LiFeF3 crystallizes in the triclinic P1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(1), one F(4), one F(5), one F(7), one F(8), and one F(9) atom to form LiF6 octahedra that share corners with three equivalent Fe(1)F6 octahedra, edges with three equivalent Fe(3)F6 octahedra, and  a faceface with one Li(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 50-54°. In the second Li site, Li(2) is bonded to one F(1), one F(2), one F(3), one F(4), one F(6), and one F(8) atom to form LiF6 octahedra that share corners with three equivalent Fe(3)F6 octahedra, edges with three equivalent Fe(1)F6 octahedra, and  a faceface with one Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 43-45°. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one F(1), one F(2), one F(3), one F(4), one F(6), and one F(8) atom. There are three inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one F(1), one F(2), one F(3), one F(4), one F(6), and one F(8) atom to form FeF6 octahedra that share corners with three equivalent Li(1)F6 octahedra, corners with three equivalent Fe(3)F6 octahedra, and edges with three equivalent Li(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 50-54°. In the second Fe site, Fe(2) is bonded in a 6-coordinate geometry to one F(2), one F(3), one F(5), one F(6), one F(7), and one F(9) atom. In the third Fe site, Fe(3) is bonded to one F(1), one F(4), one F(5), one F(7), one F(8), and one F(9) atom to form FeF6 octahedra that share corners with three equivalent Li(2)F6 octahedra, corners with three equivalent Fe(1)F6 octahedra, and edges with three equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 43-51°. There are nine inequivalent F sites. In the first F site, F(1) is bonded to one Li(1), one Li(2), one Li(3), one Fe(1), and one Fe(3) atom to form distorted FLi3Fe2 trigonal bipyramids that share  a cornercorner with one F(4)Li3Fe2 trigonal bipyramid,  a cornercorner with one F(8)Li3Fe2 trigonal bipyramid,  a cornercorner with one F(2)Li2Fe2 trigonal pyramid,  a cornercorner with one F(3)Li2Fe2 trigonal pyramid,  a cornercorner with one F(6)Li2Fe2 trigonal pyramid, edges with two equivalent F(4)Li3Fe2 trigonal bipyramids, edges with two equivalent F(8)Li3Fe2 trigonal bipyramids,  an edgeedge with one F(2)Li2Fe2 trigonal pyramid,  an edgeedge with one F(3)Li2Fe2 trigonal pyramid, and  an edgeedge with one F(6)Li2Fe2 trigonal pyramid. In the second F site, F(2) is bonded to one Li(2), one Li(3), one Fe(1), and one Fe(2) atom to form distorted FLi2Fe2 trigonal pyramids that share  a cornercorner with one F(1)Li3Fe2 trigonal bipyramid,  a cornercorner with one F(4)Li3Fe2 trigonal bipyramid,  a cornercorner with one F(8)Li3Fe2 trigonal bipyramid, corners with two equivalent F(3)Li2Fe2 trigonal pyramids, corners with two equivalent F(6)Li2Fe2 trigonal pyramids,  an edgeedge with one F(1)Li3Fe2 trigonal bipyramid,  an edgeedge with one F(4)Li3Fe2 trigonal bipyramid,  an edgeedge with one F(8)Li3Fe2 trigonal bipyramid,  an edgeedge with one F(3)Li2Fe2 trigonal pyramid, and  an edgeedge with one F(6)Li2Fe2 trigonal pyramid. In the third F site, F(3) is bonded to one Li(2), one Li(3), one Fe(1), and one Fe(2) atom to form distorted FLi2Fe2 trigonal pyramids that share  a cornercorner with one F(1)Li3Fe2 trigonal bipyramid,  a cornercorner with one F(4)Li3Fe2 trigonal bipyramid,  a cornercorner with one F(8)Li3Fe2 trigonal bipyramid, corners with two equivalent F(2)Li2Fe2 trigonal