LiFeF3 crystallizes in the triclinic P-1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(2), one F(4), one F(6), and one F(9) atom to form distorted LiF4 trigonal pyramids that share corners with two equivalent Fe(2)F6 octahedra, corners with two equivalent Fe(3)F6 octahedra,  a cornercorner with one Li(2)F4 tetrahedra, and  a cornercorner with one Li(3)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 49-70°. In the second Li site, Li(2) is bonded to one F(1), one F(5), one F(6), and one F(7) atom to form LiF4 tetrahedra that share  a cornercorner with one Fe(2)F6 octahedra, corners with four equivalent Fe(3)F6 octahedra,  a cornercorner with one Li(3)F4 tetrahedra, and  a cornercorner with one Li(1)F4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 55-70°. In the third Li site, Li(3) is bonded to one F(3), one F(7), one F(8), and one F(9) atom to form LiF4 tetrahedra that share corners with two equivalent Fe(3)F6 octahedra, corners with three equivalent Fe(2)F6 octahedra,  a cornercorner with one Li(2)F4 tetrahedra, and  a cornercorner with one Li(1)F4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 44-65°. There are three inequivalent Fe sites. In the first Fe site, Fe(1) is bonded in a 5-coordinate geometry to one F(1), one F(3), one F(9), and two equivalent F(4) atoms. In the second Fe site, Fe(2) is bonded to one F(2), one F(4), one F(5), one F(8), and two equivalent F(3) atoms to form FeF6 octahedra that share  a cornercorner with one Li(2)F4 tetrahedra, corners with three equivalent Li(3)F4 tetrahedra, corners with two equivalent Li(1)F4 trigonal pyramids,  an edgeedge with one Fe(2)F6 octahedra, and edges with two equivalent Fe(3)F6 octahedra. In the third Fe site, Fe(3) is bonded to one F(2), one F(6), one F(7), one F(8), and two equivalent F(5) atoms to form distorted FeF6 octahedra that share corners with two equivalent Li(3)F4 tetrahedra, corners with four equivalent Li(2)F4 tetrahedra, corners with two equivalent Li(1)F4 trigonal pyramids,  an edgeedge with one Fe(3)F6 octahedra, and edges with two equivalent Fe(2)F6 octahedra. There are nine inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to one Li(2) and one Fe(1) atom. In the second F site, F(2) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Fe(2), and one Fe(3) atom. In the third F site, F(3) is bonded to one Li(3), one Fe(1), and two equivalent Fe(2) atoms to form a mixture of distorted edge and corner-sharing FLiFe3 tetrahedra. In the fourth F site, F(4) is bonded to one Li(1), one Fe(2), and two equivalent Fe(1) atoms to form a mixture of distorted edge and corner-sharing FLiFe3 tetrahedra. In the fifth F site, F(5) is bonded to one Li(2), one Fe(2), and two equivalent Fe(3) atoms to form a mixture of distorted edge and corner-sharing FLiFe3 tetrahedra. In the sixth F site, F(6) is bonded in a trigonal planar geometry to one Li(1), one Li(2), and one Fe(3) atom. In the seventh F site, F(7) is bonded in a trigonal planar geometry to one Li(2), one Li(3), and one Fe(3) atom. In the eighth F site, F(8) is bonded in a distorted trigonal non-coplanar geometry to one Li(3), one Fe(2), and one Fe(3) atom. In the ninth F site, F(9) is bonded in a distorted T-shaped geometry to one Li(1), one Li(3), and one Fe(1) atom.
