LiZn2(FeO2)4 crystallizes in the orthorhombic Imm2 space group. Li(1) is bonded in a 4-coordinate geometry to one Fe(2), two equivalent Fe(3), two equivalent O(1), and two equivalent O(3) atoms. There are three inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to two equivalent O(3) and two equivalent O(4) atoms to form FeO4 tetrahedra that share corners with six equivalent Zn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 57-63°. In the second Fe site, Fe(2) is bonded in a 5-coordinate geometry to one Li(1), two equivalent O(1), and two equivalent O(2) atoms. In the third Fe site, Fe(3) is bonded in a 7-coordinate geometry to one Li(1), one O(1), one O(4), two equivalent O(2), and two equivalent O(3) atoms. Zn(1) is bonded to one O(2), one O(3), two equivalent O(1), and two equivalent O(4) atoms to form ZnO6 octahedra that share corners with three equivalent Fe(1)O4 tetrahedra and edges with two equivalent Zn(1)O6 octahedra. There are four inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to one Li(1), one Fe(2), one Fe(3), and two equivalent Zn(1) atoms. In the second O site, O(2) is bonded to one Fe(2), two equivalent Fe(3), and one Zn(1) atom to form distorted OZnFe3 tetrahedra that share  a cornercorner with one O(2)ZnFe3 tetrahedra, corners with four equivalent O(4)Zn2Fe2 trigonal pyramids, and  an edgeedge with one O(2)ZnFe3 tetrahedra. In the third O site, O(3) is bonded in a 5-coordinate geometry to one Li(1), one Fe(1), two equivalent Fe(3), and one Zn(1) atom. In the fourth O site, O(4) is bonded to one Fe(1), one Fe(3), and two equivalent Zn(1) atoms to form distorted OZn2Fe2 trigonal pyramids that share corners with four equivalent O(2)ZnFe3 tetrahedra,  a cornercorner with one O(4)Zn2Fe2 trigonal pyramid, and  an edgeedge with one O(4)Zn2Fe2 trigonal pyramid.
LiZn2(FeO2)4 crystallizes in the orthorhombic Imm2 space group. Li(1) is bonded in a 4-coordinate geometry to one Fe(2), two equivalent Fe(3), two equivalent O(1), and two equivalent O(3) atoms. The Li(1)-Fe(2) bond length is 2.19 Å. Both Li(1)-Fe(3) bond lengths are 2.28 Å. Both Li(1)-O(1) bond lengths are 1.77 Å. Both Li(1)-O(3) bond lengths are 1.94 Å. There are three inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to two equivalent O(3) and two equivalent O(4) atoms to form FeO4 tetrahedra that share corners with six equivalent Zn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 57-63°. Both Fe(1)-O(3) bond lengths are 2.00 Å. Both Fe(1)-O(4) bond lengths are 1.95 Å. In the second Fe site, Fe(2) is bonded in a 5-coordinate geometry to one Li(1), two equivalent O(1), and two equivalent O(2) atoms. Both Fe(2)-O(1) bond lengths are 2.17 Å. Both Fe(2)-O(2) bond lengths are 1.95 Å. In the third Fe site, Fe(3) is bonded in a 7-coordinate geometry to one Li(1), one O(1), one O(4), two equivalent O(2), and two equivalent O(3) atoms. The Fe(3)-O(1) bond length is 2.33 Å. The Fe(3)-O(4) bond length is 2.01 Å. Both Fe(3)-O(2) bond lengths are 1.97 Å. Both Fe(3)-O(3) bond lengths are 2.15 Å. Zn(1) is bonded to one O(2), one O(3), two equivalent O(1), and two equivalent O(4) atoms to form ZnO6 octahedra that share corners with three equivalent Fe(1)O4 tetrahedra and edges with two equivalent Zn(1)O6 octahedra. The Zn(1)-O(2) bond length is 2.18 Å. The Zn(1)-O(3) bond length is 2.27 Å. Both Zn(1)-O(1) bond lengths are 2.06 Å. Both Zn(1)-O(4) bond lengths are 2.20 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), one Fe(2), one Fe(3), and two equivalent Zn(1) atoms. In the second O site, O(2) is bonded to one Fe(2), two equivalent Fe(3), and one Zn(1) atom to form distorted OZnFe3 tetrahedra that share  a cornercorner with one O(2)ZnFe3 tetrahedra, corners with four equivalent O(4)Zn2Fe2 trigonal pyramids, and  an edgeedge with one O(2)ZnFe3 tetrahedra. In the third O site, O(3) is bonded in a 5-coordinate geometry to one Li(1), one Fe(1), two equivalent Fe(3), and one Zn(1) atom. In the fourth O site, O(4) is bonded to one Fe(1), one Fe(3), and two equivalent Zn(1) atoms to form distorted OZn2Fe2 trigonal pyramids that share corners with four equivalent O(2)ZnFe3 tetrahedra,  a cornercorner with one O(4)Zn2Fe2 trigonal pyramid, and  an edgeedge with one O(4)Zn2Fe2 trigonal pyramid.