LiZn2Al4O8 crystallizes in the monoclinic C2/m space group. Li(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form distorted LiO6 octahedra that share corners with six equivalent Al(3)O6 octahedra, edges with two equivalent Al(2)O6 octahedra, and edges with four equivalent Zn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-11°. Zn(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form ZnO6 octahedra that share edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Zn(1)O6 octahedra, edges with two equivalent Al(2)O6 octahedra, and edges with two equivalent Al(3)O6 octahedra. There are three inequivalent Al sites. In the first Al site, Al(1) is bonded in a 4-coordinate geometry to one O(1), one O(3), and two equivalent O(2) atoms. In the second Al site, Al(2) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form AlO6 octahedra that share edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Al(3)O6 octahedra, and edges with four equivalent Zn(1)O6 octahedra. In the third Al site, Al(3) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form AlO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent Al(2)O6 octahedra, and edges with four equivalent Zn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-11°. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), two equivalent Zn(1), one Al(1), and one Al(3) atom to form distorted OLiAl2Zn2 square pyramids that share corners with two equivalent O(2)LiAl3Zn square pyramids, corners with four equivalent O(1)LiAl2Zn2 square pyramids, and edges with six equivalent O(2)LiAl3Zn square pyramids. In the second O site, O(2) is bonded to one Li(1), one Zn(1), one Al(1), one Al(2), and one Al(3) atom to form OLiAl3Zn square pyramids that share  a cornercorner with one O(1)LiAl2Zn2 square pyramid, corners with five equivalent O(2)LiAl3Zn square pyramids, edges with three equivalent O(1)LiAl2Zn2 square pyramids, and edges with three equivalent O(2)LiAl3Zn square pyramids. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to two equivalent Zn(1), one Al(1), and one Al(2) atom.
LiZn2Al4O8 crystallizes in the monoclinic C2/m space group. Li(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form distorted LiO6 octahedra that share corners with six equivalent Al(3)O6 octahedra, edges with two equivalent Al(2)O6 octahedra, and edges with four equivalent Zn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-11°. Both Li(1)-O(1) bond lengths are 2.25 Å. All Li(1)-O(2) bond lengths are 2.14 Å. Zn(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form ZnO6 octahedra that share edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Zn(1)O6 octahedra, edges with two equivalent Al(2)O6 octahedra, and edges with two equivalent Al(3)O6 octahedra. Both Zn(1)-O(1) bond lengths are 2.25 Å. Both Zn(1)-O(2) bond lengths are 2.16 Å. Both Zn(1)-O(3) bond lengths are 2.00 Å. There are three inequivalent Al sites. In the first Al site, Al(1) is bonded in a 4-coordinate geometry to one O(1), one O(3), and two equivalent O(2) atoms. The Al(1)-O(1) bond length is 1.86 Å. The Al(1)-O(3) bond length is 1.79 Å. Both Al(1)-O(2) bond lengths are 1.96 Å. In the second Al site, Al(2) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form AlO6 octahedra that share edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Al(3)O6 octahedra, and edges with four equivalent Zn(1)O6 octahedra. Both Al(2)-O(3) bond lengths are 1.86 Å. All Al(2)-O(2) bond lengths are 2.02 Å. In the third Al site, Al(3) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form AlO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent Al(2)O6 octahedra, and edges with four equivalent Zn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-11°. Both Al(3)-O(1) bond lengths are 1.99 Å. All Al(3)-O(2) bond lengths are 2.03 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), two equivalent Zn(1), one Al(1), and one Al(3) atom to form distorted OLiAl2Zn2 square pyramids that share corners with two equivalent O(2)LiAl3Zn square pyramids, corners with four equivalent O(1)LiAl2Zn2 square pyramids, and edges with six equivalent O(2)LiAl3Zn square pyramids. In the second O site, O(2) is bonded to one Li(1), one Zn(1), one Al(1), one Al(2), and one Al(3) atom to form OLiAl3Zn square pyramids that share  a cornercorner with one O(1)LiAl2Zn2 square pyramid, corners with five equivalent O(2)LiAl3Zn square pyramids, edges with three equivalent O(1)LiAl2Zn2 square pyramids, and edges with three equivalent O(2)LiAl3Zn square pyramids. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to two equivalent Zn(1), one Al(1), and one Al(2) atom.