Li2Fe2OF4 crystallizes in the orthorhombic Cmc2_1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one F(1), two equivalent F(2), and two equivalent F(4) atoms to form LiOF5 octahedra that share  a cornercorner with one Fe(1)OF5 octahedra, corners with two equivalent Li(2)F6 octahedra, edges with two equivalent Li(1)OF5 octahedra, edges with two equivalent Fe(1)OF5 octahedra, and edges with three equivalent Li(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 17-59°. In the second Li site, Li(2) is bonded to one F(3), one F(4), two equivalent F(1), and two equivalent F(2) atoms to form LiF6 octahedra that share corners with two equivalent Li(1)OF5 octahedra, corners with two equivalent Fe(1)OF5 octahedra, edges with two equivalent Li(2)F6 octahedra, edges with three equivalent Li(1)OF5 octahedra, and edges with three equivalent Fe(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 14-17°. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(1), one F(2), two equivalent F(1), and two equivalent F(3) atoms to form FeOF5 octahedra that share  a cornercorner with one Li(1)OF5 octahedra, corners with two equivalent Li(2)F6 octahedra, edges with two equivalent Li(1)OF5 octahedra, edges with two equivalent Fe(1)OF5 octahedra, and edges with three equivalent Li(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 14-59°. In the second Fe site, Fe(2) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent F(3), and two equivalent F(4) atoms. O(1) is bonded to one Li(1), one Fe(1), and two equivalent Fe(2) atoms to form OLiFe3 tetrahedra that share corners with three equivalent F(1)Li3Fe2 square pyramids, corners with three equivalent F(2)Li4Fe square pyramids, corners with four equivalent F(4)Li3Fe2 square pyramids, corners with two equivalent O(1)LiFe3 tetrahedra, and  an edgeedge with one F(4)Li3Fe2 square pyramid. There are four inequivalent F sites. In the first F site, F(1) is bonded to one Li(1), two equivalent Li(2), and two equivalent Fe(1) atoms to form FLi3Fe2 square pyramids that share corners with two equivalent F(2)Li4Fe square pyramids, corners with three equivalent O(1)LiFe3 tetrahedra, edges with two equivalent F(1)Li3Fe2 square pyramids, edges with two equivalent F(4)Li3Fe2 square pyramids, and edges with three equivalent F(2)Li4Fe square pyramids. In the second F site, F(2) is bonded to two equivalent Li(1), two equivalent Li(2), and one Fe(1) atom to form FLi4Fe square pyramids that share corners with two equivalent F(1)Li3Fe2 square pyramids, corners with four equivalent F(4)Li3Fe2 square pyramids, corners with three equivalent O(1)LiFe3 tetrahedra,  an edgeedge with one F(4)Li3Fe2 square pyramid, edges with two equivalent F(2)Li4Fe square pyramids, and edges with three equivalent F(1)Li3Fe2 square pyramids. In the third F site, F(3) is bonded in a 5-coordinate geometry to one Li(2), two equivalent Fe(1), and two equivalent Fe(2) atoms. In the fourth F site, F(4) is bonded to one Li(2), two equivalent Li(1), and two equivalent Fe(2) atoms to form distorted FLi3Fe2 square pyramids that share corners with four equivalent F(2)Li4Fe square pyramids, corners with four equivalent O(1)LiFe3 tetrahedra,  an edgeedge with one F(2)Li4Fe square pyramid, edges with two equivalent F(1)Li3Fe2 square pyramids, edges with two equivalent F(4)Li3Fe2 square pyramids, and  an edgeedge with one O(1)LiFe3 tetrahedra.
