LiFe2OF5 crystallizes in the monoclinic C2 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a rectangular see-saw-like geometry to two equivalent O(1) and two equivalent F(5) atoms. In the second Li site, Li(2) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(4) atoms to form distorted LiF6 octahedra that share  an edgeedge with one Fe(4)O2F4 octahedra, edges with two equivalent Fe(3)F6 octahedra, and edges with two equivalent Fe(2)O2F4 octahedra. There are four inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to two equivalent O(1), two equivalent F(3), and two equivalent F(5) atoms to form FeO2F4 octahedra that share corners with two equivalent Fe(3)F6 octahedra, corners with two equivalent Fe(2)O2F4 octahedra, and edges with two equivalent Fe(4)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 4-19°. In the second Fe site, Fe(2) is bonded to two equivalent O(1), two equivalent F(1), and two equivalent F(2) atoms to form FeO2F4 octahedra that share corners with two equivalent Fe(3)F6 octahedra, corners with two equivalent Fe(1)O2F4 octahedra, edges with two equivalent Li(2)F6 octahedra, and edges with two equivalent Fe(4)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 8-19°. In the third Fe site, Fe(3) is bonded to two equivalent F(1), two equivalent F(4), and two equivalent F(5) atoms to form FeF6 octahedra that share corners with two equivalent Fe(1)O2F4 octahedra, corners with two equivalent Fe(2)O2F4 octahedra, and edges with two equivalent Li(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 4-8°. In the fourth Fe site, Fe(4) is bonded to two equivalent O(1), two equivalent F(2), and two equivalent F(3) atoms to form FeO2F4 octahedra that share  an edgeedge with one Li(2)F6 octahedra, edges with two equivalent Fe(1)O2F4 octahedra, and edges with two equivalent Fe(2)O2F4 octahedra. O(1) is bonded to one Li(1), one Fe(1), one Fe(2), and one Fe(4) atom to form a mixture of edge and corner-sharing OLiFe3 trigonal pyramids. There are five inequivalent F sites. In the first F site, F(1) is bonded in a T-shaped geometry to one Li(2), one Fe(2), and one Fe(3) atom. In the second F site, F(2) is bonded in a distorted trigonal non-coplanar geometry to one Li(2), one Fe(2), and one Fe(4) atom. In the third F site, F(3) is bonded in a water-like geometry to one Fe(1) and one Fe(4) atom. In the fourth F site, F(4) is bonded in a water-like geometry to one Li(2) and one Fe(3) atom. In the fifth F site, F(5) is bonded in a T-shaped geometry to one Li(1), one Fe(1), and one Fe(3) atom.
LiFe2OF5 crystallizes in the monoclinic C2 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a rectangular see-saw-like geometry to two equivalent O(1) and two equivalent F(5) atoms. Both Li(1)-O(1) bond lengths are 1.99 Å. Both Li(1)-F(5) bond lengths are 1.89 Å. In the second Li site, Li(2) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(4) atoms to form distorted LiF6 octahedra that share  an edgeedge with one Fe(4)O2F4 octahedra, edges with two equivalent Fe(3)F6 octahedra, and edges with two equivalent Fe(2)O2F4 octahedra. Both Li(2)-F(1) bond lengths are 2.19 Å. Both Li(2)-F(2) bond lengths are 2.14 Å. Both Li(2)-F(4) bond lengths are 1.87 Å. There are four inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to two equivalent O(1), two equivalent F(3), and two equivalent F(5) atoms to form FeO2F4 octahedra that share corners with two equivalent Fe(3)F6 octahedra, corners with two equivalent Fe(2)O2F4 octahedra, and edges with two equivalent Fe(4)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 4-19°. Both Fe(1)-O(1) bond lengths are 2.00 Å. Both Fe(1)-F(3) bond lengths are 2.02 Å. Both Fe(1)-F(5) bond lengths are 2.03 Å. In the second Fe site, Fe(2) is bonded to two equivalent O(1), two equivalent F(1), and two equivalent F(2) atoms to form FeO2F4 octahedra that share corners with two equivalent Fe(3)F6 octahedra, corners with two equivalent Fe(1)O2F4 octahedra, edges with two equivalent Li(2)F6 octahedra, and edges with two equivalent Fe(4)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 8-19°. Both Fe(2)-O(1) bond lengths are 2.00 Å. Both Fe(2)-F(1) bond lengths are 2.01 Å. Both Fe(2)-F(2) bond lengths are 2.02 Å. In the third Fe site, Fe(3) is bonded to two equivalent F(1), two equivalent F(4), and two equivalent F(5) atoms to form FeF6 octahedra that share corners with two equivalent Fe(1)O2F4 octahedra, corners with two equivalent Fe(2)O2F4 octahedra, and edges with two equivalent Li(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 4-8°. Both Fe(3)-F(1) bond lengths are 2.03 Å. Both Fe(3)-F(4) bond lengths are 1.85 Å. Both Fe(3)-F(5) bond lengths are 2.09 Å. In the fourth Fe site, Fe(4) is bonded to two equivalent O(1), two equivalent F(2), and two equivalent F(3) atoms to form FeO2F4 octahedra that share  an edgeedge with one Li(2)F6 octahedra, edges with two equivalent Fe(1)O2F4 octahedra, and edges with two equivalent Fe(2)O2F4 octahedra. Both Fe(4)-O(1) bond lengths are 2.00 Å. Both Fe(4)-F(2) bond lengths are 2.01 Å. Both Fe(4)-F(3) bond lengths are 1.98 Å. O(1) is bonded to one Li(1), one Fe(1), one Fe(2), and one Fe(4) atom to form a mixture of edge and corner-sharing OLiFe3 trigonal pyramids. There are five inequivalent F sites. In the first F site, F(1) is bonded in a T-shaped geometry to one Li(2), one Fe(2), and one Fe(3) atom. In the second F site, F(2) is bonded in a distorted trigonal non-coplanar geometry to one Li(2), one Fe(2), and one Fe(4) atom. In the third F site, F(3) is bonded in a water-like geometry to one Fe(1) and one Fe(4) atom. In the fourth F site, F(4) is bonded in a water-like geometry to one Li(2) and one Fe(3) atom. In the fifth F site, F(5) is bonded in a T-shaped geometry to one Li(1), one Fe(1), and one Fe(3) atom.