LiFe2O2F3 crystallizes in the monoclinic Cm space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one F(1), one F(2), one F(3), one F(4), and two equivalent F(5) atoms. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to one O(4), one F(3), one F(5), one F(6), and two equivalent F(2) atoms. There are four inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(1), two equivalent O(4), one F(2), one F(3), and one F(6) atom to form distorted FeO3F3 octahedra that share  a cornercorner with one Fe(3)O5F octahedra, corners with two equivalent Fe(1)O3F3 octahedra, and edges with two equivalent Fe(3)O5F octahedra. The corner-sharing octahedral tilt angles range from 22-25°. In the second Fe site, Fe(2) is bonded in a 6-coordinate geometry to one O(1), one O(2), two equivalent O(3), one F(1), and one F(4) atom. In the third Fe site, Fe(3) is bonded to one O(2), one O(3), one O(4), two equivalent O(1), and one F(6) atom to form distorted FeO5F octahedra that share  a cornercorner with one Fe(1)O3F3 octahedra, corners with two equivalent Fe(3)O5F octahedra,  an edgeedge with one Fe(4)O2F4 octahedra, and edges with two equivalent Fe(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 22-35°. In the fourth Fe site, Fe(4) is bonded to one O(2), one O(3), one F(1), one F(5), and two equivalent F(4) atoms to form FeO2F4 octahedra that share corners with two equivalent Fe(4)O2F4 octahedra and  an edgeedge with one Fe(3)O5F octahedra. The corner-sharing octahedral tilt angles are 21°. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Fe(1), one Fe(2), and two equivalent Fe(3) atoms to form distorted OFe4 tetrahedra that share corners with two equivalent O(1)Fe4 tetrahedra,  a cornercorner with one F(2)Li3Fe trigonal pyramid, edges with two equivalent O(3)Fe4 trigonal pyramids, and edges with two equivalent O(4)LiFe3 trigonal pyramids. In the second O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to one Fe(2), one Fe(3), and one Fe(4) atom. In the third O site, O(3) is bonded to one Fe(3), one Fe(4), and two equivalent Fe(2) atoms to form OFe4 trigonal pyramids that share  a cornercorner with one O(4)LiFe3 trigonal pyramid,  a cornercorner with one F(5)Li3Fe trigonal pyramid, corners with two equivalent O(3)Fe4 trigonal pyramids, and edges with two equivalent O(1)Fe4 tetrahedra. In the fourth O site, O(4) is bonded to one Li(2), one Fe(3), and two equivalent Fe(1) atoms to form distorted OLiFe3 trigonal pyramids that share  a cornercorner with one O(3)Fe4 trigonal pyramid,  a cornercorner with one F(5)Li3Fe trigonal pyramid, corners with two equivalent O(4)LiFe3 trigonal pyramids, edges with two equivalent O(1)Fe4 tetrahedra, and edges with two equivalent F(2)Li3Fe trigonal pyramids. There are six inequivalent F sites. In the first F site, F(1) is bonded in a distorted T-shaped geometry to one Li(1), one Fe(2), and one Fe(4) atom. In the second F site, F(2) is bonded to one Li(1), two equivalent Li(2), and one Fe(1) atom to form FLi3Fe trigonal pyramids that share  a cornercorner with one O(1)Fe4 tetrahedra, corners with two equivalent F(2)Li3Fe trigonal pyramids, edges with two equivalent O(4)LiFe3 trigonal pyramids, and edges with two equivalent F(5)Li3Fe trigonal pyramids. In the third F site, F(3) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Li(2), and one Fe(1) atom. In the fourth F site, F(4) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Fe(2), and two equivalent Fe(4) atoms. In the fifth F site, F(5) is bonded to one Li(2), two equivalent Li(1), and one Fe(4) atom to form FLi3Fe trigonal pyramids that share  a cornercorner with one O(3)Fe4 trigonal pyramid,  a cornercorner with one O(4)LiFe3 trigonal pyramid, corners with two equivalent F(5)Li3Fe trigonal pyramids, and edges with two equivalent F(2)Li3Fe trigonal pyramids. In the sixth F site, F(6) is bonded in a T-shaped geometry to one Li(2), one Fe(1), and one Fe(3) atom.
