Li5Ni3O5F3 crystallizes in the triclinic P1 space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one O(3), one O(4), one O(5), one F(1), and one F(2) atom to form LiO4F2 octahedra that share edges with two equivalent Li(2)O3F3 octahedra, edges with two equivalent Li(3)O3F3 octahedra, edges with two equivalent Li(5)O3F3 octahedra, edges with two equivalent Li(4)O5F octahedra, edges with two equivalent Ni(1)O3F3 octahedra, and edges with two equivalent Ni(2)O5F octahedra. In the second Li site, Li(2) is bonded to one O(1), one O(3), one O(4), one F(1), one F(2), and one F(3) atom to form LiO3F3 octahedra that share corners with six equivalent Li(5)O3F3 octahedra, edges with two equivalent Li(3)O3F3 octahedra, edges with two equivalent Li(1)O4F2 octahedra, edges with two equivalent Li(4)O5F octahedra, edges with two equivalent Ni(1)O3F3 octahedra, and edges with two equivalent Ni(2)O5F octahedra. The corner-sharing octahedral tilt angles range from 1-18°. In the third Li site, Li(3) is bonded to one O(1), one O(2), one O(5), one F(1), one F(2), and one F(3) atom to form distorted LiO3F3 octahedra that share corners with six equivalent Ni(1)O3F3 octahedra, edges with two equivalent Li(2)O3F3 octahedra, edges with two equivalent Li(5)O3F3 octahedra, edges with two equivalent Li(1)O4F2 octahedra, edges with two equivalent Li(4)O5F octahedra, and edges with two equivalent Ni(2)O5F octahedra. The corner-sharing octahedral tilt angles range from 3-18°. In the fourth Li site, Li(4) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one F(3) atom to form LiO5F octahedra that share corners with six equivalent Ni(2)O5F octahedra, edges with two equivalent Li(2)O3F3 octahedra, edges with two equivalent Li(3)O3F3 octahedra, edges with two equivalent Li(5)O3F3 octahedra, edges with two equivalent Li(1)O4F2 octahedra, and edges with two equivalent Ni(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 0-12°. In the fifth Li site, Li(5) is bonded to one O(1), one O(3), one O(4), one F(1), one F(2), and one F(3) atom to form LiO3F3 octahedra that share corners with six equivalent Li(2)O3F3 octahedra, edges with two equivalent Li(3)O3F3 octahedra, edges with two equivalent Li(1)O4F2 octahedra, edges with two equivalent Li(4)O5F octahedra, edges with two equivalent Ni(1)O3F3 octahedra, and edges with two equivalent Ni(2)O5F octahedra. The corner-sharing octahedral tilt angles range from 1-18°. There are three inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one O(1), one O(2), one O(5), one F(1), one F(2), and one F(3) atom to form NiO3F3 octahedra that share corners with six equivalent Li(3)O3F3 octahedra, edges with two equivalent Li(2)O3F3 octahedra, edges with two equivalent Li(5)O3F3 octahedra, edges with two equivalent Li(1)O4F2 octahedra, edges with two equivalent Li(4)O5F octahedra, and edges with two equivalent Ni(2)O5F octahedra. The corner-sharing octahedral tilt angles range from 3-18°. In the second Ni site, Ni(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one F(3) atom to form distorted NiO5F octahedra that share corners with six equivalent Li(4)O5F octahedra, edges with two equivalent Li(2)O3F3 octahedra, edges with two equivalent Li(3)O3F3 octahedra, edges with two equivalent Li(5)O3F3 octahedra, edges with two equivalent Li(1)O4F2 octahedra, and edges with two equivalent Ni(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 0-12°. In the third Ni site, Ni(3) is bonded in a distorted square co-planar geometry to one O(2), one O(3), one O(4), and one O(5) atom. There are five inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), one Li(3), one Li(4), one Li(5), one Ni(1), and one Ni(2) atom to form OLi4Ni2 octahedra that share corners