LiZn2Al4O8 crystallizes in the orthorhombic Imm2 space group. Li(1) is bonded to two equivalent O(1) and two equivalent O(3) atoms to form distorted LiO4 tetrahedra that share corners with six equivalent Al(2)O6 octahedra, corners with two equivalent Al(1)O4 tetrahedra, and  an edgeedge with one Al(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 43-62°. Zn(1) is bonded in a 5-coordinate geometry to one O(2), two equivalent O(1), and two equivalent O(4) atoms. There are three inequivalent Al sites. In the first Al site, Al(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form AlO4 tetrahedra that share corners with six equivalent Al(2)O6 octahedra and corners with two equivalent Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 54-57°. In the second Al site, Al(2) is bonded to one O(1), one O(4), two equivalent O(2), and two equivalent O(3) atoms to form AlO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Al(1)O4 tetrahedra, corners with three equivalent Al(3)O4 tetrahedra, and edges with two equivalent Al(2)O6 octahedra. In the third Al site, Al(3) is bonded to two equivalent O(3) and two equivalent O(4) atoms to form AlO4 tetrahedra that share corners with six equivalent Al(2)O6 octahedra and  an edgeedge with one Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 52-53°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to one Li(1), two equivalent Zn(1), one Al(1), and one Al(2) atom. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Zn(1), one Al(1), and two equivalent Al(2) atoms. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Al(3), and two equivalent Al(2) atoms. In the fourth O site, O(4) is bonded to two equivalent Zn(1), one Al(2), and one Al(3) atom to form a mixture of distorted edge and corner-sharing OAl2Zn2 tetrahedra.
LiZn2Al4O8 crystallizes in the orthorhombic Imm2 space group. Li(1) is bonded to two equivalent O(1) and two equivalent O(3) atoms to form distorted LiO4 tetrahedra that share corners with six equivalent Al(2)O6 octahedra, corners with two equivalent Al(1)O4 tetrahedra, and  an edgeedge with one Al(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 43-62°. Both Li(1)-O(1) bond lengths are 1.99 Å. Both Li(1)-O(3) bond lengths are 1.90 Å. Zn(1) is bonded in a 5-coordinate geometry to one O(2), two equivalent O(1), and two equivalent O(4) atoms. The Zn(1)-O(2) bond length is 2.00 Å. Both Zn(1)-O(1) bond lengths are 2.16 Å. Both Zn(1)-O(4) bond lengths are 2.06 Å. There are three inequivalent Al sites. In the first Al site, Al(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form AlO4 tetrahedra that share corners with six equivalent Al(2)O6 octahedra and corners with two equivalent Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 54-57°. Both Al(1)-O(1) bond lengths are 1.85 Å. Both Al(1)-O(2) bond lengths are 1.90 Å. In the second Al site, Al(2) is bonded to one O(1), one O(4), two equivalent O(2), and two equivalent O(3) atoms to form AlO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Al(1)O4 tetrahedra, corners with three equivalent Al(3)O4 tetrahedra, and edges with two equivalent Al(2)O6 octahedra. The Al(2)-O(1) bond length is 2.08 Å. The Al(2)-O(4) bond length is 1.92 Å. Both Al(2)-O(2) bond lengths are 2.02 Å. Both Al(2)-O(3) bond lengths are 2.00 Å. In the third Al site, Al(3) is bonded to two equivalent O(3) and two equivalent O(4) atoms to form AlO4 tetrahedra that share corners with six equivalent Al(2)O6 octahedra and  an edgeedge with one Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 52-53°. Both Al(3)-O(3) bond lengths are 1.93 Å. Both Al(3)-O(4) bond lengths are 1.80 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to one Li(1), two equivalent Zn(1), one Al(1), and one Al(2) atom. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Zn(1), one Al(1), and two equivalent Al(2) atoms. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Al(3), and two equivalent Al(2) atoms. In the fourth O site, O(4) is bonded to two equivalent Zn(1), one Al(2), and one Al(3) atom to form a mixture of distorted edge and corner-sharing OAl2Zn2 tetrahedra.