Li2Ni4OF8 is Corundum-derived structured and crystallizes in the monoclinic Cc space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(1), one F(3), one F(4), one F(6), one F(7), and one F(8) atom to form LiF6 octahedra that share corners with three equivalent Ni(1)OF5 octahedra, corners with three equivalent Ni(2)OF5 octahedra, corners with three equivalent Ni(4)OF5 octahedra, edges with three equivalent Ni(3)F6 octahedra, and  a faceface with one Li(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 44-62°. In the second Li site, Li(2) is bonded to one O(1), one F(1), one F(2), one F(3), one F(5), and one F(6) atom to form distorted LiOF5 octahedra that share corners with three equivalent Ni(3)F6 octahedra, corners with three equivalent Ni(2)OF5 octahedra, corners with three equivalent Ni(4)OF5 octahedra, edges with three equivalent Ni(1)OF5 octahedra, and  a faceface with one Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 46-63°. There are four 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(5), and one F(6) atom to form NiOF5 octahedra that share corners with three equivalent Li(1)F6 octahedra, corners with three equivalent Ni(3)F6 octahedra, corners with three equivalent Ni(4)OF5 octahedra, edges with three equivalent Li(2)OF5 octahedra, and  a faceface with one Ni(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 45-60°. In the second Ni site, Ni(2) is bonded to one O(1), one F(2), one F(4), one F(5), one F(7), and one F(8) atom to form NiOF5 octahedra that share corners with three equivalent Li(1)F6 octahedra, corners with three equivalent Li(2)OF5 octahedra, corners with three equivalent Ni(3)F6 octahedra, edges with three equivalent Ni(4)OF5 octahedra, and  a faceface with one Ni(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 45-62°. In the third Ni site, Ni(3) is bonded to one F(1), one F(3), one F(4), one F(6), one F(7), and one F(8) atom to form NiF6 octahedra that share corners with three equivalent Li(2)OF5 octahedra, corners with three equivalent Ni(1)OF5 octahedra, corners with three equivalent Ni(2)OF5 octahedra, edges with three equivalent Li(1)F6 octahedra, and  a faceface with one Ni(4)OF5 octahedra. The corner-sharing octahedral tilt angles range from 45-60°. In the fourth Ni site, Ni(4) is bonded to one O(1), one F(2), one F(4), one F(5), one F(7), and one F(8) atom to form distorted NiOF5 octahedra that share corners with three equivalent Li(1)F6 octahedra, corners with three equivalent Li(2)OF5 octahedra, corners with three equivalent Ni(1)OF5 octahedra, edges with three equivalent Ni(2)OF5 octahedra, and  a faceface with one Ni(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 44-63°. O(1) is bonded to one Li(2), one Ni(1), one Ni(2), and one Ni(4) atom to form distorted OLiNi3 trigonal pyramids that share corners with two equivalent F(3)Li2Ni2 trigonal pyramids, corners with two equivalent F(6)Li2Ni2 trigonal pyramids, corners with two equivalent F(4)LiNi3 trigonal pyramids, corners with two equivalent F(5)LiNi3 trigonal pyramids,  an edgeedge with one F(1)Li2Ni2 trigonal pyramid, and  an edgeedge with one F(5)LiNi3 trigonal pyramid. There are eight inequivalent F sites. In the first F site, F(3) is bonded to one Li(1), one Li(2), one Ni(1), and one Ni(3) atom to form distorted FLi2Ni2 trigonal pyramids