LiFe2O2F3 crystallizes in the monoclinic C2 space group. Li(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 LiO2F4 octahedra that share corners with two equivalent Li(1)O2F4 octahedra, corners with three equivalent Fe(1)O3F3 octahedra, corners with three equivalent Fe(2)O3F3 octahedra, edges with two equivalent Fe(1)O3F3 octahedra, and edges with two equivalent Fe(2)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 44-61°. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(2), two equivalent O(1), one F(3), and two equivalent F(1) atoms to form FeO3F3 octahedra that share corners with two equivalent Fe(1)O3F3 octahedra, corners with two equivalent Fe(2)O3F3 octahedra, corners with three equivalent Li(1)O2F4 octahedra,  an edgeedge with one Fe(2)O3F3 octahedra, edges with two equivalent Li(1)O2F4 octahedra, and  a faceface with one Fe(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 44-50°. In the second Fe site, Fe(2) is bonded to one O(1), two equivalent O(2), one F(4), and two equivalent F(2) atoms to form FeO3F3 octahedra that share corners with two equivalent Fe(1)O3F3 octahedra, corners with two equivalent Fe(2)O3F3 octahedra, corners with three equivalent Li(1)O2F4 octahedra,  an edgeedge with one Fe(1)O3F3 octahedra, edges with two equivalent Li(1)O2F4 octahedra, and  a faceface with one Fe(2)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 46-49°. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Fe(2), and two equivalent Fe(1) atoms to form OLiFe3 trigonal pyramids that share  a cornercorner with one F(3)Li2Fe2 trigonal pyramid, corners with three equivalent O(2)LiFe3 trigonal pyramids,  an edgeedge with one O(1)LiFe3 trigonal pyramid,  an edgeedge with one O(2)LiFe3 trigonal pyramid,  an edgeedge with one F(3)Li2Fe2 trigonal pyramid, and  an edgeedge with one F(4)Li2Fe2 trigonal pyramid. In the second O site, O(2) is bonded to one Li(1), one Fe(1), and two equivalent Fe(2) atoms to form OLiFe3 trigonal pyramids that share  a cornercorner with one F(4)Li2Fe2 trigonal pyramid, corners with three equivalent O(1)LiFe3 trigonal pyramids,  an edgeedge with one O(1)LiFe3 trigonal pyramid,  an edgeedge with one O(2)LiFe3 trigonal pyramid,  an edgeedge with one F(3)Li2Fe2 trigonal pyramid, and  an edgeedge with one F(4)Li2Fe2 trigonal pyramid. There are four inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Li(1) and two equivalent Fe(1) atoms. In the second F site, F(2) is bonded in a distorted T-shaped geometry to one Li(1) and two equivalent Fe(2) atoms. In the third F site, F(3) is bonded to two equivalent Li(1) and two equivalent Fe(1) atoms to form distorted FLi2Fe2 trigonal pyramids that share corners with two equivalent O(1)LiFe3 trigonal pyramids, corners with two equivalent F(4)Li2Fe2 trigonal pyramids, edges with two equivalent O(1)LiFe3 trigonal pyramids, and edges with two equivalent O(2)LiFe3 trigonal pyramids. In the fourth F site, F(4) is bonded to two equivalent Li(1) and two equivalent Fe(2) atoms to form distorted FLi2Fe2 trigonal pyramids that share corners with two equivalent O(2)LiFe3 trigonal pyramids, corners with two equivalent F(3)Li2Fe2 trigonal pyramids, edges with two equivalent O(1)LiFe3 trigonal pyramids, and edges with two equivalent O(2)LiFe3 trigonal pyramids.
