LiFeF3 crystallizes in the monoclinic C2/c space group. Li(1) is bonded to one F(1), one F(2), and two equivalent F(3) atoms to form LiF4 tetrahedra that share corners with three equivalent Fe(1)F6 octahedra and corners with two equivalent Li(1)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 31-63°. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form FeF6 octahedra that share corners with six equivalent Li(1)F4 tetrahedra and edges with two equivalent Fe(1)F6 octahedra. In the second Fe site, Fe(2) is bonded in a 6-coordinate geometry to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms. There are three inequivalent F sites. In the first F site, F(1) 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 second F site, F(2) is bonded in a distorted T-shaped geometry to one Li(1), one Fe(1), and one Fe(2) atom. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one Fe(2) atom.
LiFeF3 crystallizes in the monoclinic C2/c space group. Li(1) is bonded to one F(1), one F(2), and two equivalent F(3) atoms to form LiF4 tetrahedra that share corners with three equivalent Fe(1)F6 octahedra and corners with two equivalent Li(1)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 31-63°. The Li(1)-F(1) bond length is 1.95 Å. The Li(1)-F(2) bond length is 1.92 Å. There is one shorter (1.83 Å) and one longer (1.86 Å) Li(1)-F(3) bond length. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form FeF6 octahedra that share corners with six equivalent Li(1)F4 tetrahedra and edges with two equivalent Fe(1)F6 octahedra. Both Fe(1)-F(2) bond lengths are 2.01 Å. There are two shorter (2.12 Å) and two longer (2.23 Å) Fe(1)-F(1) bond lengths. In the second Fe site, Fe(2) is bonded in a 6-coordinate geometry to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms. Both Fe(2)-F(1) bond lengths are 2.27 Å. Both Fe(2)-F(2) bond lengths are 2.16 Å. Both Fe(2)-F(3) bond lengths are 2.00 Å. There are three inequivalent F sites. In the first F site, F(1) 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 second F site, F(2) is bonded in a distorted T-shaped geometry to one Li(1), one Fe(1), and one Fe(2) atom. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one Fe(2) atom.