that share corners with two equivalent O(1)LiNi3 trigonal pyramids, corners with two equivalent F(1)Li2Ni2 trigonal pyramids, corners with two equivalent F(6)Li2Ni2 trigonal pyramids, corners with two equivalent F(5)LiNi3 trigonal pyramids,  an edgeedge with one F(1)Li2Ni2 trigonal pyramid,  an edgeedge with one F(6)Li2Ni2 trigonal pyramid, and  an edgeedge with one F(4)LiNi3 trigonal pyramid. In the second F site, F(4) is bonded to one Li(1), one Ni(2), one Ni(3), and one Ni(4) atom to form distorted FLiNi3 trigonal pyramids that share corners with two equivalent O(1)LiNi3 trigonal pyramids, corners with two equivalent F(1)Li2Ni2 trigonal pyramids, corners with two equivalent F(6)Li2Ni2 trigonal pyramids,  an edgeedge with one F(3)Li2Ni2 trigonal pyramid, and  an edgeedge with one F(5)LiNi3 trigonal pyramid. In the third F site, F(5) is bonded to one Li(2), one Ni(1), one Ni(2), and one Ni(4) atom to form distorted FLiNi3 trigonal pyramids that share corners with two equivalent O(1)LiNi3 trigonal pyramids, corners with two equivalent F(1)Li2Ni2 trigonal pyramids, corners with two equivalent F(3)Li2Ni2 trigonal pyramids,  an edgeedge with one O(1)LiNi3 trigonal pyramid,  an edgeedge with one F(6)Li2Ni2 trigonal pyramid, and  an edgeedge with one F(4)LiNi3 trigonal pyramid. In the fourth F site, F(6) is bonded to one Li(1), one Li(2), one Ni(1), and one Ni(3) atom to form distorted FLi2Ni2 trigonal pyramids that share corners with two equivalent O(1)LiNi3 trigonal pyramids, corners with two equivalent F(1)Li2Ni2 trigonal pyramids, corners with two equivalent F(3)Li2Ni2 trigonal pyramids, corners with two equivalent F(4)LiNi3 trigonal pyramids,  an edgeedge with one F(1)Li2Ni2 trigonal pyramid,  an edgeedge with one F(3)Li2Ni2 trigonal pyramid, and  an edgeedge with one F(5)LiNi3 trigonal pyramid. In the fifth F site, F(7) is bonded in a rectangular see-saw-like geometry to one Li(1), one Ni(2), one Ni(3), and one Ni(4) atom. In the sixth F site, F(8) is bonded in a rectangular see-saw-like geometry to one Li(1), one Ni(2), one Ni(3), and one Ni(4) atom. In the seventh F site, F(1) is bonded to one Li(1), one Li(2), one Ni(1), and one Ni(3) atom to form distorted FLi2Ni2 trigonal pyramids that share corners with two equivalent F(3)Li2Ni2 trigonal pyramids, corners with two equivalent F(6)Li2Ni2 trigonal pyramids, corners with two equivalent F(4)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(3)Li2Ni2 trigonal pyramid, and  an edgeedge with one F(6)Li2Ni2 trigonal pyramid. In the eighth F site, F(2) is bonded in a 4-coordinate geometry to one Li(2), one Ni(1), one Ni(2), and one Ni(4) atom.
Li2Ni4OF8 is Corundum-derived structured and crystallizes in the monoclinic Cc space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(1), one F(3), one F(4), one F(6), one F(7), and one F(8) atom to form LiF6 octahedra that share corners with three equivalent Ni(1)OF5 octahedra, corners with three equivalent Ni(2)OF5 octahedra, corners with three equivalent Ni(4)OF5 octahedra, edges with three equivalent Ni(3)F6 octahedra, and  a faceface with one Li(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 44-62°. The Li(1)-F(1) bond length is 2.08 Å. The Li(1)-F(3) bond length is 2.09 Å. The Li(1)-F(4) bond length is 2.04 Å. The Li(1)-F(6) bond length is 2.08 Å. The