LiFe2O2F3 crystallizes in the monoclinic C2 space group. Li(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 LiO2F4 octahedra that share corners with two equivalent Li(1)O2F4 octahedra, corners with three equivalent Fe(1)O3F3 octahedra, corners with three equivalent Fe(2)O3F3 octahedra, edges with two equivalent Fe(1)O3F3 octahedra, and edges with two equivalent Fe(2)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 44-61°. The Li(1)-O(1) bond length is 2.25 Å. The Li(1)-O(2) bond length is 2.22 Å. The Li(1)-F(1) bond length is 2.09 Å. The Li(1)-F(2) bond length is 2.14 Å. The Li(1)-F(3) bond length is 2.08 Å. The Li(1)-F(4) bond length is 2.09 Å. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(2), two equivalent O(1), one F(3), and two equivalent F(1) atoms to form FeO3F3 octahedra that share corners with two equivalent Fe(1)O3F3 octahedra, corners with two equivalent Fe(2)O3F3 octahedra, corners with three equivalent Li(1)O2F4 octahedra,  an edgeedge with one Fe(2)O3F3 octahedra, edges with two equivalent Li(1)O2F4 octahedra, and  a faceface with one Fe(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 44-50°. The Fe(1)-O(2) bond length is 1.95 Å. There is one shorter (2.00 Å) and one longer (2.07 Å) Fe(1)-O(1) bond length. The Fe(1)-F(3) bond length is 2.20 Å. There is one shorter (1.99 Å) and one longer (2.02 Å) Fe(1)-F(1) bond length. In the second Fe site, Fe(2) is bonded to one O(1), two equivalent O(2), one F(4), and two equivalent F(2) atoms to form FeO3F3 octahedra that share corners with two equivalent Fe(1)O3F3 octahedra, corners with two equivalent Fe(2)O3F3 octahedra, corners with three equivalent Li(1)O2F4 octahedra,  an edgeedge with one Fe(1)O3F3 octahedra, edges with two equivalent Li(1)O2F4 octahedra, and  a faceface with one Fe(2)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 46-49°. The Fe(2)-O(1) bond length is 1.95 Å. There is one shorter (1.99 Å) and one longer (2.07 Å) Fe(2)-O(2) bond length. The Fe(2)-F(4) bond length is 2.18 Å. There is one shorter (1.99 Å) and one longer (2.02 Å) Fe(2)-F(2) bond length. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Fe(2), and two equivalent Fe(1) atoms to form OLiFe3 trigonal pyramids that share  a cornercorner with one F(3)Li2Fe2 trigonal pyramid, corners with three equivalent O(2)LiFe3 trigonal pyramids,  an edgeedge with one O(1)LiFe3 trigonal pyramid,  an edgeedge with one O(2)LiFe3 trigonal pyramid,  an edgeedge with one F(3)Li2Fe2 trigonal pyramid, and  an edgeedge with one F(4)Li2Fe2 trigonal pyramid. In the second O site, O(2) is bonded to one Li(1), one Fe(1), and two equivalent Fe(2) atoms to form OLiFe3 trigonal pyramids that share  a cornercorner with one F(4)Li2Fe2 trigonal pyramid, corners with three equivalent O(1)LiFe3 trigonal pyramids,  an edgeedge with one O(1)LiFe3 trigonal pyramid,  an edgeedge with one O(2)LiFe3 trigonal pyramid,  an edgeedge with one F(3)Li2Fe2 trigonal pyramid, and  an edgeedge with one F(4)Li2Fe2 trigonal pyramid. There are four inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Li(1) and two equivalent Fe(1) atoms. In the second F site, F(2) is bonded in a distorted T-shaped geometry to one Li(1) and two equivalent Fe(2) atoms. In the third F site, F(3) is bonded to two equivalent Li(1) and two equivalent Fe(1) atoms to form distorted FLi2Fe2 trigonal pyramids that share corners with two equivalent O(1)LiFe3 trigonal pyramids, corners with two equivalent F(4)Li2Fe2 trigonal pyramids, edges with two equivalent O(1)LiFe3 trigonal pyramids, and edges with two equivalent O(2)LiFe3 trigonal pyramids. In the fourth F site, F(4) is bonded to two equivalent Li(1) and two equivalent Fe(2) atoms to form distorted FLi2Fe2 trigonal pyramids that share corners with two equivalent O(2)LiFe3 trigonal pyramids, corners with two equivalent F(3)Li2Fe2 trigonal pyramids, edges with two equivalent O(1)LiFe3 trigonal pyramids, and edges with two equivalent O(2)LiFe3 trigonal pyramids.