent O(2)Li3Zr2 square pyramids. In the second O site, O(2) is bonded to one Li(2), two equivalent Li(1), and two equivalent Zr(2) atoms to form OLi3Zr2 square pyramids that share corners with four equivalent O(3)Li3Zr3 octahedra,  a cornercorner with one O(2)Li3Zr2 square pyramid, corners with four equivalent O(1)Li3Zr2 square pyramids, edges with two equivalent O(3)Li3Zr3 octahedra, edges with two equivalent O(2)Li3Zr2 square pyramids, and edges with four equivalent O(1)Li3Zr2 square pyramids. The corner-sharing octahedral tilt angles range from 2-7°. In the third O site, O(3) is bonded to one Li(3), two equivalent Li(1), one Zr(1), and two equivalent Zr(2) atoms to form OLi3Zr3 octahedra that share corners with two equivalent O(3)Li3Zr3 octahedra, corners with four equivalent O(2)Li3Zr2 square pyramids, edges with two equivalent O(3)Li3Zr3 octahedra, edges with two equivalent O(2)Li3Zr2 square pyramids, and edges with eight equivalent O(1)Li3Zr2 square pyramids. The corner-sharing octahedra are not tilted.