ZnFeO2 crystallizes in the triclinic P1 space group. There are four inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(2), two equivalent O(4), and two equivalent O(5) atoms to form distorted FeO5 trigonal bipyramids that share corners with two equivalent Fe(2)O6 octahedra, corners with two equivalent Fe(3)O6 octahedra, corners with two equivalent Zn(1)O5 square pyramids, corners with two equivalent Zn(2)O5 square pyramids,  an edgeedge with one Zn(2)O5 square pyramid, and edges with two equivalent Fe(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 49-55°. In the second Fe site, Fe(2) is bonded to one O(4), one O(8), two equivalent O(3), and two equivalent O(6) atoms to form FeO6 octahedra that share corners with two equivalent Zn(1)O5 square pyramids, corners with two equivalent Zn(2)O5 square pyramids, corners with two equivalent Fe(1)O5 trigonal bipyramids, edges with two equivalent Fe(2)O6 octahedra, edges with two equivalent Fe(3)O6 octahedra, and  a faceface with one Zn(1)O5 square pyramid. In the third Fe site, Fe(3) is bonded to one O(1), one O(6), two equivalent O(2), and two equivalent O(8) atoms to form distorted FeO6 octahedra that share corners with two equivalent Zn(1)O5 square pyramids, corners with two equivalent Zn(2)O5 square pyramids, corners with two equivalent Fe(1)O5 trigonal bipyramids, edges with two equivalent Fe(2)O6 octahedra, edges with two equivalent Fe(3)O6 octahedra, and  a faceface with one Zn(2)O5 square pyramid. In the fourth Fe site, Fe(4) is bonded in a 6-coordinate geometry to one O(3), one O(5), two equivalent O(1), and two equivalent O(7) atoms. There are four inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one O(4), two equivalent O(6), and two equivalent O(7) atoms to form distorted ZnO5 square pyramids that share corners with two equivalent Fe(2)O6 octahedra, corners with two equivalent Fe(3)O6 octahedra, corners with two equivalent Fe(1)O5 trigonal bipyramids, edges with two equivalent Zn(1)O5 square pyramids, and  a faceface with one Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 45-54°. In the second Zn site, Zn(2) is bonded to one O(1), two equivalent O(5), and two equivalent O(8) atoms to form distorted ZnO5 square pyramids that share corners with two equivalent Fe(2)O6 octahedra, corners with two equivalent Fe(3)O6 octahedra, corners with two equivalent Fe(1)O5 trigonal bipyramids, edges with two equivalent Zn(2)O5 square pyramids,  an edgeedge with one Fe(1)O5 trigonal bipyramid, and  a faceface with one Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-58°. In the third Zn site, Zn(3) is bonded in a distorted T-shaped geometry to one O(3), one O(7), and one O(8) atom. In the fourth Zn site, Zn(4) is bonded in a 3-coordinate geometry to one O(5), one O(6), and two equivalent O(2) atoms. There are eight inequivalent O sites. In the first O site, O(1) is bonded to one Fe(3), two equivalent Fe(4), and one Zn(2) atom to form distorted OZnFe3 trigonal pyramids that share corners with two equivalent O(2)Zn2Fe3 trigonal bipyramids, corners with two equivalent O(7)Zn3Fe2 trigonal bipyramids, corners with two equivalent O(1)ZnFe3 trigonal pyramids, corners with two equivalent O(3)ZnFe3 trigonal pyramids, edges with two equivalent O(5)Zn3Fe3 square pyramids, and  an edgeedge with one O(7)Zn3Fe2 trigonal bipyramid. In the second O site, O(2) is bonded to one Fe(1), two equivalent