LiNi3OF5 is Corundum-derived structured and crystallizes in the triclinic P1 space group. Li(1) is bonded to one O(1), one F(1), one F(2), one F(3), one F(4), and one F(5) atom to form distorted LiOF5 octahedra that share corners with three equivalent Ni(1)OF5 octahedra, corners with six equivalent Ni(2)OF5 octahedra, edges with three equivalent Ni(3)OF5 octahedra, and  a faceface with one Ni(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 47-63°. There are three inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one O(1), one F(1), one F(2), one F(3), one F(4), and one F(5) atom to form NiOF5 octahedra that share corners with three equivalent Li(1)OF5 octahedra, corners with six equivalent Ni(3)OF5 octahedra, edges with three equivalent Ni(2)OF5 octahedra, and  a faceface with one Li(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 43-63°. In the second Ni site, Ni(2) is bonded to one O(1), one F(1), one F(2), one F(3), one F(4), and one F(5) atom to form NiOF5 octahedra that share corners with three equivalent Ni(3)OF5 octahedra, corners with six equivalent Li(1)OF5 octahedra, edges with three equivalent Ni(1)OF5 octahedra, and  a faceface with one Ni(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 47-62°. In the third Ni site, Ni(3) is bonded to one O(1), one F(1), one F(2), one F(3), one F(4), and one F(5) atom to form distorted NiOF5 octahedra that share corners with three equivalent Ni(2)OF5 octahedra, corners with six equivalent Ni(1)OF5 octahedra, edges with three equivalent Li(1)OF5 octahedra, and  a faceface with one Ni(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 43-62°. O(1) is bonded to one Li(1), one Ni(1), one Ni(2), and one Ni(3) atom to form OLiNi3 trigonal pyramids that share corners with two equivalent F(2)LiNi3 trigonal pyramids, corners with two equivalent F(5)LiNi3 trigonal pyramids, corners with four equivalent F(3)LiNi3 trigonal pyramids,  an edgeedge with one F(2)LiNi3 trigonal pyramid, and  an edgeedge with one F(5)LiNi3 trigonal pyramid. There are five inequivalent F sites. In the first F site, F(1) is bonded in a distorted see-saw-like geometry to one Li(1), one Ni(1), one Ni(2), and one Ni(3) atom. In the second F site, F(2) is bonded to one Li(1), one Ni(1), one Ni(2), and one Ni(3) atom to form distorted FLiNi3 trigonal pyramids that share corners with two equivalent O(1)LiNi3 trigonal pyramids, corners with two equivalent F(5)LiNi3 trigonal pyramids,  an edgeedge with one O(1)LiNi3 trigonal pyramid,  an edgeedge with one F(5)LiNi3 trigonal pyramid, and edges with two equivalent F(3)LiNi3 trigonal pyramids. In the third F site, F(3) is bonded to one Li(1), one Ni(1), one Ni(2), and one Ni(3) atom to form distorted FLiNi3 trigonal pyramids that share corners with four equivalent O(1)LiNi3 trigonal pyramids, corners with four equivalent F(5)LiNi3 trigonal pyramids, and edges with two equivalent F(2)LiNi3 trigonal pyramids. In the fourth F site, F(4) is bonded in a rectangular see-saw-like geometry to one Li(1), one Ni(1), one Ni(2), and one Ni(3) atom. In the fifth F site, F(5) is bonded to one Li(1), one Ni(1), one Ni(2), and one Ni(3) atom to form distorted FLiNi3 trigonal pyramids that share corners with two equivalent O(1)LiNi3 trigonal pyramids, corners with two equivalent F(2)LiNi3 trigonal pyramids, corners with four equivalent F(3)LiNi3 trigonal pyramids,  an edgeedge with one O(1)LiNi3 trigonal pyramid, and  an edgeedge with one F(2)LiNi3 trigonal pyramid.
