LiFeF4 crystallizes in the trigonal P3_1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(4), one F(6), one F(7), and two equivalent F(5) atoms to form LiF5 trigonal bipyramids that share  a cornercorner with one Fe(2)F6 octahedra, corners with two equivalent Fe(1)F7 pentagonal bipyramids,  a cornercorner with one Li(2)F5 trigonal bipyramid, corners with two equivalent Li(1)F5 trigonal bipyramids,  an edgeedge with one Fe(2)F6 octahedra, and  an edgeedge with one Li(2)F5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 53°. In the second Li site, Li(2) is bonded to one F(2), one F(3), one F(4), one F(6), and one F(7) atom to form distorted LiF5 trigonal bipyramids that share corners with three equivalent Fe(2)F6 octahedra, corners with two equivalent Fe(1)F7 pentagonal bipyramids,  a cornercorner with one Li(1)F5 trigonal bipyramid,  an edgeedge with one Fe(1)F7 pentagonal bipyramid, and  an edgeedge with one Li(1)F5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 44-56°. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one F(2), one F(3), one F(4), one F(7), one F(8), and two equivalent F(1) atoms to form distorted FeF7 pentagonal bipyramids that share corners with two equivalent Fe(1)F7 pentagonal bipyramids, corners with two equivalent Li(1)F5 trigonal bipyramids, corners with two equivalent Li(2)F5 trigonal bipyramids, edges with two equivalent Fe(2)F6 octahedra, and  an edgeedge with one Li(2)F5 trigonal bipyramid. In the second Fe site, Fe(2) is bonded to one F(2), one F(3), one F(5), one F(6), and two equivalent F(8) atoms to form distorted FeF6 octahedra that share corners with two equivalent Fe(2)F6 octahedra,  a cornercorner with one Li(1)F5 trigonal bipyramid, corners with three equivalent Li(2)F5 trigonal bipyramids, edges with two equivalent Fe(1)F7 pentagonal bipyramids, and  an edgeedge with one Li(1)F5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 28°. There are eight inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to two equivalent Fe(1) atoms. In the second F site, F(2) is bonded in a trigonal planar geometry to one Li(2), one Fe(1), and one Fe(2) atom. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Li(2), one Fe(1), and one Fe(2) atom. In the fourth F site, F(4) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one Fe(1) atom. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one Fe(2) atom. In the sixth F site, F(6) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one Fe(2) atom. In the seventh F site, F(7) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Li(2), and one Fe(1) atom. In the eighth F site, F(8) is bonded in a 3-coordinate geometry to one Fe(1) and two equivalent Fe(2) atoms.
LiFeF4 crystallizes in the trigonal P3_1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(4), one F(6), one F(7), and two equivalent F(5) atoms to form LiF5 trigonal bipyramids that share  a cornercorner with one Fe(2)F6 octahedra, corners with two equivalent Fe(1)F7 pentagonal bipyramids,  a cornercorner with one Li(2)F5 trigonal bipyramid, corners with two equivalent Li(1)F5 trigonal bipyramids,  an edgeedge with one Fe(2)F6 octahedra, and  an edgeedge with one Li(2)F5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 53°. The Li(1)-F(4) bond length is 1.96 Å. The Li(1)-F(6) bond length is 2.08 Å. The Li(1)-F(7) bond length is 2.09 Å. There is one shorter (1.95 Å) and one longer (2.00 Å) Li(1)-F(5) bond length. In the second Li site, Li(2) is bonded to one F(2), one F(3), one F(4), one F(6), and one F(7) atom to form distorted LiF5 trigonal bipyramids that share corners with three equivalent Fe(2)F6 octahedra, corners with two equivalent Fe(1)F7 pentagonal bipyramids,  a cornercorner with one Li(1)F5 trigonal bipyramid,  an edgeedge with one Fe(1)F7 pentagonal bipyramid, and  an edgeedge with one Li(1)F5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 44-56°. The Li(2)-F(2) bond length is 2.06 Å. The Li(2)-F(3) bond length is 2.05 Å. The Li(2)-F(4) bond length is 1.98 Å. The Li(2)-F(6) bond length is 1.94 Å. The Li(2)-F(7) bond length is 2.12 Å. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one F(2), one F(3), one F(4), one F(7), one F(8), and two equivalent F(1) atoms to form distorted FeF7 pentagonal bipyramids that share corners with two equivalent Fe(1)F7 pentagonal bipyramids, corners with two equivalent Li(1)F5 trigonal bipyramids, corners with two equivalent Li(2)F5 trigonal bipyramids, edges with two equivalent Fe(2)F6 octahedra, and  an edgeedge with one Li(2)F5 trigonal bipyramid. The Fe(1)-F(2) bond length is 2.25 Å. The Fe(1)-F(3) bond length is 2.10 Å. The Fe(1)-F(4) bond length is 1.91 Å. The Fe(1)-F(7) bond length is 1.92 Å. The Fe(1)-F(8) bond length is 2.37 Å. There is one shorter (1.96 Å) and one longer (2.03 Å) Fe(1)-F(1) bond length. In the second Fe site, Fe(2) is bonded to one F(2), one F(3), one F(5), one F(6), and two equivalent F(8) atoms to form distorted FeF6 octahedra that share corners with two equivalent Fe(2)F6 octahedra,  a cornercorner with one Li(1)F5 trigonal bipyramid, corners with three equivalent Li(2)F5 trigonal bipyramids, edges with two equivalent Fe(1)F7 pentagonal bipyramids, and  an edgeedge with one Li(1)F5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 28°. The Fe(2)-F(2) bond length is 1.98 Å. The Fe(2)-F(3) bond length is 1.96 Å. The Fe(2)-F(5) bond length is 1.93 Å. The Fe(2)-F(6) bond length is 1.91 Å. There is one shorter (2.04 Å) and one longer (2.13 Å) Fe(2)-F(8) bond length. There are eight inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to two equivalent Fe(1) atoms. In the second F site, F(2) is bonded in a trigonal planar geometry to one Li(2), one Fe(1), and one Fe(2) atom. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Li(2), one Fe(1), and one Fe(2) atom. In the fourth F site, F(4) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one Fe(1) atom. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one Fe(2) atom. In the sixth F site, F(6) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one Fe(2) atom. In the seventh F site, F(7) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Li(2), and one Fe(1) atom. In the eighth F site, F(8) is bonded in a 3-coordinate geometry to one Fe(1) and two equivalent Fe(2) atoms.