Li3Fe4F19 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(17), one F(18), one F(5), one F(6), and two equivalent F(3) atoms to form distorted LiF6 octahedra that share  a cornercorner with one Li(3)F6 octahedra,  a cornercorner with one Fe(2)F7 pentagonal bipyramid, corners with two equivalent Fe(1)F7 pentagonal bipyramids, corners with two equivalent Fe(3)F7 pentagonal bipyramids,  an edgeedge with one Li(1)F6 octahedra, and  an edgeedge with one Fe(1)F7 pentagonal bipyramid. The corner-sharing octahedral tilt angles are 58°. In the second Li site, Li(2) is bonded to one F(1), one F(12), one F(15), one F(19), one F(8), and one F(9) atom to form LiF6 octahedra that share  a cornercorner with one Li(3)F6 octahedra,  a cornercorner with one Fe(1)F7 pentagonal bipyramid, corners with two equivalent Fe(2)F7 pentagonal bipyramids, corners with two equivalent Fe(4)F7 pentagonal bipyramids,  an edgeedge with one Fe(2)F7 pentagonal bipyramid, and  an edgeedge with one Fe(4)F7 pentagonal bipyramid. The corner-sharing octahedral tilt angles are 65°. In the third Li site, Li(3) is bonded to one F(10), one F(13), one F(14), one F(15), one F(18), and one F(7) atom to form LiF6 octahedra that share  a cornercorner with one Li(1)F6 octahedra,  a cornercorner with one Li(2)F6 octahedra,  a cornercorner with one Fe(4)F7 pentagonal bipyramid, corners with two equivalent Fe(2)F7 pentagonal bipyramids, corners with two equivalent Fe(3)F7 pentagonal bipyramids, and  an edgeedge with one Fe(3)F7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 58-65°. There are four inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one F(11), one F(16), one F(17), one F(2), one F(3), one F(6), and one F(9) atom to form distorted FeF7 pentagonal bipyramids that share  a cornercorner with one Li(2)F6 octahedra, corners with two equivalent Li(1)F6 octahedra,  a cornercorner with one Fe(3)F7 pentagonal bipyramid, corners with two equivalent Fe(4)F7 pentagonal bipyramids,  an edgeedge with one Li(1)F6 octahedra, and  an edgeedge with one Fe(2)F7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 2-41°. In the second Fe site, Fe(2) is bonded to one F(10), one F(12), one F(13), one F(6), one F(9), and two equivalent F(8) atoms to form distorted FeF7 pentagonal bipyramids that share  a cornercorner with one Li(1)F6 octahedra, corners with two equivalent Li(2)F6 octahedra, corners with two equivalent Li(3)F6 octahedra,  an edgeedge with one Li(2)F6 octahedra,  an edgeedge with one Fe(1)F7 pentagonal bipyramid, and  an edgeedge with one Fe(2)F7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 1-41°. In the third Fe site, Fe(3) is bonded to one F(11), one F(14), one F(18), one F(4), one F(5), and two equivalent F(7) atoms to form FeF7 pentagonal bipyramids that share corners with two equivalent Li(1)F6 octahedra, corners with two equivalent Li(3)F6 octahedra,  a cornercorner with one Fe(1)F7 pentagonal bipyramid,  a cornercorner with one Fe(4)F7 pentagonal bipyramid,  an edgeedge with one Li(3)F6 octahedra, and  an edgeedge with one Fe(3)F7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 6-50°. In the fourth Fe site, Fe(4) is bonded to one F(1), one F(15), one F(16), one F(2), one F(4), and two equivalent F(19) atoms to form distorted FeF7 pentagonal bipyramids that share  a cornercorner with one Li(3)F6 octahedra, corners with two equivalent Li(2)F6 octahedra,  a cornercorner with one Fe(3)F7 pentagonal bipyramid, corners with two equivalent Fe(1)F7 pentagonal bipyramids,  an edgeedge with one Li(2)F6 octahedra, and  an edgeedge with one Fe(4)F7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 11-41°. There are nineteen inequivalent F sites. In the first F site, F(1) is bonded in a linear geometry to one Li(2) and one Fe(4) atom. In the second F site, F(2) is bonded in a linear geometry to one Fe(1) and one Fe(4) atom. In the third F site, F(3) is bonded in a 3-coordinate geometry to two equivalent Li(1) and one Fe(1) atom. In the fourth F site, F(4) is bonded in a linear geometry to one Fe(3) and one Fe(4) atom. In the fifth F site, F(5) is bonded in a linear geometry to one Li(1) and one Fe(3) atom. In the sixth F site, F(6) is bonded in a 3-coordinate geometry to one Li(1), one Fe(1), and one Fe(2) atom. In the seventh F site, F(7) is bonded in a distorted trigonal planar geometry to one