Li2FeOF3 crystallizes in the monoclinic Pc space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one F(1), one F(3), one F(4), one F(5), and one F(6) atom to form LiOF5 octahedra that share  a cornercorner with one Li(2)O2F4 octahedra, corners with two equivalent Fe(1)O2F4 octahedra, corners with two equivalent Fe(2)O2F4 octahedra,  an edgeedge with one Fe(1)O2F4 octahedra,  an edgeedge with one Fe(2)O2F4 octahedra, edges with two equivalent Li(2)O2F4 octahedra, edges with two equivalent Li(3)O2F4 octahedra, and edges with two equivalent Li(4)OF5 octahedra. The corner-sharing octahedral tilt angles range from 6-22°. In the second Li site, Li(2) is bonded to one O(1), one O(2), one F(1), one F(4), one F(5), and one F(6) atom to form distorted LiO2F4 octahedra that share  a cornercorner with one Li(1)OF5 octahedra,  a cornercorner with one Li(4)OF5 octahedra, corners with two equivalent Li(3)O2F4 octahedra,  an edgeedge with one Li(3)O2F4 octahedra, edges with two equivalent Li(1)OF5 octahedra, edges with two equivalent Li(4)OF5 octahedra, edges with two equivalent Fe(1)O2F4 octahedra, and edges with two equivalent Fe(2)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 4-24°. In the third Li site, Li(3) is bonded to one O(1), one O(2), one F(1), one F(2), one F(3), and one F(6) atom to form distorted LiO2F4 octahedra that share  a cornercorner with one Fe(1)O2F4 octahedra,  a cornercorner with one Fe(2)O2F4 octahedra, corners with two equivalent Li(2)O2F4 octahedra,  an edgeedge with one Li(2)O2F4 octahedra, edges with two equivalent Li(1)OF5 octahedra, edges with two equivalent Li(4)OF5 octahedra, edges with two equivalent Fe(1)O2F4 octahedra, and edges with two equivalent Fe(2)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 3-24°. In the fourth Li site, Li(4) is bonded to one O(2), one F(1), one F(2), one F(4), one F(5), and one F(6) atom to form LiOF5 octahedra that share  a cornercorner with one Li(2)O2F4 octahedra, corners with two equivalent Fe(1)O2F4 octahedra, corners with two equivalent Fe(2)O2F4 octahedra,  an edgeedge with one Fe(1)O2F4 octahedra,  an edgeedge with one Fe(2)O2F4 octahedra, edges with two equivalent Li(2)O2F4 octahedra, edges with two equivalent Li(3)O2F4 octahedra, and edges with two equivalent Li(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 4-17°. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(1), one O(2), one F(1), one F(2), one F(3), and one F(4) atom to form FeO2F4 octahedra that share  a cornercorner with one Li(3)O2F4 octahedra, corners with two equivalent Li(1)OF5 octahedra, corners with two equivalent Li(4)OF5 octahedra,  an edgeedge with one Li(1)OF5 octahedra,  an edgeedge with one Li(4)OF5 octahedra, edges with two equivalent Li(2)O2F4 octahedra, edges with two equivalent Li(3)O2F4 octahedra, and edges with two equivalent Fe(2)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 6-13°. In the second Fe site, Fe(2) is bonded to one O(1), one O(2), one F(2), one F(3), one F(5), and one F(6) atom to form FeO2F4 octahedra that share  a cornercorner with one Li(3)O2F4 octahedra, corners with two equivalent Li(1)OF5 octahedra, corners with two equivalent Li(4)OF5 octahedra,  an edgeedge with one Li(1)OF5 octahedra,  an edgeedge with one Li(4)OF5 octahedra, edges with two equivalent Li(2)O2F4 octahedra, edges with two equivalent Li(3)O2F4 octahedra, and edges with two equivalent Fe(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 3-22°. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Li(3), one Fe(1), and one Fe(2) atom to form OLi3Fe2 square pyramids that share corners with two equivalent F(6)Li4Fe square pyramids, corners with two equivalent O(2)Li3Fe2 trigonal bipyramids,  an edgeedge with one F(6)Li4Fe square pyramid, edges with two equivalent F(1)Li4Fe square pyramids, and  an edgeedge with one O(2)Li3Fe2 trigonal bipyramid. In the second O site, O(2) is bonded to one Li(2), one Li(3), one Li(4), one Fe(1), and one Fe(2) atom to form OLi3Fe2 trigonal bipyramids that share corners with two equivalent O(1)Li3Fe2 square pyramids, corners with two equivalent F(1)Li4Fe square pyramids,  an edgeedge with one O(1)Li3Fe2 square pyramid,  an edgeedge with one F(1)Li4Fe