LiFeF3 crystallizes in the orthorhombic Pnma space group. Li(1) is bonded to one F(2), one F(3), and two equivalent F(1) atoms to form distorted LiF4 trigonal pyramids that share corners with four equivalent Fe(1)F6 octahedra, corners with two equivalent Li(1)F4 trigonal pyramids, and edges with two equivalent Fe(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 35-73°. Fe(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form FeF6 octahedra that share corners with two equivalent Fe(1)F6 octahedra, corners with four equivalent Li(1)F4 trigonal pyramids, edges with two equivalent Fe(1)F6 octahedra, and edges with two equivalent Li(1)F4 trigonal pyramids. The corner-sharing octahedral tilt angles are 18°. There are three inequivalent F sites. In the first F site, F(1) is bonded to two equivalent Li(1) and two equivalent Fe(1) atoms to form corner-sharing FLi2Fe2 trigonal pyramids. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Li(1) and two equivalent Fe(1) atoms. In the third F site, F(3) is bonded in a T-shaped geometry to one Li(1) and two equivalent Fe(1) atoms.
LiFeF3 crystallizes in the orthorhombic Pnma space group. Li(1) is bonded to one F(2), one F(3), and two equivalent F(1) atoms to form distorted LiF4 trigonal pyramids that share corners with four equivalent Fe(1)F6 octahedra, corners with two equivalent Li(1)F4 trigonal pyramids, and edges with two equivalent Fe(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 35-73°. The Li(1)-F(2) bond length is 1.85 Å. The Li(1)-F(3) bond length is 1.95 Å. Both Li(1)-F(1) bond lengths are 2.09 Å. Fe(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form FeF6 octahedra that share corners with two equivalent Fe(1)F6 octahedra, corners with four equivalent Li(1)F4 trigonal pyramids, edges with two equivalent Fe(1)F6 octahedra, and edges with two equivalent Li(1)F4 trigonal pyramids. The corner-sharing octahedral tilt angles are 18°. There is one shorter (2.13 Å) and one longer (2.22 Å) Fe(1)-F(1) bond length. There is one shorter (2.07 Å) and one longer (2.09 Å) Fe(1)-F(2) bond length. Both Fe(1)-F(3) bond lengths are 2.02 Å. There are three inequivalent F sites. In the first F site, F(1) is bonded to two equivalent Li(1) and two equivalent Fe(1) atoms to form corner-sharing FLi2Fe2 trigonal pyramids. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Li(1) and two equivalent Fe(1) atoms. In the third F site, F(3) is bonded in a T-shaped geometry to one Li(1) and two equivalent Fe(1) atoms.