Li(1)-F(7) bond length is 2.02 Å. The Li(1)-F(8) bond length is 2.05 Å. In the second Li site, Li(2) is bonded to one O(1), one F(1), one F(2), one F(3), one F(5), and one F(6) atom to form distorted LiOF5 octahedra that share corners with three equivalent Ni(3)F6 octahedra, corners with three equivalent Ni(2)OF5 octahedra, corners with three equivalent Ni(4)OF5 octahedra, edges with three equivalent Ni(1)OF5 octahedra, and  a faceface with one Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 46-63°. The Li(2)-O(1) bond length is 1.93 Å. The Li(2)-F(1) bond length is 2.15 Å. The Li(2)-F(2) bond length is 1.98 Å. The Li(2)-F(3) bond length is 2.22 Å. The Li(2)-F(5) bond length is 2.04 Å. The Li(2)-F(6) bond length is 2.26 Å. There are four 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(5), and one F(6) atom to form NiOF5 octahedra that share corners with three equivalent Li(1)F6 octahedra, corners with three equivalent Ni(3)F6 octahedra, corners with three equivalent Ni(4)OF5 octahedra, edges with three equivalent Li(2)OF5 octahedra, and  a faceface with one Ni(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 45-60°. The Ni(1)-O(1) bond length is 1.96 Å. The Ni(1)-F(1) bond length is 2.04 Å. The Ni(1)-F(2) bond length is 2.18 Å. The Ni(1)-F(3) bond length is 2.07 Å. The Ni(1)-F(5) bond length is 2.11 Å. The Ni(1)-F(6) bond length is 2.03 Å. In the second Ni site, Ni(2) is bonded to one O(1), one F(2), one F(4), one F(5), one F(7), and one F(8) atom to form NiOF5 octahedra that share corners with three equivalent Li(1)F6 octahedra, corners with three equivalent Li(2)OF5 octahedra, corners with three equivalent Ni(3)F6 octahedra, edges with three equivalent Ni(4)OF5 octahedra, and  a faceface with one Ni(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 45-62°. The Ni(2)-O(1) bond length is 1.95 Å. The Ni(2)-F(2) bond length is 2.08 Å. The Ni(2)-F(4) bond length is 2.07 Å. The Ni(2)-F(5) bond length is 2.17 Å. The Ni(2)-F(7) bond length is 2.07 Å. The Ni(2)-F(8) bond length is 2.05 Å. In the third Ni site, Ni(3) is bonded to one F(1), one F(3), one F(4), one F(6), one F(7), and one F(8) atom to form NiF6 octahedra that share corners with three equivalent Li(2)OF5 octahedra, corners with three equivalent Ni(1)OF5 octahedra, corners with three equivalent Ni(2)OF5 octahedra, edges with three equivalent Li(1)F6 octahedra, and  a faceface with one Ni(4)OF5 octahedra. The corner-sharing octahedral tilt angles range from 45-60°. The Ni(3)-F(1) bond length is 1.99 Å. The Ni(3)-F(3) bond length is 2.00 Å. The Ni(3)-F(4) bond length is 2.10 Å. The Ni(3)-F(6) bond length is 1.99 Å. The Ni(3)-F(7) bond length is 2.07 Å. The Ni(3)-F(8) bond length is 2.07 Å. In the fourth Ni site, Ni(4) is bonded to one O(1), one F(2), one F(4), one F(5), one F(7), and one F(8) atom to form distorted NiOF5 octahedra that share corners with three equivalent Li(1)F6 octahedra, corners with three equivalent Li(2)OF5 octahedra, corners with three equivalent Ni(1)OF5 octahedra, edges with three equivalent Ni(2)OF5 octahedra, and  a faceface with one Ni(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 44-63°. The Ni(4)-O(1) bond length is 1.91 Å. The Ni(4)-F(2) bond length is 2.03 Å. The Ni(4)-F(4) bond length is 2.20 Å. The Ni(4)-F(5) bond length is 2.01 Å. The Ni(4)-F(7) bond length