square pyramid, and edges with two equivalent F(6)Li4Fe square pyramids. There are six inequivalent F sites. In the first F site, F(1) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), and one Fe(1) atom to form distorted FLi4Fe square pyramids that share corners with two equivalent F(6)Li4Fe square pyramids, corners with two equivalent O(2)Li3Fe2 trigonal bipyramids,  an edgeedge with one F(6)Li4Fe square pyramid, edges with two equivalent O(1)Li3Fe2 square pyramids, and  an edgeedge with one O(2)Li3Fe2 trigonal bipyramid. In the second F site, F(2) is bonded in a rectangular see-saw-like geometry to one Li(3), one Li(4), one Fe(1), and one Fe(2) atom. In the third F site, F(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(3), one Fe(1), and one Fe(2) atom. In the fourth F site, F(4) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one Li(4), and one Fe(1) atom. In the fifth F site, F(5) is bonded in a see-saw-like geometry to one Li(1), one Li(2), one Li(4), and one Fe(2) atom. In the sixth F site, F(6) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), and one Fe(2) atom to form FLi4Fe square pyramids that share corners with two equivalent O(1)Li3Fe2 square pyramids, corners with two equivalent F(1)Li4Fe square pyramids,  an edgeedge with one O(1)Li3Fe2 square pyramid,  an edgeedge with one F(1)Li4Fe square pyramid, and edges with two equivalent O(2)Li3Fe2 trigonal bipyramids.
Li2FeOF3 crystallizes in the monoclinic Pc space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one F(1), one F(3), one F(4), one F(5), and one F(6) atom to form LiOF5 octahedra that share  a cornercorner with one Li(2)O2F4 octahedra, corners with two equivalent Fe(1)O2F4 octahedra, corners with two equivalent Fe(2)O2F4 octahedra,  an edgeedge with one Fe(1)O2F4 octahedra,  an edgeedge with one Fe(2)O2F4 octahedra, edges with two equivalent Li(2)O2F4 octahedra, edges with two equivalent Li(3)O2F4 octahedra, and edges with two equivalent Li(4)OF5 octahedra. The corner-sharing octahedral tilt angles range from 6-22°. The Li(1)-O(1) bond length is 2.20 Å. The Li(1)-F(1) bond length is 2.02 Å. The Li(1)-F(3) bond length is 2.29 Å. The Li(1)-F(4) bond length is 2.04 Å. The Li(1)-F(5) bond length is 2.09 Å. The Li(1)-F(6) bond length is 2.03 Å. In the second Li site, Li(2) is bonded to one O(1), one O(2), one F(1), one F(4), one F(5), and one F(6) atom to form distorted LiO2F4 octahedra that share  a cornercorner with one Li(1)OF5 octahedra,  a cornercorner with one Li(4)OF5 octahedra, corners with two equivalent Li(3)O2F4 octahedra,  an edgeedge with one Li(3)O2F4 octahedra, edges with two equivalent Li(1)OF5 octahedra, edges with two equivalent Li(4)OF5 octahedra, edges with two equivalent Fe(1)O2F4 octahedra, and edges with two equivalent Fe(2)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 4-24°. The Li(2)-O(1) bond length is 2.03 Å. The Li(2)-O(2) bond length is 2.09 Å. The Li(2)-F(1) bond length is 2.45 Å. The Li(2)-F(4) bond length is 2.18 Å. The Li(2)-F(5) bond length is 1.97 Å. The Li(2)-F(6) bond length is 1.99 Å. In the third Li site, Li(3) is bonded to one O(1), one O(2), one F(1), one F(2), one F(3), and one F(6) atom to form distorted LiO2F4 octahedra that share  a cornercorner with one Fe(1)O2F4 octahedra,  a cornercorner with one Fe(2)O2F4 octahedra, corners with two equivalent Li(2)O2F4 octahedra,  an edgeedge with one Li(2)O2F4 octahedra, edges with two equivalent Li(1)OF5 octahedra, edges with two equivalent Li(4)OF5 octahedra, edges with two equivalent Fe(1)O2F4 octahedra, and edges with two equivalent Fe(2)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 3-24°. The Li(3)-O(1) bond length is 2.32 Å. The Li(3)-O(2) bond length is 2.01 Å. The Li(3)-F(1) bond length is 2.01 Å. The Li(3)-F(2) bond length is 2.02 Å. The Li(3)-F(3) bond length is 2.46 Å. The Li(3)-F(6) bond length is 1.99 Å. In the fourth Li site, Li(4) is bonded to one O(2), one F(1), one F(2), one F(4), one F(5), and one F(6) atom to form LiOF5 octahedra that share  a cornercorner with one Li(2)O2F4 octahedra, corners with two equivalent Fe(1)O2F4 octahedra, corners with two equivalent Fe(2)O2F4 octahedra,  an edgeedge with one Fe(1)O2F4 octahedra,  an edgeedge with one Fe(2)O2F4 octahedra, edges with two equivalent Li(2)O2F4 octahedra, edges with two equivalent Li(3)O2F4 octahedra, and edges with two equivalent Li(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 4-17°. The Li(4)-O(2) bond length is 2.15 Å. The Li(4)-F(1) bond length is 2.10 Å. The Li(4)-F(2) bond length is 2.05 Å. The Li(4)-F(4) bond length is 2.06 Å. The Li(4)-F(5) bond length is 2.03 Å. The Li(4)-F(6) bond length is 2.17 Å. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(1), one O(2), one F(1), one F(2), one F(3), and one F(4) atom to form FeO2F4 octahedra that share  a cornercorner with one Li(3)O2F4 octahedra, corners with two equivalent Li(1)OF5 octahedra, corners with two equivalent Li(4)OF5 octahedra,  an edgeedge with one Li(1)OF5 octahedra,  an edgeedge with one Li(4)OF5 octahedra, edges with two equivalent Li(2)O2F4 octahedra, edges with two equivalent Li(3)O2F4 octahedra, and edges with two equivalent Fe(2)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 6-13°. The Fe(1)-O(1) bond length is 1.94 Å. The Fe(1)-O(2) bond length is 1.94 Å. The Fe(1)-F(1) bond length is 2.03 Å. The Fe(1)-F(2) bond length is 2.13 Å. The Fe(1)-F(3) bond length is 2.06 Å. The Fe(1)-F(4) bond length is 1.99 Å. In the second Fe site, Fe(2) is bonded to one O(1), one O(2), one F(2), one F(3), one F(5), and one F(6) atom to form FeO2F4 octahedra that share  a cornercorner with one Li(3)O2F4 octahedra, corners with two equivalent Li(1)OF5 octahedra, corners with two equivalent Li(4)OF5 octahedra,  an edgeedge with one Li(1)OF5 octahedra,  an edgeedge with one Li(4)OF5 octahedra, edges with two equivalent Li(2)O2F4 octahedra, edges with two equivalent Li(3)O2F4 octahedra, and edges with two equivalent Fe(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 3-22°. The Fe(2)-O(1) bond length is 1.92 Å. The Fe(2)-O(2) bond length is 1.95 Å. The Fe(2)-F(2) bond length is 2.08 Å. The Fe(2)-F(3) bond length is 2.03 Å. The Fe(2)-F(5) bond length is 2.01 Å. The Fe(2)-F(6) bond length is 2.11 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Li(3), one Fe(1), and one Fe(2) atom to form OLi3Fe2 square pyramids that share corners with two equivalent F(6)Li4Fe square pyramids, corners with two equivalent O(2)Li3Fe2 trigonal bipyramids,  an edgeedge with one F(6)Li4Fe square pyramid, edges with two equivalent F(1)Li4Fe square pyramids, and  an edgeedge with one O(2)Li3Fe2 trigonal bipyramid. In the second O site, O(2) is bonded to one Li(2), one Li(3), one Li(4), one Fe(1), and one Fe(2) atom to form OLi3Fe2 trigonal bipyramids that share corners with two equivalent O(1)Li3Fe2 square pyramids, corners with two equivalent F(1)Li4Fe square pyramids,  an edgeedge with one O(1)Li3Fe2 square pyramid,  an edgeedge with one F(1)Li4Fe square pyramid, and edges with two equivalent F(6)Li4Fe square pyramids. There are six inequivalent F sites. In the first F site, F(1) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), and one Fe(1) atom to form distorted FLi4Fe square pyramids that share corners with two equivalent F(6)Li4Fe square pyramids, corners with two equivalent O(2)Li3Fe2 trigonal bipyramids,  an edgeedge with one F(6)Li4Fe square pyramid, edges with two equivalent O(1)Li3Fe2 square pyramids, and  an edgeedge with one O(2)Li3Fe2 trigonal bipyramid. In the second F site, F(2) is bonded in a rectangular see-saw-like geometry to one Li(3), one Li(4), one Fe(1), and one Fe(2) atom. In the third F site, F(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(3), one Fe(1), and one Fe(2) atom. In the fourth F site, F(4) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one Li(4), and one Fe(1) atom. In the fifth F site, F(5) is bonded in a see-saw-like geometry to one Li(1), one Li(2), one Li(4), and one Fe(2) atom. In the sixth F site, F(6) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), and one Fe(2) atom to form FLi4Fe square pyramids that share corners with two equivalent O(1)Li3Fe2 square pyramids, corners with two equivalent F(1)Li4Fe square pyramids,  an edgeedge with one O(1)Li3Fe2 square pyramid,  an edgeedge with one F(1)Li4Fe square pyramid, and edges with two equivalent O(2)Li3Fe2 trigonal bipyramids.