pyramids, corners with two equivalent F(6)Li2Fe2 trigonal pyramids,  an edgeedge with one F(1)Li3Fe2 trigonal bipyramid,  an edgeedge with one F(4)Li3Fe2 trigonal bipyramid,  an edgeedge with one F(8)Li3Fe2 trigonal bipyramid,  an edgeedge with one F(2)Li2Fe2 trigonal pyramid, and  an edgeedge with one F(6)Li2Fe2 trigonal pyramid. In the fourth F site, F(4) is bonded to one Li(1), one Li(2), one Li(3), one Fe(1), and one Fe(3) atom to form distorted FLi3Fe2 trigonal bipyramids that share  a cornercorner with one F(1)Li3Fe2 trigonal bipyramid,  a cornercorner with one F(8)Li3Fe2 trigonal bipyramid,  a cornercorner with one F(2)Li2Fe2 trigonal pyramid,  a cornercorner with one F(3)Li2Fe2 trigonal pyramid,  a cornercorner with one F(6)Li2Fe2 trigonal pyramid, edges with two equivalent F(1)Li3Fe2 trigonal bipyramids, edges with two equivalent F(8)Li3Fe2 trigonal bipyramids,  an edgeedge with one F(2)Li2Fe2 trigonal pyramid,  an edgeedge with one F(3)Li2Fe2 trigonal pyramid, and  an edgeedge with one F(6)Li2Fe2 trigonal pyramid. In the fifth F site, F(5) is bonded in a distorted T-shaped geometry to one Li(1), one Fe(2), and one Fe(3) atom. In the sixth F site, F(6) is bonded to one Li(2), one Li(3), one Fe(1), and one Fe(2) atom to form distorted FLi2Fe2 trigonal pyramids that share  a cornercorner with one F(1)Li3Fe2 trigonal bipyramid,  a cornercorner with one F(4)Li3Fe2 trigonal bipyramid,  a cornercorner with one F(8)Li3Fe2 trigonal bipyramid, corners with two equivalent F(2)Li2Fe2 trigonal pyramids, corners with two equivalent F(3)Li2Fe2 trigonal pyramids,  an edgeedge with one F(1)Li3Fe2 trigonal bipyramid,  an edgeedge with one F(4)Li3Fe2 trigonal bipyramid,  an edgeedge with one F(8)Li3Fe2 trigonal bipyramid,  an edgeedge with one F(2)Li2Fe2 trigonal pyramid, and  an edgeedge with one F(3)Li2Fe2 trigonal pyramid. In the seventh F site, F(7) is bonded in a distorted T-shaped geometry to one Li(1), one Fe(2), and one Fe(3) atom. In the eighth F site, F(8) is bonded to one Li(1), one Li(2), one Li(3), one Fe(1), and one Fe(3) atom to form distorted FLi3Fe2 trigonal bipyramids that share  a cornercorner with one F(1)Li3Fe2 trigonal bipyramid,  a cornercorner with one F(4)Li3Fe2 trigonal bipyramid,  a cornercorner with one F(2)Li2Fe2 trigonal pyramid,  a cornercorner with one F(3)Li2Fe2 trigonal pyramid,  a cornercorner with one F(6)Li2Fe2 trigonal pyramid, edges with two equivalent F(1)Li3Fe2 trigonal bipyramids, edges with two equivalent F(4)Li3Fe2 trigonal bipyramids,  an edgeedge with one F(2)Li2Fe2 trigonal pyramid,  an edgeedge with one F(3)Li2Fe2 trigonal pyramid, and  an edgeedge with one F(6)Li2Fe2 trigonal pyramid. In the ninth F site, F(9) is bonded in a distorted T-shaped geometry to one Li(1), one Fe(2), and one Fe(3) atom.
LiFeF3 crystallizes in the triclinic P1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(1), one F(4), one F(5), one F(7), one F(8), and one F(9) atom to form LiF6 octahedra that share corners with three equivalent Fe(1)F6 octahedra, edges with three equivalent Fe(3)F6 octahedra, and  a faceface with one Li(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 50-54°. The Li(1)-F(1) bond length is 2.19 Å. The Li(1)-F(4) bond length is 2.18 Å. The Li(1)-F(5) bond length is 1.95 Å. The Li(1)-F(7) bond length is 1.94 Å. The Li(1)-F(8) bond length is 2.14 Å. The Li(1)-F(9) bond length is 1.97 Å. In the second Li site, Li(2) is bonded to one F(1), one F(2), one F(3), one F(4), one F(6), and one F(8) atom to form LiF6 octahedra that share corners with three equivalent Fe(3)F6 octahedra, edges with three equivalent Fe(1)F6 octahedra, and  a faceface with one Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 43-45°. The Li(2)-F(1) bond length is 2.00 Å. The Li(2)-F(2) bond length is 1.99 Å. The Li(2)-F(3) bond length is 2.00 Å. The Li(2)-F(4) bond length is 2.04 Å. The Li(2)-F(6) bond length is 1.99 Å. The Li(2)-F(8) bond length is 2.05 Å. