LiFeF3 crystallizes in the trigonal R-3 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)F5 trigonal bipyramids, corners with two equivalent Li(1)F4 trigonal pyramids, and  an edgeedge with one Fe(1)F5 trigonal bipyramid. Fe(1) is bonded to one F(1), two equivalent F(2), and two equivalent F(3) atoms to form FeF5 trigonal bipyramids that share corners with two equivalent Fe(1)F5 trigonal bipyramids, corners with four equivalent Li(1)F4 trigonal pyramids,  an edgeedge with one Fe(1)F5 trigonal bipyramid, and  an edgeedge with one Li(1)F4 trigonal pyramid. There are three inequivalent F sites. In the first F site, F(1) is bonded in a distorted T-shaped geometry to two equivalent Li(1) and one Fe(1) atom. 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 3-coordinate geometry to one Li(1) and two equivalent Fe(1) atoms.
LiFeF3 crystallizes in the trigonal R-3 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)F5 trigonal bipyramids, corners with two equivalent Li(1)F4 trigonal pyramids, and  an edgeedge with one Fe(1)F5 trigonal bipyramid. The Li(1)-F(2) bond length is 2.04 Å. The Li(1)-F(3) bond length is 1.94 Å. There is one shorter (1.86 Å) and one longer (1.98 Å) Li(1)-F(1) bond length. Fe(1) is bonded to one F(1), two equivalent F(2), and two equivalent F(3) atoms to form FeF5 trigonal bipyramids that share corners with two equivalent Fe(1)F5 trigonal bipyramids, corners with four equivalent Li(1)F4 trigonal pyramids,  an edgeedge with one Fe(1)F5 trigonal bipyramid, and  an edgeedge with one Li(1)F4 trigonal pyramid. The Fe(1)-F(1) bond length is 2.01 Å. There is one shorter (2.01 Å) and one longer (2.09 Å) Fe(1)-F(2) bond length. There is one shorter (2.04 Å) and one longer (2.13 Å) Fe(1)-F(3) bond length. There are three inequivalent F sites. In the first F site, F(1) is bonded in a distorted T-shaped geometry to two equivalent Li(1) and one Fe(1) atom. 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 3-coordinate geometry to one Li(1) and two equivalent Fe(1) atoms.