LiNi3OF5 is Corundum-derived structured and crystallizes in the triclinic P1 space group. Li(1) is bonded to one O(1), one F(1), one F(2), one F(3), one F(4), and one F(5) atom to form distorted LiOF5 octahedra that share corners with three equivalent Ni(1)OF5 octahedra, corners with six equivalent Ni(2)OF5 octahedra, edges with three equivalent Ni(3)OF5 octahedra, and  a faceface with one Ni(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 47-63°. The Li(1)-O(1) bond length is 2.06 Å. The Li(1)-F(1) bond length is 1.98 Å. The Li(1)-F(2) bond length is 2.35 Å. The Li(1)-F(3) bond length is 2.09 Å. The Li(1)-F(4) bond length is 1.97 Å. The Li(1)-F(5) bond length is 2.13 Å. There are three inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one O(1), one F(1), one F(2), one F(3), one F(4), and one F(5) atom to form NiOF5 octahedra that share corners with three equivalent Li(1)OF5 octahedra, corners with six equivalent Ni(3)OF5 octahedra, edges with three equivalent Ni(2)OF5 octahedra, and  a faceface with one Li(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 43-63°. The Ni(1)-O(1) bond length is 1.94 Å. The Ni(1)-F(1) bond length is 2.08 Å. The Ni(1)-F(2) bond length is 2.06 Å. The Ni(1)-F(3) bond length is 2.04 Å. The Ni(1)-F(4) bond length is 2.05 Å. The Ni(1)-F(5) bond length is 2.17 Å. In the second Ni site, Ni(2) is bonded to one O(1), one F(1), one F(2), one F(3), one F(4), and one F(5) atom to form NiOF5 octahedra that share corners with three equivalent Ni(3)OF5 octahedra, corners with six equivalent Li(1)OF5 octahedra, edges with three equivalent Ni(1)OF5 octahedra, and  a faceface with one Ni(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 47-62°. The Ni(2)-O(1) bond length is 1.93 Å. The Ni(2)-F(1) bond length is 2.07 Å. The Ni(2)-F(2) bond length is 2.05 Å. The Ni(2)-F(3) bond length is 2.17 Å. The Ni(2)-F(4) bond length is 2.11 Å. The Ni(2)-F(5) bond length is 2.01 Å. In the third Ni site, Ni(3) is bonded to one O(1), one F(1), one F(2), one F(3), one F(4), and one F(5) atom to form distorted NiOF5 octahedra that share corners with three equivalent Ni(2)OF5 octahedra, corners with six equivalent Ni(1)OF5 octahedra, edges with three equivalent Li(1)OF5 octahedra, and  a faceface with one Ni(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 43-62°. The Ni(3)-O(1) bond length is 1.92 Å. The Ni(3)-F(1) bond length is 2.20 Å. The Ni(3)-F(2) bond length is 2.02 Å. The Ni(3)-F(3) bond length is 2.13 Å. The Ni(3)-F(4) bond length is 2.13 Å. The Ni(3)-F(5) bond length is 2.05 Å. O(1) is bonded to one Li(1), one Ni(1), one Ni(2), and one Ni(3) atom to form OLiNi3 trigonal pyramids that share corners with two equivalent F(2)LiNi3 trigonal pyramids, corners with two equivalent F(5)LiNi3 trigonal pyramids, corners with four equivalent F(3)LiNi3 trigonal pyramids,  an edgeedge with one F(2)LiNi3 trigonal pyramid, and  an edgeedge with one F(5)LiNi3 trigonal pyramid. There are five inequivalent F sites. In the first F site, F(1) is bonded in a distorted see-saw-like geometry to one Li(1), one Ni(1), one Ni(2), and one Ni(3) atom. In the second F site, F(2) is bonded to one Li(1), one Ni(1), one Ni(2), and one Ni(3) atom to form distorted FLiNi3 trigonal pyramids that share corners with two equivalent O(1)LiNi3 trigonal pyramids, corners with two equivalent F(5)LiNi3 trigonal pyramids,  an edgeedge with one O(1)LiNi3 trigonal pyramid,  an edgeedge with one F(5)LiNi3 trigonal pyramid, and edges with two equivalent F(3)LiNi3 trigonal pyramids. In the third F site, F(3) is bonded to one Li(1), one Ni(1), one Ni(2), and one Ni(3) atom to form distorted FLiNi3 trigonal pyramids that share corners with four equivalent O(1)LiNi3 trigonal pyramids, corners with four equivalent F(5)LiNi3 trigonal pyramids, and edges with two equivalent F(2)LiNi3 trigonal pyramids. In the fourth F site, F(4) is bonded in a rectangular see-saw-like geometry to one Li(1), one Ni(1), one Ni(2), and one Ni(3) atom. In the fifth F site, F(5) is bonded to one Li(1), one Ni(1), one Ni(2), and one Ni(3) atom to form distorted FLiNi3 trigonal pyramids that share corners with two equivalent O(1)LiNi3 trigonal pyramids, corners with two equivalent F(2)LiNi3 trigonal pyramids, corners with four equivalent F(3)LiNi3 trigonal pyramids,  an edgeedge with one O(1)LiNi3 trigonal pyramid, and  an edgeedge with one F(2)LiNi3 trigonal pyramid.