with six equivalent F(3)Li4Ni2 octahedra, edges with two equivalent O(2)Li3Ni3 octahedra, edges with two equivalent O(5)Li3Ni3 octahedra, edges with two equivalent O(3)Li4Ni2 octahedra, and edges with two equivalent O(4)Li4Ni2 octahedra. The corner-sharing octahedral tilt angles range from 1-6°. In the second O site, O(2) is bonded to one Li(1), one Li(3), one Li(4), one Ni(1), one Ni(2), and one Ni(3) atom to form OLi3Ni3 octahedra that share corners with six equivalent O(5)Li3Ni3 octahedra, edges with two equivalent O(1)Li4Ni2 octahedra, edges with two equivalent O(3)Li4Ni2 octahedra, edges with two equivalent O(4)Li4Ni2 octahedra, and edges with two equivalent F(3)Li4Ni2 octahedra. The corner-sharing octahedral tilt angles range from 1-8°. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Li(4), one Li(5), one Ni(2), and one Ni(3) atom to form OLi4Ni2 octahedra that share corners with six equivalent O(4)Li4Ni2 octahedra, edges with two equivalent O(2)Li3Ni3 octahedra, edges with two equivalent O(5)Li3Ni3 octahedra, edges with two equivalent O(1)Li4Ni2 octahedra, and edges with two equivalent F(3)Li4Ni2 octahedra. The corner-sharing octahedral tilt angles range from 0-7°. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one Li(4), one Li(5), one Ni(2), and one Ni(3) atom to form OLi4Ni2 octahedra that share corners with six equivalent O(3)Li4Ni2 octahedra, edges with two equivalent O(2)Li3Ni3 octahedra, edges with two equivalent O(5)Li3Ni3 octahedra, edges with two equivalent O(1)Li4Ni2 octahedra, and edges with two equivalent F(3)Li4Ni2 octahedra. The corner-sharing octahedral tilt angles range from 0-7°. In the fifth O site, O(5) is bonded to one Li(1), one Li(3), one Li(4), one Ni(1), one Ni(2), and one Ni(3) atom to form OLi3Ni3 octahedra that share corners with six equivalent O(2)Li3Ni3 octahedra, edges with two equivalent O(1)Li4Ni2 octahedra, edges with two equivalent O(3)Li4Ni2 octahedra, edges with two equivalent O(4)Li4Ni2 octahedra, and edges with two equivalent F(3)Li4Ni2 octahedra. The corner-sharing octahedral tilt angles range from 1-8°. There are three inequivalent F sites. In the first F site, F(1) is bonded in a 5-coordinate geometry to one Li(1), one Li(2), one Li(3), one Li(5), and one Ni(1) atom. In the second F site, F(2) is bonded in a 5-coordinate geometry to one Li(1), one Li(2), one Li(3), one Li(5), and one Ni(1) atom. In the third F site, F(3) is bonded to one Li(2), one Li(3), one Li(4), one Li(5), one Ni(1), and one Ni(2) atom to form distorted FLi4Ni2 octahedra that share corners with six equivalent O(1)Li4Ni2 octahedra, edges with two equivalent O(2)Li3Ni3 octahedra, edges with two equivalent O(5)Li3Ni3 octahedra, edges with two equivalent O(3)Li4Ni2 octahedra, and edges with two equivalent O(4)Li4Ni2 octahedra. The corner-sharing octahedral tilt angles range from 1-6°.
Li5Ni3O5F3 crystallizes in the triclinic P1 space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one O(3), one O(4), one O(5), one F(1), and one F(2) atom to form LiO4F2 octahedra that share edges with two equivalent Li(2)O3F3 octahedra, edges with two equivalent Li(3)O3F3 octahedra, edges with two equivalent Li(5)O3F3 octahedra, edges with two equivalent Li(4)O5F octahedra, edges with two equivalent Ni(1)O3F3 octahedra, and edges with two equivalent Ni(2)O5F octahedra. The Li(1)-O(2) bond length is 2.12 Å. The Li(1)-O(3) bond length is 2.15 Å. The Li(1)-O(4) bond length is 2.15 Å. The Li(1)-O(5) bond length is 2.12 Å. The Li(1)-F(1) bond length is 1.90 Å. The Li(1)-F(2) bond length is 1.90 Å. In the second Li site, Li(2) is bonded to one O(1), one O(3), one O(4), one F(1), one F(2), and one F(3) atom to form LiO3F3 octahedra that share corners