LiZn2(FeO2)4 crystallizes in the monoclinic C2/m space group. Li(1) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form distorted LiO6 octahedra that share corners with six equivalent Fe(3)O6 octahedra, edges with two equivalent Fe(2)O6 octahedra, and edges with four equivalent Zn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-4°. There are three inequivalent Fe sites. In the first Fe site, Fe(1) is bonded in a 4-coordinate geometry to one O(1), one O(2), and two equivalent O(3) atoms. In the second Fe site, Fe(2) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form FeO6 octahedra that share edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Fe(3)O6 octahedra, and edges with four equivalent Zn(1)O6 octahedra. In the third Fe site, Fe(3) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form FeO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent Fe(2)O6 octahedra, and edges with four equivalent Zn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-4°. 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 Fe(2)O6 octahedra, edges with two equivalent Fe(3)O6 octahedra, and edges with two equivalent Zn(1)O6 octahedra. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Fe(1), one Fe(2), and two equivalent Zn(1) atoms to form distorted OZn2Fe2 trigonal pyramids that share corners with three equivalent O(2)LiZn2Fe2 square pyramids, corners with six equivalent O(3)LiZnFe3 square pyramids, corners with three equivalent O(1)Zn2Fe2 trigonal pyramids,  an edgeedge with one O(2)LiZn2Fe2 square pyramid, and edges with two equivalent O(3)LiZnFe3 square pyramids. In the second O site, O(2) is bonded to one Li(1), one Fe(1), one Fe(3), and two equivalent Zn(1) atoms to form OLiZn2Fe2 square pyramids that share corners with two equivalent O(3)LiZnFe3 square pyramids, corners with four equivalent O(2)LiZn2Fe2 square pyramids, corners with three equivalent O(1)Zn2Fe2 trigonal pyramids, edges with six equivalent O(3)LiZnFe3 square pyramids, and  an edgeedge with one O(1)Zn2Fe2 trigonal pyramid. In the third O site, O(3) is bonded to one Li(1), one Fe(1), one Fe(2), one Fe(3), and one Zn(1) atom to form OLiZnFe3 square pyramids that share  a cornercorner with one O(2)LiZn2Fe2 square pyramid, corners with five equivalent O(3)LiZnFe3 square pyramids, corners with three equivalent O(1)Zn2Fe2 trigonal pyramids, edges with three equivalent O(2)LiZn2Fe2 square pyramids, edges with three equivalent O(3)LiZnFe3 square pyramids, and  an edgeedge with one O(1)Zn2Fe2 trigonal pyramid.
LiZn2(FeO2)4 crystallizes in the monoclinic C2/m space group. Li(1) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form distorted LiO6 octahedra that share corners with six equivalent Fe(3)O6 octahedra, edges with two equivalent Fe(2)O6 octahedra, and edges with four equivalent Zn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-4°. Both Li(1)-O(2) bond lengths are 2.21 Å. All Li(1)-O(3) bond lengths are 2.09 Å. There are three inequivalent Fe sites. In the first Fe site, Fe(1) is bonded in a 4-coordinate geometry to one O(1), one O(2), and two equivalent O(3) atoms. The Fe(1)-O(1) bond length is 1.90 Å. The Fe(1)-O(2) bond length is 1.92 Å. Both Fe(1)-O(3) bond lengths are 1.97 Å. In the second Fe site, Fe(2) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form FeO6 octahedra that share edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Fe(3)O6 octahedra, and edges with four equivalent Zn(1)O6 octahedra. Both Fe(2)-O(1) bond lengths are 2.01 Å. All Fe(2)-O(3) bond lengths are 2.10 Å. In the third Fe site, Fe(3) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form FeO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent Fe(2)O6 octahedra, and edges with four equivalent Zn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-4°. Both Fe(3)-O(2) bond lengths are 2.14 Å. All Fe(3)-O(3) bond lengths are 2.22 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 Fe(2)O6 octahedra, edges with two equivalent Fe(3)O6 octahedra, and edges with two equivalent Zn(1)O6 octahedra. Both Zn(1)-O(1) bond lengths are 2.01 Å. Both Zn(1)-O(2) bond lengths are 2.20 Å. Both Zn(1)-O(3) bond lengths are 2.22 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Fe(1), one Fe(2), and two equivalent Zn(1) atoms to form distorted OZn2Fe2 trigonal pyramids that share corners with three equivalent O(2)LiZn2Fe2 square pyramids, corners with six equivalent O(3)LiZnFe3 square pyramids, corners with three equivalent O(1)Zn2Fe2 trigonal pyramids,  an edgeedge with one O(2)LiZn2Fe2 square pyramid, and edges with two equivalent O(3)LiZnFe3 square pyramids. In the second O site, O(2) is bonded to one Li(1), one Fe(1), one Fe(3), and two equivalent Zn(1) atoms to form OLiZn2Fe2 square pyramids that share corners with two equivalent O(3)LiZnFe3 square pyramids, corners with four equivalent O(2)LiZn2Fe2 square pyramids, corners with three equivalent O(1)Zn2Fe2 trigonal pyramids, edges with six equivalent O(3)LiZnFe3 square pyramids, and  an edgeedge with one O(1)Zn2Fe2 trigonal pyramid. In the third O site, O(3) is bonded to one Li(1), one Fe(1), one Fe(2), one Fe(3), and one Zn(1) atom to form OLiZnFe3 square pyramids that share  a cornercorner with one O(2)LiZn2Fe2 square pyramid, corners with five equivalent O(3)LiZnFe3 square pyramids, corners with three equivalent O(1)Zn2Fe2 trigonal pyramids, edges with three equivalent O(2)LiZn2Fe2 square pyramids, edges with three equivalent O(3)LiZnFe3 square pyramids, and  an edgeedge with one O(1)Zn2Fe2 trigonal pyramid.