LiFeF4 crystallizes in the monoclinic C2/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(1), one F(2), two equivalent F(3), and two equivalent F(5) atoms to form LiF6 octahedra that share corners with two equivalent Fe(1)F4 tetrahedra, corners with four equivalent Fe(2)F4 tetrahedra, and edges with two equivalent Li(2)F6 octahedra. In the second Li site, Li(2) is bonded to two equivalent F(1), two equivalent F(4), and two equivalent F(5) atoms to form LiF6 octahedra that share corners with two equivalent Fe(2)F4 tetrahedra, corners with four equivalent Fe(1)F4 tetrahedra,  an edgeedge with one Li(2)F6 octahedra, and edges with two equivalent Li(1)F6 octahedra. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one F(1), one F(2), and two equivalent F(4) atoms to form FeF4 tetrahedra that share corners with two equivalent Li(1)F6 octahedra and corners with four equivalent Li(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 16-60°. In the second Fe site, Fe(2) is bonded to two equivalent F(3) and two equivalent F(5) atoms to form FeF4 tetrahedra that share corners with two equivalent Li(2)F6 octahedra and corners with four equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 20-59°. There are five inequivalent F sites. In the first F site, F(1) is bonded to one Li(1), two equivalent Li(2), and one Fe(1) atom to form distorted edge-sharing FLi3Fe trigonal pyramids. In the second F site, F(2) is bonded in a bent 150 degrees geometry to one Li(1) and one Fe(1) atom. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one Li(1) and one Fe(2) atom. In the fourth F site, F(4) is bonded in a linear geometry to one Li(2) and one Fe(1) atom. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one Fe(2) atom.
LiFeF4 crystallizes in the monoclinic C2/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(1), one F(2), two equivalent F(3), and two equivalent F(5) atoms to form LiF6 octahedra that share corners with two equivalent Fe(1)F4 tetrahedra, corners with four equivalent Fe(2)F4 tetrahedra, and edges with two equivalent Li(2)F6 octahedra. The Li(1)-F(1) bond length is 2.15 Å. The Li(1)-F(2) bond length is 2.02 Å. Both Li(1)-F(3) bond lengths are 2.01 Å. Both Li(1)-F(5) bond lengths are 2.16 Å. In the second Li site, Li(2) is bonded to two equivalent F(1), two equivalent F(4), and two equivalent F(5) atoms to form LiF6 octahedra that share corners with two equivalent Fe(2)F4 tetrahedra, corners with four equivalent Fe(1)F4 tetrahedra,  an edgeedge with one Li(2)F6 octahedra, and edges with two equivalent Li(1)F6 octahedra. Both Li(2)-F(1) bond lengths are 2.21 Å. Both Li(2)-F(4) bond lengths are 1.97 Å. Both Li(2)-F(5) bond lengths are 2.04 Å. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one F(1), one F(2), and two equivalent F(4) atoms to form FeF4 tetrahedra that share corners with two equivalent Li(1)F6 octahedra and corners with four equivalent Li(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 16-60°. The Fe(1)-F(1) bond length is 1.87 Å. The Fe(1)-F(2) bond length is 1.86 Å. Both Fe(1)-F(4) bond lengths are 1.83 Å. In the second Fe site, Fe(2) is bonded to two equivalent F(3) and two equivalent F(5) atoms to form FeF4 tetrahedra that share corners with two equivalent Li(2)F6 octahedra and corners with four equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 20-59°. Both Fe(2)-F(3) bond lengths are 1.84 Å. Both Fe(2)-F(5) bond lengths are 1.86 Å. There are five inequivalent F sites. In the first F site, F(1) is bonded to one Li(1), two equivalent Li(2), and one Fe(1) atom to form distorted edge-sharing FLi3Fe trigonal pyramids. In the second F site, F(2) is bonded in a bent 150 degrees geometry to one Li(1) and one Fe(1) atom. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one Li(1) and one Fe(2) atom. In the fourth F site, F(4) is bonded in a linear geometry to one Li(2) and one Fe(1) atom. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one Fe(2) atom.