with six equivalent Li(5)O3F3 octahedra, edges with two equivalent Li(3)O3F3 octahedra, edges with two equivalent Li(1)O4F2 octahedra, edges with two equivalent Li(4)O5F octahedra, edges with two equivalent Ni(1)O3F3 octahedra, and edges with two equivalent Ni(2)O5F octahedra. The corner-sharing octahedral tilt angles range from 1-18°. The Li(2)-O(1) bond length is 1.95 Å. The Li(2)-O(3) bond length is 2.18 Å. The Li(2)-O(4) bond length is 2.22 Å. The Li(2)-F(1) bond length is 2.00 Å. The Li(2)-F(2) bond length is 2.01 Å. The Li(2)-F(3) bond length is 2.04 Å. In the third Li site, Li(3) is bonded to one O(1), one O(2), one O(5), one F(1), one F(2), and one F(3) atom to form distorted LiO3F3 octahedra that share corners with six equivalent Ni(1)O3F3 octahedra, edges with two equivalent Li(2)O3F3 octahedra, edges with two equivalent Li(5)O3F3 octahedra, edges with two equivalent Li(1)O4F2 octahedra, edges with two equivalent Li(4)O5F octahedra, and edges with two equivalent Ni(2)O5F octahedra. The corner-sharing octahedral tilt angles range from 3-18°. The Li(3)-O(1) bond length is 1.91 Å. The Li(3)-O(2) bond length is 2.33 Å. The Li(3)-O(5) bond length is 2.40 Å. The Li(3)-F(1) bond length is 1.96 Å. The Li(3)-F(2) bond length is 1.98 Å. The Li(3)-F(3) bond length is 1.98 Å. In the fourth Li site, Li(4) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one F(3) atom to form LiO5F octahedra that share corners with six equivalent Ni(2)O5F octahedra, edges with two equivalent Li(2)O3F3 octahedra, edges with two equivalent Li(3)O3F3 octahedra, edges with two equivalent Li(5)O3F3 octahedra, edges with two equivalent Li(1)O4F2 octahedra, and edges with two equivalent Ni(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 0-12°. The Li(4)-O(1) bond length is 2.11 Å. The Li(4)-O(2) bond length is 2.07 Å. The Li(4)-O(3) bond length is 2.12 Å. The Li(4)-O(4) bond length is 2.12 Å. The Li(4)-O(5) bond length is 2.07 Å. The Li(4)-F(3) bond length is 2.22 Å. In the fifth Li site, Li(5) is bonded to one O(1), one O(3), one O(4), one F(1), one F(2), and one F(3) atom to form LiO3F3 octahedra that share corners with six equivalent Li(2)O3F3 octahedra, edges with two equivalent Li(3)O3F3 octahedra, edges with two equivalent Li(1)O4F2 octahedra, edges with two equivalent Li(4)O5F octahedra, edges with two equivalent Ni(1)O3F3 octahedra, and edges with two equivalent Ni(2)O5F octahedra. The corner-sharing octahedral tilt angles range from 1-18°. The Li(5)-O(1) bond length is 1.95 Å. The Li(5)-O(3) bond length is 2.25 Å. The Li(5)-O(4) bond length is 2.19 Å. The Li(5)-F(1) bond length is 1.99 Å. The Li(5)-F(2) bond length is 1.99 Å. The Li(5)-F(3) bond length is 2.02 Å. There are three inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one O(1), one O(2), one O(5), one F(1), one F(2), and one F(3) atom to form NiO3F3 octahedra that share corners with six equivalent Li(3)O3F3 octahedra, edges with two equivalent Li(2)O3F3 octahedra, edges with two equivalent Li(5)O3F3 octahedra, edges with two equivalent Li(1)O4F2 octahedra, edges with two equivalent Li(4)O5F octahedra, and edges with two equivalent Ni(2)O5F octahedra. The corner-sharing octahedral tilt angles range from 3-18°. The Ni(1)-O(1) bond length is 1.93 Å. The Ni(1)-O(2) bond length is 2.06 Å. The Ni(1)-O(5) bond length is 2.03 Å. The Ni(1)-F(1) bond length is 2.05 Å. The Ni(1)-F(2) bond length is 2.05 Å. The Ni(1)-F(3) bond length is 2.07 Å. In the second Ni site, Ni(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one F(3) atom to form distorted NiO5F octahedra that share corners with six equivalent Li(4)O5F octahedra, edges with two equivalent Li(2)O3F3 octahedra, edges with two equivalent Li(3)O3F3 