Li(3) and two equivalent Fe(3) atoms. In the eighth F site, F(8) is bonded in a distorted trigonal planar geometry to one Li(2) and two equivalent Fe(2) atoms. In the ninth F site, F(9) is bonded in a trigonal planar geometry to one Li(2), one Fe(1), and one Fe(2) atom. In the tenth F site, F(10) is bonded in a linear geometry to one Li(3) and one Fe(2) atom. In the eleventh F site, F(11) is bonded in a linear geometry to one Fe(1) and one Fe(3) atom. In the twelfth F site, F(12) is bonded in a linear geometry to one Li(2) and one Fe(2) atom. In the thirteenth F site, F(13) is bonded in a linear geometry to one Li(3) and one Fe(2) atom. In the fourteenth F site, F(14) is bonded in a linear geometry to one Li(3) and one Fe(3) atom. In the fifteenth F site, F(15) is bonded in a distorted trigonal planar geometry to one Li(2), one Li(3), and one Fe(4) atom. In the sixteenth F site, F(16) is bonded in a linear geometry to one Fe(1) and one Fe(4) atom. In the seventeenth F site, F(17) is bonded in a linear geometry to one Li(1) and one Fe(1) atom. In the eighteenth F site, F(18) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(3), and one Fe(3) atom. In the nineteenth F site, F(19) is bonded in a distorted trigonal planar geometry to one Li(2) and two equivalent Fe(4) atoms.
Li3Fe4F19 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(17), one F(18), one F(5), one F(6), and two equivalent F(3) atoms to form distorted LiF6 octahedra that share  a cornercorner with one Li(3)F6 octahedra,  a cornercorner with one Fe(2)F7 pentagonal bipyramid, corners with two equivalent Fe(1)F7 pentagonal bipyramids, corners with two equivalent Fe(3)F7 pentagonal bipyramids,  an edgeedge with one Li(1)F6 octahedra, and  an edgeedge with one Fe(1)F7 pentagonal bipyramid. The corner-sharing octahedral tilt angles are 58°. The Li(1)-F(17) bond length is 1.96 Å. The Li(1)-F(18) bond length is 2.06 Å. The Li(1)-F(5) bond length is 2.25 Å. The Li(1)-F(6) bond length is 2.02 Å. There is one shorter (2.03 Å) and one longer (2.34 Å) Li(1)-F(3) bond length. In the second Li site, Li(2) is bonded to one F(1), one F(12), one F(15), one F(19), one F(8), and one F(9) atom to form LiF6 octahedra that share  a cornercorner with one Li(3)F6 octahedra,  a cornercorner with one Fe(1)F7 pentagonal bipyramid, corners with two equivalent Fe(2)F7 pentagonal bipyramids, corners with two equivalent Fe(4)F7 pentagonal bipyramids,  an edgeedge with one Fe(2)F7 pentagonal bipyramid, and  an edgeedge with one Fe(4)F7 pentagonal bipyramid. The corner-sharing octahedral tilt angles are 65°. The Li(2)-F(1) bond length is 2.08 Å. The Li(2)-F(12) bond length is 2.25 Å. The Li(2)-F(15) bond length is 2.15 Å. The Li(2)-F(19) bond length is 1.98 Å. The Li(2)-F(8) bond length is 2.05 Å. The Li(2)-F(9) bond length is 2.07 Å. In the third Li site, Li(3) is bonded to one F(10), one F(13), one F(14), one F(15), one F(18), and one F(7) atom to form LiF6 octahedra that share  a cornercorner with one Li(1)F6 octahedra,  a cornercorner with one Li(2)F6 octahedra,  a cornercorner with one Fe(4)F7 pentagonal bipyramid, corners with two equivalent Fe(2)F7 pentagonal bipyramids, corners with two equivalent Fe(3)F7 pentagonal bipyramids, and  an edgeedge with one Fe(3)F7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 58-65°. The Li(3)-F(10) bond length is 2.07 Å. The Li(3)-F(13) bond length is 1.99 Å. The Li(3)-F(14) bond length is 2.08 Å. The Li(3)-F(15) bond length is 2.31 Å. The Li(3)-F(18) bond length is 2.35 Å. The Li(3)-F(7) bond length is 1.97 Å. There are four inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one F(11), one F(16), one F(17), one F(2), one F(3), one F(6), and one F(9) atom to form distorted FeF7 pentagonal bipyramids that share  a cornercorner with one Li(2)F6 octahedra, corners with two equivalent Li(1)F6 octahedra,  a cornercorner with one Fe(3)F7 pentagonal bipyramid, corners with two equivalent Fe(4)F7 pentagonal bipyramids,  an edgeedge with one Li(1)F6 octahedra, and  an edgeedge with one Fe(2)F7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 2-41°. The Fe(1)-F(11) bond length is 2.30 Å. The Fe(1)-F(16) bond length is 2.00 Å. The Fe(1)-F(17) bond length is 1.83 Å. The Fe(1)-F(2) bond length is 2.01 Å. The Fe(1)-F(3) bond length is 1.97 Å. The Fe(1)-F(6) bond length is 1.96 Å. The Fe(1)-F(9) bond length