LiFe2O2F3 crystallizes in the monoclinic Cm space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one F(1), one F(2), one F(3), one F(4), and two equivalent F(5) atoms. The Li(1)-F(1) bond length is 2.06 Å. The Li(1)-F(2) bond length is 2.10 Å. The Li(1)-F(3) bond length is 1.89 Å. The Li(1)-F(4) bond length is 2.37 Å. Both Li(1)-F(5) bond lengths are 2.13 Å. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to one O(4), one F(3), one F(5), one F(6), and two equivalent F(2) atoms. The Li(2)-O(4) bond length is 2.49 Å. The Li(2)-F(3) bond length is 1.92 Å. The Li(2)-F(5) bond length is 2.14 Å. The Li(2)-F(6) bond length is 2.15 Å. Both Li(2)-F(2) bond lengths are 2.03 Å. There are four inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(1), two equivalent O(4), one F(2), one F(3), and one F(6) atom to form distorted FeO3F3 octahedra that share  a cornercorner with one Fe(3)O5F octahedra, corners with two equivalent Fe(1)O3F3 octahedra, and edges with two equivalent Fe(3)O5F octahedra. The corner-sharing octahedral tilt angles range from 22-25°. The Fe(1)-O(1) bond length is 2.17 Å. Both Fe(1)-O(4) bond lengths are 1.98 Å. The Fe(1)-F(2) bond length is 2.02 Å. The Fe(1)-F(3) bond length is 1.96 Å. The Fe(1)-F(6) bond length is 2.03 Å. In the second Fe site, Fe(2) is bonded in a 6-coordinate geometry to one O(1), one O(2), two equivalent O(3), one F(1), and one F(4) atom. The Fe(2)-O(1) bond length is 2.00 Å. The Fe(2)-O(2) bond length is 1.88 Å. Both Fe(2)-O(3) bond lengths are 2.03 Å. The Fe(2)-F(1) bond length is 2.10 Å. The Fe(2)-F(4) bond length is 2.46 Å. In the third Fe site, Fe(3) is bonded to one O(2), one O(3), one O(4), two equivalent O(1), and one F(6) atom to form distorted FeO5F octahedra that share  a cornercorner with one Fe(1)O3F3 octahedra, corners with two equivalent Fe(3)O5F octahedra,  an edgeedge with one Fe(4)O2F4 octahedra, and edges with two equivalent Fe(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 22-35°. The Fe(3)-O(2) bond length is 1.99 Å. The Fe(3)-O(3) bond length is 2.24 Å. The Fe(3)-O(4) bond length is 1.99 Å. Both Fe(3)-O(1) bond lengths are 2.03 Å. The Fe(3)-F(6) bond length is 2.00 Å. In the fourth Fe site, Fe(4) is bonded to one O(2), one O(3), one F(1), one F(5), and two equivalent F(4) atoms to form FeO2F4 octahedra that share corners with two equivalent Fe(4)O2F4 octahedra and  an edgeedge with one Fe(3)O5F octahedra. The corner-sharing octahedral tilt angles are 21°. The Fe(4)-O(2) bond length is 1.94 Å. The Fe(4)-O(3) bond length is 2.05 Å. The Fe(4)-F(1) bond length is 2.02 Å. The Fe(4)-F(5) bond length is 1.98 Å. Both Fe(4)-F(4) bond lengths are 1.97 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Fe(1), one Fe(2), and two equivalent Fe(3) atoms to form distorted OFe4 tetrahedra that share corners with two equivalent O(1)Fe4 tetrahedra,  a cornercorner with one F(2)Li3Fe trigonal pyramid, edges with two equivalent O(3)Fe4 trigonal pyramids, and edges with two equivalent O(4)LiFe3 trigonal pyramids. In the second O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to one Fe(2), one Fe(3), and one Fe(4) atom. In the third O site, O(3) is bonded to one Fe(3), one Fe(4), and two equivalent Fe(2) atoms to form OFe4 trigonal pyramids that share  a cornercorner with one O(4)LiFe3 trigonal pyramid,  a cornercorner with one F(5)Li3Fe trigonal pyramid, corners with two equivalent O(3)Fe4 trigonal pyramids, and edges with two equivalent O(1)Fe4 tetrahedra. In the fourth O site, O(4) is bonded to one Li(2), one Fe(3), and two equivalent Fe(1) atoms to form distorted OLiFe3 trigonal pyramids that share  a cornercorner with one O(3)Fe4 trigonal pyramid,  a cornercorner with one F(5)Li3Fe trigonal pyramid, corners with two equivalent O(4)LiFe3 trigonal pyramids, edges with two equivalent O(1)Fe4 tetrahedra, and edges with two equivalent F(2)Li3Fe trigonal pyramids. There are six inequivalent F sites. In the first F site, F(1) is bonded in a distorted T-shaped geometry to one Li(1), one Fe(2), and one Fe(4) atom. In the second F site, F(2) is bonded to one Li(1), two equivalent Li(2), and one Fe(1) atom to form FLi3Fe trigonal pyramids that share  a cornercorner with one O(1)Fe4 tetrahedra, corners with two equivalent F(2)Li3Fe trigonal pyramids, edges with two equivalent O(4)LiFe3 trigonal pyramids, and edges with two equivalent F(5)Li3Fe trigonal pyramids. In the third F site, F(3) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Li(2), and one Fe(1) atom. In the fourth F site, F(4) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Fe(2), and two equivalent Fe(4) atoms. In the fifth F site, F(5) is bonded to one Li(2), two equivalent Li(1), and one Fe(4) atom to form FLi3Fe trigonal pyramids that share  a cornercorner with one O(3)Fe4 trigonal pyramid,  a cornercorner with one O(4)LiFe3 trigonal pyramid, corners with two equivalent F(5)Li3Fe trigonal pyramids, and edges with two equivalent F(2)Li3Fe trigonal pyramids. In the sixth F site, F(6) is bonded in a T-shaped geometry to one Li(2), one Fe(1), and one Fe(3) atom.