Fe(3), and two equivalent Zn(4) atoms to form distorted OZn2Fe3 trigonal bipyramids that share corners with two equivalent O(1)ZnFe3 trigonal pyramids, corners with two equivalent O(4)ZnFe3 trigonal pyramids, edges with two equivalent O(5)Zn3Fe3 square pyramids, and edges with two equivalent O(2)Zn2Fe3 trigonal bipyramids. In the third O site, O(3) is bonded to one Fe(4), two equivalent Fe(2), and one Zn(3) atom to form distorted OZnFe3 trigonal pyramids that share  a cornercorner with one O(5)Zn3Fe3 square pyramid,  a cornercorner with one O(7)Zn3Fe2 trigonal bipyramid, corners with two equivalent O(1)ZnFe3 trigonal pyramids, corners with two equivalent O(3)ZnFe3 trigonal pyramids, corners with two equivalent O(4)ZnFe3 trigonal pyramids, and  an edgeedge with one O(7)Zn3Fe2 trigonal bipyramid. In the fourth O site, O(4) is bonded to one Fe(2), two equivalent Fe(1), and one Zn(1) atom to form OZnFe3 trigonal pyramids that share corners with two equivalent O(5)Zn3Fe3 square pyramids, corners with two equivalent O(2)Zn2Fe3 trigonal bipyramids, corners with two equivalent O(7)Zn3Fe2 trigonal bipyramids, corners with two equivalent O(3)ZnFe3 trigonal pyramids, corners with two equivalent O(4)ZnFe3 trigonal pyramids, and  an edgeedge with one O(5)Zn3Fe3 square pyramid. In the fifth O site, O(5) is bonded to one Fe(4), two equivalent Fe(1), one Zn(4), and two equivalent Zn(2) atoms to form distorted OZn3Fe3 square pyramids that share corners with two equivalent O(7)Zn3Fe2 trigonal bipyramids,  a cornercorner with one O(3)ZnFe3 trigonal pyramid, corners with two equivalent O(4)ZnFe3 trigonal pyramids, edges with two equivalent O(5)Zn3Fe3 square pyramids, edges with two equivalent O(2)Zn2Fe3 trigonal bipyramids,  an edgeedge with one O(4)ZnFe3 trigonal pyramid, and edges with two equivalent O(1)ZnFe3 trigonal pyramids. In the sixth O site, O(6) is bonded in a 6-coordinate geometry to one Fe(3), two equivalent Fe(2), one Zn(4), and two equivalent Zn(1) atoms. In the seventh O site, O(7) is bonded to two equivalent Fe(4), one Zn(3), and two equivalent Zn(1) atoms to form distorted OZn3Fe2 trigonal bipyramids that share corners with two equivalent O(5)Zn3Fe3 square pyramids,  a cornercorner with one O(3)ZnFe3 trigonal pyramid, corners with two equivalent O(1)ZnFe3 trigonal pyramids, corners with two equivalent O(4)ZnFe3 trigonal pyramids, edges with two equivalent O(7)Zn3Fe2 trigonal bipyramids,  an edgeedge with one O(1)ZnFe3 trigonal pyramid, and  an edgeedge with one O(3)ZnFe3 trigonal pyramid. In the eighth O site, O(8) is bonded in a 6-coordinate geometry to one Fe(2), two equivalent Fe(3), one Zn(3), and two equivalent Zn(2) atoms.
ZnFeO2 crystallizes in the triclinic P1 space group. There are four inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(2), two equivalent O(4), and two equivalent O(5) atoms to form distorted FeO5 trigonal bipyramids that share corners with two equivalent Fe(2)O6 octahedra, corners with two equivalent Fe(3)O6 octahedra, corners with two equivalent Zn(1)O5 square pyramids, corners with two equivalent Zn(2)O5 square pyramids,  an edgeedge with one Zn(2)O5 square pyramid, and edges with two equivalent Fe(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 49-55°. The Fe(1)-O(2) bond length is 1.97 Å. There is one shorter (1.99 Å) and one longer (2.01 Å) Fe(1)-O(4) bond length. There is one shorter (2.06 Å) and one longer (2.14 Å) Fe(1)-O(5) bond length. In the second Fe site, Fe(2) is bonded to one O(4), one O(8), two equivalent O(3), and two equivalent O(6) atoms to form FeO6 octahedra that share corners with two equivalent Zn(1)O5 square pyramids, corners with two equivalent Zn(2)O5 square pyramids, corners with two equivalent Fe(1)O5 trigonal bipyramids, edges with two equivalent Fe(2)O6 octahedra, edges with two equivalent Fe(3)O6 octahedra, and  a faceface with one Zn(1)O5 square pyramid. The Fe(2)-O(4) bond length is 2.06 Å. The Fe(2)-O(8) bond length is 2.05 Å. There is one shorter (2.00 Å) and one longer (2.02 Å) Fe(2)-O(3) bond length. There is one shorter (2.15 Å) and one longer (2.18 Å) Fe(2)-O(6) bond length. In the third Fe site, Fe(3) is bonded to one O(1), one O(6), two equivalent O(2), and two equivalent O(8) atoms to form distorted FeO6 octahedra that share corners with two equivalent Zn(1)O5 square pyramids, corners with two equivalent Zn(2)O5 square pyramids, corners with two equivalent Fe(1)O5 trigonal bipyramids, edges with two equivalent Fe(2)O6 octahedra, edges with two equivalent Fe(3)O6 octahedra, and  a faceface with one Zn(2)O5 square pyramid. The Fe(3)-O(1) bond length is 2.00 Å. The Fe(3)-O(6) bond length is 2.15 Å. Both Fe(3)-O(2) bond lengths are 2.24 Å. There is one shorter (2.27 Å) and one longer (2.36 Å) Fe(3)-O(8) bond length. In the fourth Fe site, Fe(4) is bonded in a 6-coordinate geometry to one O(3), one O(5), two equivalent O(1), and two equivalent O(7) atoms. The Fe(4)-O(3) bond length is 2.16 Å. The Fe(4)-O(5) bond length is 2.71 Å. Both Fe(4)-O(1) bond lengths are 2.01 Å. There is one shorter (2.25 Å) and one longer (2.26 Å) Fe(4)-O(7) bond length. There are four inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one O(4), two equivalent O(6), and two equivalent O(7) atoms to form distorted ZnO5 square pyramids that share corners with two equivalent Fe(2)O6 octahedra, corners with two equivalent Fe(3)O6 octahedra, corners with two equivalent Fe(1)O5 trigonal bipyramids, edges with two equivalent Zn(1)O5 square pyramids, and  a faceface with one Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 45-54°. The Zn(1)-O(4) bond length is 2.11 Å. There is one shorter (2.16 Å) and one longer (2.41 Å) Zn(1)-O(6) bond length. There is one shorter (2.02 Å) and one longer (2.09 Å) Zn(1)-O(7) bond length. In the second Zn site, Zn(2) is bonded to one O(1), two equivalent O(5), and two equivalent O(8) atoms to form distorted ZnO5 square pyramids that share corners with two equivalent Fe(2)O6 octahedra, corners with two equivalent Fe(3)O6 octahedra, corners with two equivalent Fe(1)O5 trigonal bipyramids, edges with two equivalent Zn(2)O5 square pyramids,  an edgeedge with one Fe(1)O5 trigonal bipyramid, and  a faceface with one Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-58°. The Zn(2)-O(1) bond length is 2.00 Å. There is one shorter (2.19 Å) and one longer (2.21 Å) Zn(2)-O(5) bond length. There is one shorter (2.07 Å) and one longer (2.40 Å) Zn(2)-O(8) bond length. In the third Zn site, Zn(3) is bonded in a distorted T-shaped geometry to one O(3), one O(7), and one O(8) atom. The Zn(3)-O(3) bond length is 2.00 Å. The Zn(3)-O(7) bond length is 2.15 Å. The Zn(3)-O(8) bond length is 2.27 Å. In the fourth Zn site, Zn(4) is bonded in a 3-coordinate geometry to one O(5), one O(6), and two equivalent O(2) atoms. The Zn(4)-O(5) bond