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one F(1), one F(2), one F(3), one F(4), one F(6), and one F(8) atom. The Li(3)-F(1) bond length is 2.42 Å. The Li(3)-F(2) bond length is 1.93 Å. The Li(3)-F(3) bond length is 1.94 Å. The Li(3)-F(4) bond length is 2.42 Å. The Li(3)-F(6) bond length is 1.92 Å. The Li(3)-F(8) bond length is 2.41 Å. There are three inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one F(1), one F(2), one F(3), one F(4), one F(6), and one F(8) atom to form FeF6 octahedra that share corners with three equivalent Li(1)F6 octahedra, corners with three equivalent Fe(3)F6 octahedra, and edges with three equivalent Li(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 50-54°. The Fe(1)-F(1) bond length is 2.14 Å. The Fe(1)-F(2) bond length is 2.13 Å. The Fe(1)-F(3) bond length is 2.10 Å. The Fe(1)-F(4) bond length is 2.14 Å. The Fe(1)-F(6) bond length is 2.14 Å. The Fe(1)-F(8) bond length is 2.08 Å. In the second Fe site, Fe(2) is bonded in a 6-coordinate geometry to one F(2), one F(3), one F(5), one F(6), one F(7), and one F(9) atom. The Fe(2)-F(2) bond length is 2.21 Å. The Fe(2)-F(3) bond length is 2.21 Å. The Fe(2)-F(5) bond length is 2.04 Å. The Fe(2)-F(6) bond length is 2.20 Å. The Fe(2)-F(7) bond length is 2.05 Å. The Fe(2)-F(9) bond length is 2.08 Å. In the third Fe site, Fe(3) is bonded to one F(1), one F(4), one F(5), one F(7), one F(8), and one F(9) atom to form FeF6 octahedra that share corners with three equivalent Li(2)F6 octahedra, corners with three equivalent Fe(1)F6 octahedra, and edges with three equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 43-51°. The Fe(3)-F(1) bond length is 2.21 Å. The Fe(3)-F(4) bond length is 2.17 Å. The Fe(3)-F(5) bond length is 2.04 Å. The Fe(3)-F(7) bond length is 2.03 Å. The Fe(3)-F(8) bond length is 2.25 Å. The Fe(3)-F(9) bond length is 2.02 Å. There are nine inequivalent F sites. In the first F site, F(1) is bonded to one Li(1), one Li(2), one Li(3), one Fe(1), and one Fe(3) atom to form distorted FLi3Fe2 trigonal bipyramids that share  a cornercorner with one F(4)Li3Fe2 trigonal bipyramid,  a cornercorner with one F(8)Li3Fe2 trigonal bipyramid,  a cornercorner with one F(2)Li2Fe2 trigonal pyramid,  a cornercorner with one F(3)Li2Fe2 trigonal pyramid,  a cornercorner with one F(6)Li2Fe2 trigonal pyramid, edges with two equivalent F(4)Li3Fe2 trigonal bipyramids, edges with two equivalent F(8)Li3Fe2 trigonal bipyramids,  an edgeedge with one F(2)Li2Fe2 trigonal pyramid,  an edgeedge with one F(3)Li2Fe2 trigonal pyramid, and  an edgeedge with one F(6)Li2Fe2 trigonal pyramid. In the second F site, F(2) is bonded to one Li(2), one Li(3), one Fe(1), and one Fe(2) atom to form distorted FLi2Fe2 trigonal pyramids that share  a cornercorner with one F(1)Li3Fe2 trigonal bipyramid,  a cornercorner with one F(4)Li3Fe2 trigonal bipyramid,  a cornercorner with one F(8)Li3Fe2 trigonal bipyramid, corners with two equivalent F(3)Li2Fe2 trigonal pyramids, corners