Li2Fe2OF4 crystallizes in the orthorhombic Cmc2_1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one F(1), two equivalent F(2), and two equivalent F(4) atoms to form LiOF5 octahedra that share  a cornercorner with one Fe(1)OF5 octahedra, corners with two equivalent Li(2)F6 octahedra, edges with two equivalent Li(1)OF5 octahedra, edges with two equivalent Fe(1)OF5 octahedra, and edges with three equivalent Li(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 17-59°. The Li(1)-O(1) bond length is 2.00 Å. The Li(1)-F(1) bond length is 2.10 Å. Both Li(1)-F(2) bond lengths are 2.19 Å. Both Li(1)-F(4) bond lengths are 2.16 Å. In the second Li site, Li(2) is bonded to one F(3), one F(4), two equivalent F(1), and two equivalent F(2) atoms to form LiF6 octahedra that share corners with two equivalent Li(1)OF5 octahedra, corners with two equivalent Fe(1)OF5 octahedra, edges with two equivalent Li(2)F6 octahedra, edges with three equivalent Li(1)OF5 octahedra, and edges with three equivalent Fe(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 14-17°. The Li(2)-F(3) bond length is 2.04 Å. The Li(2)-F(4) bond length is 1.99 Å. Both Li(2)-F(1) bond lengths are 2.11 Å. Both Li(2)-F(2) bond lengths are 2.11 Å. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(1), one F(2), two equivalent F(1), and two equivalent F(3) atoms to form FeOF5 octahedra that share  a cornercorner with one Li(1)OF5 octahedra, corners with two equivalent Li(2)F6 octahedra, edges with two equivalent Li(1)OF5 octahedra, edges with two equivalent Fe(1)OF5 octahedra, and edges with three equivalent Li(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 14-59°. The Fe(1)-O(1) bond length is 1.94 Å. The Fe(1)-F(2) bond length is 2.11 Å. Both Fe(1)-F(1) bond lengths are 2.20 Å. Both Fe(1)-F(3) bond lengths are 2.18 Å. In the second Fe site, Fe(2) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent F(3), and two equivalent F(4) atoms. Both Fe(2)-O(1) bond lengths are 1.98 Å. Both Fe(2)-F(3) bond lengths are 2.49 Å. Both Fe(2)-F(4) bond lengths are 2.25 Å. O(1) is bonded to one Li(1), one Fe(1), and two equivalent Fe(2) atoms to form OLiFe3 tetrahedra that share corners with three equivalent F(1)Li3Fe2 square pyramids, corners with three equivalent F(2)Li4Fe square pyramids, corners with four equivalent F(4)Li3Fe2 square pyramids, corners with two equivalent O(1)LiFe3 tetrahedra, and  an edgeedge with one F(4)Li3Fe2 square pyramid. There are four inequivalent F sites. In the first F site, F(1) is bonded to one Li(1), two equivalent Li(2), and two equivalent Fe(1) atoms to form FLi3Fe2 square pyramids that share corners with two equivalent F(2)Li4Fe square pyramids, corners with three equivalent O(1)LiFe3 tetrahedra, edges with two equivalent F(1)Li3Fe2 square pyramids, edges with two equivalent F(4)Li3Fe2 square pyramids, and edges with three equivalent F(2)Li4Fe square pyramids. In the second F site, F(2) is bonded to two equivalent Li(1), two equivalent Li(2), and one Fe(1) atom to form FLi4Fe square pyramids that share corners with two equivalent F(1)Li3Fe2 square pyramids, corners with four equivalent F(4)Li3Fe2 square pyramids, corners with three equivalent O(1)LiFe3 tetrahedra,  an edgeedge with one F(4)Li3Fe2 square pyramid, edges with two equivalent F(2)Li4Fe square pyramids, and edges with three equivalent F(1)Li3Fe2 square pyramids. In the third F site, F(3) is bonded in a 5-coordinate geometry to one Li(2), two equivalent Fe(1), and two equivalent Fe(2) atoms. In the fourth F site, F(4) is bonded to one Li(2), two equivalent Li(1), and two equivalent Fe(2) atoms to form distorted FLi3Fe2 square pyramids that share corners with four equivalent F(2)Li4Fe square pyramids, corners with four equivalent O(1)LiFe3 tetrahedra,  an edgeedge with one F(2)Li4Fe square pyramid, edges with two equivalent F(1)Li3Fe2 square pyramids, edges with two equivalent F(4)Li3Fe2 square pyramids, and  an edgeedge with one O(1)LiFe3 tetrahedra.