LiFeF3 crystallizes in the triclinic P-1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(2), one F(4), one F(6), and one F(9) atom to form distorted LiF4 trigonal pyramids that share corners with two equivalent Fe(2)F6 octahedra, corners with two equivalent Fe(3)F6 octahedra,  a cornercorner with one Li(2)F4 tetrahedra, and  a cornercorner with one Li(3)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 49-70°. The Li(1)-F(2) bond length is 1.89 Å. The Li(1)-F(4) bond length is 1.98 Å. The Li(1)-F(6) bond length is 1.78 Å. The Li(1)-F(9) bond length is 1.93 Å. In the second Li site, Li(2) is bonded to one F(1), one F(5), one F(6), and one F(7) atom to form LiF4 tetrahedra that share  a cornercorner with one Fe(2)F6 octahedra, corners with four equivalent Fe(3)F6 octahedra,  a cornercorner with one Li(3)F4 tetrahedra, and  a cornercorner with one Li(1)F4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 55-70°. The Li(2)-F(1) bond length is 1.81 Å. The Li(2)-F(5) bond length is 1.95 Å. The Li(2)-F(6) bond length is 1.85 Å. The Li(2)-F(7) bond length is 1.88 Å. In the third Li site, Li(3) is bonded to one F(3), one F(7), one F(8), and one F(9) atom to form LiF4 tetrahedra that share corners with two equivalent Fe(3)F6 octahedra, corners with three equivalent Fe(2)F6 octahedra,  a cornercorner with one Li(2)F4 tetrahedra, and  a cornercorner with one Li(1)F4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 44-65°. The Li(3)-F(3) bond length is 1.97 Å. The Li(3)-F(7) bond length is 1.87 Å. The Li(3)-F(8) bond length is 1.93 Å. The Li(3)-F(9) bond length is 1.93 Å. There are three inequivalent Fe sites. In the first Fe site, Fe(1) is bonded in a 5-coordinate geometry to one F(1), one F(3), one F(9), and two equivalent F(4) atoms. The Fe(1)-F(1) bond length is 1.87 Å. The Fe(1)-F(3) bond length is 2.20 Å. The Fe(1)-F(9) bond length is 1.98 Å. There is one shorter (2.25 Å) and one longer (2.32 Å) Fe(1)-F(4) bond length. In the second Fe site, Fe(2) is bonded to one F(2), one F(4), one F(5), one F(8), and two equivalent F(3) atoms to form FeF6 octahedra that share  a cornercorner with one Li(2)F4 tetrahedra, corners with three equivalent Li(3)F4 tetrahedra, corners with two equivalent Li(1)F4 trigonal pyramids,  an edgeedge with one Fe(2)F6 octahedra, and edges with two equivalent Fe(3)F6 octahedra. The Fe(2)-F(2) bond length is 2.02 Å. The Fe(2)-F(4) bond length is 2.14 Å. The Fe(2)-F(5) bond length is 2.22 Å. The Fe(2)-F(8) bond length is 2.04 Å. There is one shorter (2.19 Å) and one longer (2.21 Å) Fe(2)-F(3) bond length. In the third Fe site, Fe(3) is bonded to one F(2), one F(6), one F(7), one F(8), and two equivalent F(5) atoms to form distorted FeF6 octahedra that share corners with two equivalent Li(3)F4 tetrahedra, corners with four equivalent Li(2)F4 tetrahedra, corners with two equivalent Li(1)F4 trigonal pyramids,  an edgeedge with one Fe(3)F6 octahedra, and edges with two equivalent Fe(2)F6 octahedra. The Fe(3)-F(2) bond length is 2.21 Å. The Fe(3)-F(6) bond length is 2.01 Å. The Fe(3)-F(7) bond length is 1.98 Å. The Fe(3)-F(8) bond length is 2.24 Å. There is one shorter (2.18 Å) and one longer (2.23 Å) Fe(3)-F(5) bond length. There are nine inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to one Li(2) and one Fe(1) atom. In the second F site, F(2) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Fe(2), and one Fe(3) atom. In the third F site, F(3) is bonded to one Li(3), one Fe(1), and two equivalent Fe(2) atoms to form a mixture of distorted edge and corner-sharing FLiFe3 tetrahedra. In the fourth F site, F(4) is bonded to one Li(1), one Fe(2), and two equivalent Fe(1) atoms to form a mixture of distorted edge and corner-sharing FLiFe3 tetrahedra. In the fifth F site, F(5) is bonded to one Li(2), one Fe(2), and two equivalent Fe(3) atoms to form a mixture of distorted edge and corner-sharing FLiFe3 tetrahedra. In the sixth F site, F(6) is bonded in a trigonal planar geometry to one Li(1), one Li(2), and one Fe(3) atom. In the seventh F site, F(7) is bonded in a trigonal planar geometry to one Li(2), one Li(3), and one Fe(3) atom. In the eighth F site, F(8) is bonded in a distorted trigonal non-coplanar geometry to one Li(3), one Fe(2), and one Fe(3) atom. In the ninth F site, F(9) is bonded in a distorted T-shaped geometry to one Li(1), one Li(3), and one Fe(1) atom.