length is 2.19 Å. The Zn(4)-O(6) bond length is 2.52 Å. There is one shorter (2.12 Å) and one longer (2.13 Å) Zn(4)-O(2) bond length. There are eight inequivalent O sites. In the first O site, O(1) is bonded to one Fe(3), two equivalent Fe(4), and one Zn(2) atom to form distorted OZnFe3 trigonal pyramids that share corners with two equivalent O(2)Zn2Fe3 trigonal bipyramids, corners with two equivalent O(7)Zn3Fe2 trigonal bipyramids, corners with two equivalent O(1)ZnFe3 trigonal pyramids, corners with two equivalent O(3)ZnFe3 trigonal pyramids, edges with two equivalent O(5)Zn3Fe3 square pyramids, and  an edgeedge with one O(7)Zn3Fe2 trigonal bipyramid. In the second O site, O(2) is bonded to one Fe(1), two equivalent Fe(3), and two equivalent Zn(4) atoms to form distorted OZn2Fe3 trigonal bipyramids that share corners with two equivalent O(1)ZnFe3 trigonal pyramids, corners with two equivalent O(4)ZnFe3 trigonal pyramids, edges with two equivalent O(5)Zn3Fe3 square pyramids, and edges with two equivalent O(2)Zn2Fe3 trigonal bipyramids. In the third O site, O(3) is bonded to one Fe(4), two equivalent Fe(2), and one Zn(3) atom to form distorted OZnFe3 trigonal pyramids that share  a cornercorner with one O(5)Zn3Fe3 square pyramid,  a cornercorner with one O(7)Zn3Fe2 trigonal bipyramid, corners with two equivalent O(1)ZnFe3 trigonal pyramids, corners with two equivalent O(3)ZnFe3 trigonal pyramids, corners with two equivalent O(4)ZnFe3 trigonal pyramids, and  an edgeedge with one O(7)Zn3Fe2 trigonal bipyramid. In the fourth O site, O(4) is bonded to one Fe(2), two equivalent Fe(1), and one Zn(1) atom to form OZnFe3 trigonal pyramids that share corners with two equivalent O(5)Zn3Fe3 square pyramids, corners with two equivalent O(2)Zn2Fe3 trigonal bipyramids, corners with two equivalent O(7)Zn3Fe2 trigonal bipyramids, corners with two equivalent O(3)ZnFe3 trigonal pyramids, corners with two equivalent O(4)ZnFe3 trigonal pyramids, and  an edgeedge with one O(5)Zn3Fe3 square pyramid. In the fifth O site, O(5) is bonded to one Fe(4), two equivalent Fe(1), one Zn(4), and two equivalent Zn(2) atoms to form distorted OZn3Fe3 square pyramids that share corners with two equivalent O(7)Zn3Fe2 trigonal bipyramids,  a cornercorner with one O(3)ZnFe3 trigonal pyramid, corners with two equivalent O(4)ZnFe3 trigonal pyramids, edges with two equivalent O(5)Zn3Fe3 square pyramids, edges with two equivalent O(2)Zn2Fe3 trigonal bipyramids,  an edgeedge with one O(4)ZnFe3 trigonal pyramid, and edges with two equivalent O(1)ZnFe3 trigonal pyramids. In the sixth O site, O(6) is bonded in a 6-coordinate geometry to one Fe(3), two equivalent Fe(2), one Zn(4), and two equivalent Zn(1) atoms. In the seventh O site, O(7) is bonded to two equivalent Fe(4), one Zn(3), and two equivalent Zn(1) atoms to form distorted OZn3Fe2 trigonal bipyramids that share corners with two equivalent O(5)Zn3Fe3 square pyramids,  a cornercorner with one O(3)ZnFe3 trigonal pyramid, corners with two equivalent O(1)ZnFe3 trigonal pyramids, corners with two equivalent O(4)ZnFe3 trigonal pyramids, edges with two equivalent O(7)Zn3Fe2 trigonal bipyramids,  an edgeedge with one O(1)ZnFe3 trigonal pyramid, and  an edgeedge with one O(3)ZnFe3 trigonal pyramid. In the eighth O site, O(8) is bonded in a 6-coordinate geometry to one Fe(2), two equivalent Fe(3), one Zn(3), and two equivalent Zn(2) atoms.