octahedra, edges with two equivalent Li(5)O3F3 octahedra, edges with two equivalent Li(1)O4F2 octahedra, and edges with two equivalent Ni(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 0-12°. The Ni(2)-O(1) bond length is 2.04 Å. The Ni(2)-O(2) bond length is 1.91 Å. The Ni(2)-O(3) bond length is 1.88 Å. The Ni(2)-O(4) bond length is 1.88 Å. The Ni(2)-O(5) bond length is 1.90 Å. The Ni(2)-F(3) bond length is 2.42 Å. In the third Ni site, Ni(3) is bonded in a distorted square co-planar geometry to one O(2), one O(3), one O(4), and one O(5) atom. The Ni(3)-O(2) bond length is 1.87 Å. The Ni(3)-O(3) bond length is 1.80 Å. The Ni(3)-O(4) bond length is 1.80 Å. The Ni(3)-O(5) bond length is 1.88 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), one Li(3), one Li(4), one Li(5), one Ni(1), and one Ni(2) atom to form OLi4Ni2 octahedra that share corners with six equivalent F(3)Li4Ni2 octahedra, edges with two equivalent O(2)Li3Ni3 octahedra, edges with two equivalent O(5)Li3Ni3 octahedra, edges with two equivalent O(3)Li4Ni2 octahedra, and edges with two equivalent O(4)Li4Ni2 octahedra. The corner-sharing octahedral tilt angles range from 1-6°. In the second O site, O(2) is bonded to one Li(1), one Li(3), one Li(4), one Ni(1), one Ni(2), and one Ni(3) atom to form OLi3Ni3 octahedra that share corners with six equivalent O(5)Li3Ni3 octahedra, edges with two equivalent O(1)Li4Ni2 octahedra, edges with two equivalent O(3)Li4Ni2 octahedra, edges with two equivalent O(4)Li4Ni2 octahedra, and edges with two equivalent F(3)Li4Ni2 octahedra. The corner-sharing octahedral tilt angles range from 1-8°. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Li(4), one Li(5), one Ni(2), and one Ni(3) atom to form OLi4Ni2 octahedra that share corners with six equivalent O(4)Li4Ni2 octahedra, edges with two equivalent O(2)Li3Ni3 octahedra, edges with two equivalent O(5)Li3Ni3 octahedra, edges with two equivalent O(1)Li4Ni2 octahedra, and edges with two equivalent F(3)Li4Ni2 octahedra. The corner-sharing octahedral tilt angles range from 0-7°. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one Li(4), one Li(5), one Ni(2), and one Ni(3) atom to form OLi4Ni2 octahedra that share corners with six equivalent O(3)Li4Ni2 octahedra, edges with two equivalent O(2)Li3Ni3 octahedra, edges with two equivalent O(5)Li3Ni3 octahedra, edges with two equivalent O(1)Li4Ni2 octahedra, and edges with two equivalent F(3)Li4Ni2 octahedra. The corner-sharing octahedral tilt angles range from 0-7°. In the fifth O site, O(5) is bonded to one Li(1), one Li(3), one Li(4), one Ni(1), one Ni(2), and one Ni(3) atom to form OLi3Ni3 octahedra that share corners with six equivalent O(2)Li3Ni3 octahedra, edges with two equivalent O(1)Li4Ni2 octahedra, edges with two equivalent O(3)Li4Ni2 octahedra, edges with two equivalent O(4)Li4Ni2 octahedra, and edges with two equivalent F(3)Li4Ni2 octahedra. The corner-sharing octahedral tilt angles range from 1-8°. There are three inequivalent F sites. In the first F site, F(1) is bonded in a 5-coordinate geometry to one Li(1), one Li(2), one Li(3), one Li(5), and one Ni(1) atom. In the second F site, F(2) is bonded in a 5-coordinate geometry to one Li(1), one Li(2), one Li(3), one Li(5), and one Ni(1) atom. In the third F site, F(3) is bonded to one Li(2), one Li(3), one Li(4), one Li(5), one Ni(1), and one Ni(2) atom to form distorted FLi4Ni2 octahedra that share corners with six equivalent O(1)Li4Ni2 octahedra, edges with two equivalent O(2)Li3Ni3 octahedra, edges with two equivalent O(5)Li3Ni3 octahedra, edges with two equivalent O(3)Li4Ni2 octahedra, and edges with two equivalent O(4)Li4Ni2 octahedra. The corner-sharing octahedral tilt angles range from 1-6°.