with two equivalent F(6)Li2Fe2 trigonal pyramids,  an edgeedge with one F(1)Li3Fe2 trigonal bipyramid,  an edgeedge with one F(4)Li3Fe2 trigonal bipyramid,  an edgeedge with one F(8)Li3Fe2 trigonal bipyramid,  an edgeedge with one F(3)Li2Fe2 trigonal pyramid, and  an edgeedge with one F(6)Li2Fe2 trigonal pyramid. In the third F site, F(3) is bonded to one Li(2), one Li(3), one Fe(1), and one Fe(2) atom to form distorted FLi2Fe2 trigonal pyramids that share  a cornercorner with one F(1)Li3Fe2 trigonal bipyramid,  a cornercorner with one F(4)Li3Fe2 trigonal bipyramid,  a cornercorner with one F(8)Li3Fe2 trigonal bipyramid, corners with two equivalent F(2)Li2Fe2 trigonal pyramids, corners with two equivalent F(6)Li2Fe2 trigonal pyramids,  an edgeedge with one F(1)Li3Fe2 trigonal bipyramid,  an edgeedge with one F(4)Li3Fe2 trigonal bipyramid,  an edgeedge with one F(8)Li3Fe2 trigonal bipyramid,  an edgeedge with one F(2)Li2Fe2 trigonal pyramid, and  an edgeedge with one F(6)Li2Fe2 trigonal pyramid. In the fourth F site, F(4) is bonded to one Li(1), one Li(2), one Li(3), one Fe(1), and one Fe(3) atom to form distorted FLi3Fe2 trigonal bipyramids that share  a cornercorner with one F(1)Li3Fe2 trigonal bipyramid,  a cornercorner with one F(8)Li3Fe2 trigonal bipyramid,  a cornercorner with one F(2)Li2Fe2 trigonal pyramid,  a cornercorner with one F(3)Li2Fe2 trigonal pyramid,  a cornercorner with one F(6)Li2Fe2 trigonal pyramid, edges with two equivalent F(1)Li3Fe2 trigonal bipyramids, edges with two equivalent F(8)Li3Fe2 trigonal bipyramids,  an edgeedge with one F(2)Li2Fe2 trigonal pyramid,  an edgeedge with one F(3)Li2Fe2 trigonal pyramid, and  an edgeedge with one F(6)Li2Fe2 trigonal pyramid. In the fifth F site, F(5) is bonded in a distorted T-shaped geometry to one Li(1), one Fe(2), and one Fe(3) atom. In the sixth F site, F(6) is bonded to one Li(2), one Li(3), one Fe(1), and one Fe(2) atom to form distorted FLi2Fe2 trigonal pyramids that share  a cornercorner with one F(1)Li3Fe2 trigonal bipyramid,  a cornercorner with one F(4)Li3Fe2 trigonal bipyramid,  a cornercorner with one F(8)Li3Fe2 trigonal bipyramid, corners with two equivalent F(2)Li2Fe2 trigonal pyramids, corners with two equivalent F(3)Li2Fe2 trigonal pyramids,  an edgeedge with one F(1)Li3Fe2 trigonal bipyramid,  an edgeedge with one F(4)Li3Fe2 trigonal bipyramid,  an edgeedge with one F(8)Li3Fe2 trigonal bipyramid,  an edgeedge with one F(2)Li2Fe2 trigonal pyramid, and  an edgeedge with one F(3)Li2Fe2 trigonal pyramid. In the seventh F site, F(7) is bonded in a distorted T-shaped geometry to one Li(1), one Fe(2), and one Fe(3) atom. In the eighth F site, F(8) is bonded to one Li(1), one Li(2), one Li(3), one Fe(1), and one Fe(3) atom to form distorted FLi3Fe2 trigonal bipyramids that share  a cornercorner with one F(1)Li3Fe2 trigonal bipyramid,  a cornercorner with one F(4)Li3Fe2 trigonal bipyramid,  a cornercorner with one F(2)Li2Fe2 trigonal pyramid,  a cornercorner with one F(3)Li2Fe2 trigonal pyramid,  a cornercorner with one F(6)Li2Fe2 trigonal pyramid, edges with two equivalent F(1)Li3Fe2 trigonal bipyramids, edges with two equivalent F(4)Li3Fe2 trigonal bipyramids,  an edgeedge with one F(2)Li2Fe2 trigonal pyramid,  an edgeedge with one F(3)Li2Fe2 trigonal pyramid, and  an edgeedge with one F(6)Li2Fe2 trigonal pyramid. In the ninth F site, F(9) is bonded in a distorted T-shaped geometry to one Li(1), one Fe(2), and one Fe(3) atom.