Li3Y3ZrO8 crystallizes in the orthorhombic C222 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a square co-planar geometry to two equivalent O(2) and two equivalent O(3) atoms. In the second Li site, Li(2) is bonded in a rectangular see-saw-like geometry to four equivalent O(1) atoms. There are two inequivalent Y sites. In the first Y site, Y(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form YO6 octahedra that share corners with four equivalent Y(1)O6 octahedra, edges with two equivalent Y(2)O6 octahedra, and edges with two equivalent Zr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 20-25°. In the second Y site, Y(2) is bonded to two equivalent O(3) and four equivalent O(1) atoms to form YO6 octahedra that share corners with four equivalent Zr(1)O6 octahedra and edges with four equivalent Y(1)O6 octahedra. The corner-sharing octahedral tilt angles are 19°. Zr(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form ZrO6 octahedra that share corners with four equivalent Y(2)O6 octahedra and edges with four equivalent Y(1)O6 octahedra. The corner-sharing octahedral tilt angles are 19°. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted see-saw-like geometry to one Li(2), one Y(1), one Y(2), and one Zr(1) atom. In the second O site, O(2) is bonded to two equivalent Li(1), two equivalent Y(1), and one Zr(1) atom to form distorted OLi2Y2Zr square pyramids that share  a cornercorner with one O(2)Li2Y2Zr square pyramid, corners with four equivalent O(3)Li2Y3 square pyramids, edges with two equivalent O(2)Li2Y2Zr square pyramids, and edges with two equivalent O(3)Li2Y3 square pyramids. In the third O site, O(3) is bonded to two equivalent Li(1), one Y(2), and two equivalent Y(1) atoms to form OLi2Y3 square pyramids that share  a cornercorner with one O(3)Li2Y3 square pyramid, corners with four equivalent O(2)Li2Y2Zr square pyramids, edges with two equivalent O(2)Li2Y2Zr square pyramids, and edges with two equivalent O(3)Li2Y3 square pyramids.
Li3Y3ZrO8 crystallizes in the orthorhombic C222 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a square co-planar geometry to two equivalent O(2) and two equivalent O(3) atoms. Both Li(1)-O(2) bond lengths are 2.27 Å. Both Li(1)-O(3) bond lengths are 2.19 Å. In the second Li site, Li(2) is bonded in a rectangular see-saw-like geometry to four equivalent O(1) atoms. All Li(2)-O(1) bond lengths are 2.07 Å. There are two inequivalent Y sites. In the first Y site, Y(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form YO6 octahedra that share corners with four equivalent Y(1)O6 octahedra, edges with two equivalent Y(2)O6 octahedra, and edges with two equivalent Zr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 20-25°. Both Y(1)-O(1) bond lengths are 2.35 Å. Both Y(1)-O(2) bond lengths are 2.23 Å. Both Y(1)-O(3) bond lengths are 2.23 Å. In the second Y site, Y(2) is bonded to two equivalent O(3) and four equivalent O(1) atoms to form YO6 octahedra that share corners with four equivalent Zr(1)O6 octahedra and edges with four equivalent Y(1)O6 octahedra. The corner-sharing octahedral tilt angles are 19°. Both Y(2)-O(3) bond lengths are 2.29 Å. All Y(2)-O(1) bond lengths are 2.29 Å. Zr(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form ZrO6 octahedra that share corners with four equivalent Y(2)O6 octahedra and edges with four equivalent Y(1)O6 octahedra. The corner-sharing octahedral tilt angles are 19°. Both Zr(1)-O(2) bond lengths are 2.19 Å. All Zr(1)-O(1) bond lengths are 2.14 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted see-saw-like geometry to one Li(2), one Y(1), one Y(2), and one Zr(1) atom. In the second O site, O(2) is bonded to two equivalent Li(1), two equivalent Y(1), and one Zr(1) atom to form distorted OLi2Y2Zr square pyramids that share  a cornercorner with one O(2)Li2Y2Zr square pyramid, corners with four equivalent O(3)Li2Y3 square pyramids, edges with two equivalent O(2)Li2Y2Zr square pyramids, and edges with two equivalent O(3)Li2Y3 square pyramids. In the third O site, O(3) is bonded to two equivalent Li(1), one Y(2), and two equivalent Y(1) atoms to form OLi2Y3 square pyramids that share  a cornercorner with one O(3)Li2Y3 square pyramid, corners with four equivalent O(2)Li2Y2Zr square pyramids, edges with two equivalent O(2)Li2Y2Zr square pyramids, and edges with two equivalent O(3)Li2Y3 square pyramids.