Li3Zr4F19 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(13), one F(18), one F(5), one F(6), one F(7), and one F(9) atom to form distorted LiF6 octahedra that share  a cornercorner with one Li(2)F6 octahedra,  a cornercorner with one Zr(2)F7 pentagonal bipyramid, corners with two equivalent Zr(1)F7 pentagonal bipyramids, corners with two equivalent Zr(4)F7 pentagonal bipyramids,  an edgeedge with one Zr(1)F7 pentagonal bipyramid, and  an edgeedge with one Zr(4)F7 pentagonal bipyramid. The corner-sharing octahedral tilt angles are 63°. In the second Li site, Li(2) is bonded to one F(11), one F(12), one F(2), one F(3), one F(4), and one F(6) atom to form distorted LiF6 octahedra that share  a cornercorner with one Li(1)F6 octahedra,  a cornercorner with one Li(3)F6 octahedra,  a cornercorner with one Zr(4)F7 pentagonal bipyramid, corners with two equivalent Zr(1)F7 pentagonal bipyramids, corners with two equivalent Zr(3)F7 pentagonal bipyramids, and  an edgeedge with one Zr(3)F7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 59-63°. In the third Li site, Li(3) is bonded to one F(10), one F(15), one F(17), one F(4), and two equivalent F(8) atoms to form distorted LiF6 octahedra that share  a cornercorner with one Li(2)F6 octahedra,  a cornercorner with one Zr(1)F7 pentagonal bipyramid, corners with two equivalent Zr(2)F7 pentagonal bipyramids, corners with two equivalent Zr(3)F7 pentagonal bipyramids,  an edgeedge with one Li(3)F6 octahedra, and  an edgeedge with one Zr(2)F7 pentagonal bipyramid. The corner-sharing octahedral tilt angles are 59°. There are four inequivalent Zr sites. In the first Zr site, Zr(1) is bonded to one F(11), one F(13), one F(15), one F(2), one F(9), and two equivalent F(7) atoms to form ZrF7 pentagonal bipyramids that share  a cornercorner with one Li(3)F6 octahedra, corners with two equivalent Li(1)F6 octahedra, corners with two equivalent Li(2)F6 octahedra,  an edgeedge with one Li(1)F6 octahedra,  an edgeedge with one Zr(1)F7 pentagonal bipyramid, and  an edgeedge with one Zr(2)F7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 6-45°. In the second Zr site, Zr(2) is bonded to one F(14), one F(15), one F(16), one F(17), one F(19), one F(8), and one F(9) atom to form ZrF7 pentagonal bipyramids that share  a cornercorner with one Li(1)F6 octahedra, corners with two equivalent Li(3)F6 octahedra,  a cornercorner with one Zr(3)F7 pentagonal bipyramid, corners with two equivalent Zr(4)F7 pentagonal bipyramids,  an edgeedge with one Li(3)F6 octahedra, and  an edgeedge with one Zr(1)F7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 9-45°. In the third Zr site, Zr(3) is bonded to one F(1), one F(10), one F(19), one F(3), one F(4), and two equivalent F(12) atoms to form ZrF7 pentagonal bipyramids that share corners with two equivalent Li(2)F6 octahedra, corners with two equivalent Li(3)F6 octahedra,  a cornercorner with one Zr(2)F7 pentagonal bipyramid,  a cornercorner with one Zr(4)F7 pentagonal bipyramid,  an edgeedge with one Li(2)F6 octahedra, and  an edgeedge with one Zr(3)F7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 4-52°. In the fourth Zr site, Zr(4) is bonded to one F(1), one F(14), one F(16), one F(18), one F(6), and two equivalent F(5) atoms to form ZrF7 pentagonal bipyramids that share  a cornercorner with one Li(2)F6 octahedra, corners with two equivalent Li(1)F6 octahedra,  a cornercorner with one Zr(3)F7 pentagonal bipyramid, corners with two equivalent Zr(2)F7 pentagonal bipyramids,  an edgeedge with one Li(1)F6 octahedra, and  an edgeedge with one Zr(4)F7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 10-49°. There are nineteen inequivalent F sites. In the first F site, F(1) is bonded in a linear geometry to one Zr(3) and one Zr(4) atom. In the second F site, F(2) is bonded in a linear geometry to one Li(2) and one Zr(1) atom. In the third F site, F(3) is bonded in a linear geometry to one Li(2) and one Zr(3) atom. In the fourth F site, F(4) is bonded in a trigonal planar geometry to one Li(2), one Li(3), and one Zr(3) atom. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to one Li(1) and two equivalent Zr(4) atoms. In the sixth F site, F(6) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one Zr(4) atom. In the seventh F site, F(7) is bonded in a trigonal planar geometry to one Li(1) and two equivalent Zr(1) atoms. In the eighth F site, F(8) is bonded in a trigonal planar geometry to two equivalent Li(3) and one Zr(2) atom. In the ninth F site, F(9) is bonded in a trigonal planar geometry to one Li(1), one Zr(1), and one Zr(2) atom. In the tenth F site, F(10) is bonded in a linear geometry to one Li(3) and one Zr(3) atom. In the eleventh F site, F(11) is bonded in a linear geometry to one Li(2) and one Zr(1) atom. In the twelfth F site, F(12) is bonded in a distorted trigonal planar geometry to one Li(2) and two equivalent Zr(3) atoms. In the thirteenth F site, F(13) is bonded in a linear geometry to one Li(1) and one Zr(1) atom. In the fourteenth F site, F(14) is bonded in a linear geometry to one Zr(2) and one Zr(4) atom. In the fifteenth F site, F(15) is bonded in a trigonal planar geometry to one Li(3), one Zr(1), and one Zr(2) atom. In the sixteenth F site, F(16) is bonded in a linear geometry to one Zr(2) and one Zr(4) atom. In the seventeenth F site, F(17) is bonded in a linear geometry to one Li(3) and one Zr(2) atom. In the eighteenth F site, F(18) is bonded in a linear geometry to one Li(1) and one Zr(4) atom. In the nineteenth F site, F(19) is bonded in a linear geometry to one Zr(2) and one Zr(3) atom.
Li3Zr4F19 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(13), one F(18), one F(5), one F(6), one F(7), and one F(9) atom to form distorted LiF6 octahedra that share  a cornercorner with one Li(2)F6 octahedra,  a cornercorner with one Zr(2)F7 pentagonal bipyramid, corners with two equivalent Zr(1)F7 pentagonal bipyramids, corners with two equivalent Zr(4)F7 pentagonal bipyramids,  an edgeedge with one Zr(1)F7 pentagonal bipyramid, and  an edgeedge with one Zr(4)F7 pentagonal bipyramid. The corner-sharing octahedral tilt angles are 63°. The Li(1)-F(13) bond length is 1.91 Å. The Li(1)-F(18) bond length is 1.94 Å. The Li(1)-F(5) bond length is 2.14 Å. The Li(1)-F(6) bond length is 2.03 Å. The Li(1)-F(7) bond length is 2.17 Å. The Li(1)-F(9) bond length is 2.21 Å. In the second Li site, Li(2) is bonded to one F(11), one F(12), one F(2), one F(3), one F(4), and one F(6) atom to form distorted LiF6 octahedra that share  a cornercorner with one Li(1)F6 octahedra,  a cornercorner with one Li(3)F6 octahedra,  a cornercorner with one Zr(4)F7 pentagonal bipyramid, corners with two equivalent Zr(1)F7 pentagonal bipyramids, corners with two equivalent Zr(3)F7 pentagonal bipyramids, and  an edgeedge with one Zr(3)F7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 59-63°. The Li(2)-F(11) bond length is 1.91 Å. The Li(2)-F(12) bond length is 2.14 Å. The Li(2)-F(2) bond length is 1.88 Å. The Li(2)-F(3) bond length is 1.90 Å. The Li(2)-F(4) bond length is 2.12 Å. The Li(2)-F(6) bond length is 2.48 Å. In the third Li site, Li(3) is bonded to one F(10), one F(15), one F(17), one F(4), and two equivalent F(8) atoms to form distorted LiF6 octahedra that share  a cornercorner with one Li(2)F6 octahedra,  a cornercorner with one Zr(1)F7 pentagonal bipyramid, corners with two equivalent Zr(2)F7 pentagonal bipyramids, corners with two equivalent Zr(3)F7 pentagonal bipyramids,  an edgeedge with one Li(3)F6 octahedra, and  an edgeedge with one Zr(2)F7 pentagonal bipyramid. The corner-sharing octahedral tilt angles are 59°. The Li(3)-F(10) bond length is 1.89 Å. The Li(3)-F(15) bond length is 2.24 Å. The Li(3)-F(17) bond length is 1.93 Å. The Li(3)-F(4) bond length is 2.11 Å. There is one shorter (2.01 Å) and one longer (2.20 Å) Li(3)-F(8) bond length. There are four inequivalent Zr sites. In the first Zr site, Zr(1) is bonded to one F(11), one F(13), one F(15), one F(2), one F(9), and two equivalent F(7) atoms to form ZrF7 pentagonal bipyramids that share  a cornercorner with one Li(3)F6 octahedra, corners with two equivalent Li(1)F6 octahedra, corners with two equivalent Li(2)F6 octahedra,  an edgeedge with one Li(1)F6 octahedra,  an edgeedge with one Zr(1)F7 pentagonal bipyramid, and  an edgeedge with one Zr(2)F7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 6-45°. The Zr(1)-F(11) bond length is 1.97 Å. The Zr(1)-F(13) bond length is 2.00 Å. The Zr(1)-F(15) bond length is 2.14 Å. The Zr(1)-F(2) bond length is 1.95 Å. The Zr(1)-F(9) bond length is 2.19 Å. There is one shorter (2.13 Å) and one longer (2.18 