is 2.15 Å. The Ni(4)-F(8) bond length is 2.21 Å. O(1) is bonded to one Li(2), one Ni(1), one Ni(2), and one Ni(4) atom to form distorted OLiNi3 trigonal pyramids that share corners with two equivalent F(3)Li2Ni2 trigonal pyramids, corners with two equivalent F(6)Li2Ni2 trigonal pyramids, corners with two equivalent F(4)LiNi3 trigonal pyramids, corners with two equivalent F(5)LiNi3 trigonal pyramids,  an edgeedge with one F(1)Li2Ni2 trigonal pyramid, and  an edgeedge with one F(5)LiNi3 trigonal pyramid. There are eight inequivalent F sites. In the first F site, F(3) is bonded to one Li(1), one Li(2), one Ni(1), and one Ni(3) atom to form distorted FLi2Ni2 trigonal pyramids that share corners with two equivalent O(1)LiNi3 trigonal pyramids, corners with two equivalent F(1)Li2Ni2 trigonal pyramids, corners with two equivalent F(6)Li2Ni2 trigonal pyramids, corners with two equivalent F(5)LiNi3 trigonal pyramids,  an edgeedge with one F(1)Li2Ni2 trigonal pyramid,  an edgeedge with one F(6)Li2Ni2 trigonal pyramid, and  an edgeedge with one F(4)LiNi3 trigonal pyramid. In the second F site, F(4) is bonded to one Li(1), one Ni(2), one Ni(3), and one Ni(4) atom to form distorted FLiNi3 trigonal pyramids that share corners with two equivalent O(1)LiNi3 trigonal pyramids, corners with two equivalent F(1)Li2Ni2 trigonal pyramids, corners with two equivalent F(6)Li2Ni2 trigonal pyramids,  an edgeedge with one F(3)Li2Ni2 trigonal pyramid, and  an edgeedge with one F(5)LiNi3 trigonal pyramid. In the third F site, F(5) is bonded to one Li(2), one Ni(1), one Ni(2), and one Ni(4) atom to form distorted FLiNi3 trigonal pyramids that share corners with two equivalent O(1)LiNi3 trigonal pyramids, corners with two equivalent F(1)Li2Ni2 trigonal pyramids, corners with two equivalent F(3)Li2Ni2 trigonal pyramids,  an edgeedge with one O(1)LiNi3 trigonal pyramid,  an edgeedge with one F(6)Li2Ni2 trigonal pyramid, and  an edgeedge with one F(4)LiNi3 trigonal pyramid. In the fourth F site, F(6) is bonded to one Li(1), one Li(2), one Ni(1), and one Ni(3) atom to form distorted FLi2Ni2 trigonal pyramids that share corners with two equivalent O(1)LiNi3 trigonal pyramids, corners with two equivalent F(1)Li2Ni2 trigonal pyramids, corners with two equivalent F(3)Li2Ni2 trigonal pyramids, corners with two equivalent F(4)LiNi3 trigonal pyramids,  an edgeedge with one F(1)Li2Ni2 trigonal pyramid,  an edgeedge with one F(3)Li2Ni2 trigonal pyramid, and  an edgeedge with one F(5)LiNi3 trigonal pyramid. In the fifth F site, F(7) is bonded in a rectangular see-saw-like geometry to one Li(1), one Ni(2), one Ni(3), and one Ni(4) atom. In the sixth F site, F(8) is bonded in a rectangular see-saw-like geometry to one Li(1), one Ni(2), one Ni(3), and one Ni(4) atom. In the seventh F site, F(1) is bonded to one Li(1), one Li(2), one Ni(1), and one Ni(3) atom to form distorted FLi2Ni2 trigonal pyramids that share corners with two equivalent F(3)Li2Ni2 trigonal pyramids, corners with two equivalent F(6)Li2Ni2 trigonal pyramids, corners with two equivalent F(4)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(3)Li2Ni2 trigonal pyramid, and  an edgeedge with one F(6)Li2Ni2 trigonal pyramid. In the eighth F site, F(2) is bonded in a 4-coordinate geometry to one Li(2), one Ni(1), one Ni(2), and one Ni(4) atom.