is 2.04 Å. In the second Fe site, Fe(2) is bonded to one F(10), one F(12), one F(13), one F(6), one F(9), and two equivalent F(8) atoms to form distorted FeF7 pentagonal bipyramids that share  a cornercorner with one Li(1)F6 octahedra, corners with two equivalent Li(2)F6 octahedra, corners with two equivalent Li(3)F6 octahedra,  an edgeedge with one Li(2)F6 octahedra,  an edgeedge with one Fe(1)F7 pentagonal bipyramid, and  an edgeedge with one Fe(2)F7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 1-41°. The Fe(2)-F(10) bond length is 1.78 Å. The Fe(2)-F(12) bond length is 1.79 Å. The Fe(2)-F(13) bond length is 1.83 Å. The Fe(2)-F(6) bond length is 2.33 Å. The Fe(2)-F(9) bond length is 2.04 Å. There is one shorter (1.97 Å) and one longer (2.22 Å) Fe(2)-F(8) bond length. In the third Fe site, Fe(3) is bonded to one F(11), one F(14), one F(18), one F(4), one F(5), and two equivalent F(7) atoms to form FeF7 pentagonal bipyramids that share corners with two equivalent Li(1)F6 octahedra, corners with two equivalent Li(3)F6 octahedra,  a cornercorner with one Fe(1)F7 pentagonal bipyramid,  a cornercorner with one Fe(4)F7 pentagonal bipyramid,  an edgeedge with one Li(3)F6 octahedra, and  an edgeedge with one Fe(3)F7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 6-50°. The Fe(3)-F(11) bond length is 2.11 Å. The Fe(3)-F(14) bond length is 1.78 Å. The Fe(3)-F(18) bond length is 1.87 Å. The Fe(3)-F(4) bond length is 2.03 Å. The Fe(3)-F(5) bond length is 1.79 Å. There is one shorter (1.94 Å) and one longer (2.20 Å) Fe(3)-F(7) bond length. In the fourth Fe site, Fe(4) is bonded to one F(1), one F(15), one F(16), one F(2), one F(4), and two equivalent F(19) atoms to form distorted FeF7 pentagonal bipyramids that share  a cornercorner with one Li(3)F6 octahedra, corners with two equivalent Li(2)F6 octahedra,  a cornercorner with one Fe(3)F7 pentagonal bipyramid, corners with two equivalent Fe(1)F7 pentagonal bipyramids,  an edgeedge with one Li(2)F6 octahedra, and  an edgeedge with one Fe(4)F7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 11-41°. The Fe(4)-F(1) bond length is 1.80 Å. The Fe(4)-F(15) bond length is 1.93 Å. The Fe(4)-F(16) bond length is 1.92 Å. The Fe(4)-F(2) bond length is 1.95 Å. The Fe(4)-F(4) bond length is 2.28 Å. There is one shorter (1.98 Å) and one longer (2.20 Å) Fe(4)-F(19) bond length. There are nineteen inequivalent F sites. In the first F site, F(1) is bonded in a linear geometry to one Li(2) and one Fe(4) atom. In the second F site, F(2) is bonded in a linear geometry to one Fe(1) and one Fe(4) atom. In the third F site, F(3) is bonded in a 3-coordinate geometry to two equivalent Li(1) and one Fe(1) atom. In the fourth F site, F(4) is bonded in a linear geometry to one Fe(3) and one Fe(4) atom. In the fifth F site, F(5) is bonded in a linear geometry to one Li(1) and one Fe(3) atom. In the sixth F site, F(6) is bonded in a 3-coordinate geometry to one Li(1), one Fe(1), and one Fe(2) atom. In the seventh F site, F(7) is bonded in a distorted trigonal planar geometry to one Li(3) and two equivalent Fe(3) atoms. In the eighth F site, F(8) is bonded in a distorted trigonal planar geometry to one Li(2) and two equivalent Fe(2) atoms. In the ninth F site, F(9) is bonded in a trigonal planar geometry to one Li(2), one Fe(1), and one Fe(2) atom. In the tenth F site, F(10) is bonded in a linear geometry to one Li(3) and one Fe(2) atom. In the eleventh F site, F(11) is bonded in a linear geometry to one Fe(1) and one Fe(3) atom. In the twelfth F site, F(12) is bonded in a linear geometry to one Li(2) and one Fe(2) atom. In the thirteenth F site, F(13) is bonded in a linear geometry to one Li(3) and one Fe(2) atom. In the fourteenth F site, F(14) is bonded in a linear geometry to one Li(3) and one Fe(3) atom. In the fifteenth F site, F(15) is bonded in a distorted trigonal planar geometry to one Li(2), one Li(3), and one Fe(4) atom. In the sixteenth F site, F(16) is bonded in a linear geometry to one Fe(1) and one Fe(4) atom. In the seventeenth F site, F(17) is bonded in a linear geometry to one Li(1) and one Fe(1) atom. In the eighteenth F site, F(18) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(3), and one Fe(3) atom. In the nineteenth F site, F(19) is bonded in a distorted trigonal planar geometry to one Li(2) and two equivalent Fe(4) atoms.