Å) Zr(1)-F(7) bond length. In the second Zr site, Zr(2) is bonded to one F(14), one F(15), one F(16), one F(17), one F(19), one F(8), and one F(9) atom to form ZrF7 pentagonal bipyramids that share  a cornercorner with one Li(1)F6 octahedra, corners with two equivalent Li(3)F6 octahedra,  a cornercorner with one Zr(3)F7 pentagonal bipyramid, corners with two equivalent Zr(4)F7 pentagonal bipyramids,  an edgeedge with one Li(3)F6 octahedra, and  an edgeedge with one Zr(1)F7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 9-45°. The Zr(2)-F(14) bond length is 2.10 Å. The Zr(2)-F(15) bond length is 2.15 Å. The Zr(2)-F(16) bond length is 2.10 Å. The Zr(2)-F(17) bond length is 1.94 Å. The Zr(2)-F(19) bond length is 2.09 Å. The Zr(2)-F(8) bond length is 1.97 Å. The Zr(2)-F(9) bond length is 2.13 Å. In the third Zr site, Zr(3) is bonded to one F(1), one F(10), one F(19), one F(3), one F(4), and two equivalent F(12) atoms to form ZrF7 pentagonal bipyramids that share corners with two equivalent Li(2)F6 octahedra, corners with two equivalent Li(3)F6 octahedra,  a cornercorner with one Zr(2)F7 pentagonal bipyramid,  a cornercorner with one Zr(4)F7 pentagonal bipyramid,  an edgeedge with one Li(2)F6 octahedra, and  an edgeedge with one Zr(3)F7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 4-52°. The Zr(3)-F(1) bond length is 2.17 Å. The Zr(3)-F(10) bond length is 1.99 Å. The Zr(3)-F(19) bond length is 2.09 Å. The Zr(3)-F(3) bond length is 1.97 Å. The Zr(3)-F(4) bond length is 2.01 Å. There is one shorter (2.14 Å) and one longer (2.15 Å) Zr(3)-F(12) bond length. In the fourth Zr site, Zr(4) is bonded to one F(1), one F(14), one F(16), one F(18), one F(6), and two equivalent F(5) atoms to form ZrF7 pentagonal bipyramids that share  a cornercorner with one Li(2)F6 octahedra, corners with two equivalent Li(1)F6 octahedra,  a cornercorner with one Zr(3)F7 pentagonal bipyramid, corners with two equivalent Zr(2)F7 pentagonal bipyramids,  an edgeedge with one Li(1)F6 octahedra, and  an edgeedge with one Zr(4)F7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 10-49°. The Zr(4)-F(1) bond length is 2.07 Å. The Zr(4)-F(14) bond length is 2.10 Å. The Zr(4)-F(16) bond length is 2.12 Å. The Zr(4)-F(18) bond length is 1.95 Å. The Zr(4)-F(6) bond length is 1.99 Å. There is one shorter (2.15 Å) and one longer (2.18 Å) Zr(4)-F(5) bond length. There are nineteen inequivalent F sites. In the first F site, F(1) is bonded in a linear geometry to one Zr(3) and one Zr(4) atom. In the second F site, F(2) is bonded in a linear geometry to one Li(2) and one Zr(1) atom. In the third F site, F(3) is bonded in a linear geometry to one Li(2) and one Zr(3) atom. In the fourth F site, F(4) is bonded in a trigonal planar geometry to one Li(2), one Li(3), and one Zr(3) atom. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to one Li(1) and two equivalent Zr(4) atoms. In the sixth F site, F(6) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one Zr(4) atom. In the seventh F site, F(7) is bonded in a trigonal planar geometry to one Li(1) and two equivalent Zr(1) atoms. In the eighth F site, F(8) is bonded in a trigonal planar geometry to two equivalent Li(3) and one Zr(2) atom. In the ninth F site, F(9) is bonded in a trigonal planar geometry to one Li(1), one Zr(1), and one Zr(2) atom. In the tenth F site, F(10) is bonded in a linear geometry to one Li(3) and one Zr(3) atom. In the eleventh F site, F(11) is bonded in a linear geometry to one Li(2) and one Zr(1) atom. In the twelfth F site, F(12) is bonded in a distorted trigonal planar geometry to one Li(2) and two equivalent Zr(3) atoms. In the thirteenth F site, F(13) is bonded in a linear geometry to one Li(1) and one Zr(1) atom. In the fourteenth F site, F(14) is bonded in a linear geometry to one Zr(2) and one Zr(4) atom. In the fifteenth F site, F(15) is bonded in a trigonal planar geometry to one Li(3), one Zr(1), and one Zr(2) atom. In the sixteenth F site, F(16) is bonded in a linear geometry to one Zr(2) and one Zr(4) atom. In the seventeenth F site, F(17) is bonded in a linear geometry to one Li(3) and one Zr(2) atom. In the eighteenth F site, F(18) is bonded in a linear geometry to one Li(1) and one Zr(4) atom. In the nineteenth F site, F(19) is bonded in a linear geometry to one Zr(2) and one Zr(3) atom.