Li6NiOF6 is alpha Po-derived structured and crystallizes in the monoclinic C2/m space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1); two equivalent F(1); and two equivalent F(3,4) atoms to form LiO2F4 octahedra that share corners with two equivalent Li(5,6)F6 octahedra; corners with two equivalent Li(1)O2F4 octahedra; corners with two equivalent Li(2)O2F4 octahedra;  an edgeedge with one Li(5,6)F6 octahedra;  an edgeedge with one Li(1)O2F4 octahedra; edges with two equivalent Li(2)O2F4 octahedra; edges with four equivalent Li(3,4)F6 octahedra; and edges with four equivalent Ni(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. In the second Li site, Li(2) is bonded to two equivalent O(1); two equivalent F(2); and two equivalent F(3,4) atoms to form LiO2F4 octahedra that share corners with two equivalent Li(5,6)F6 octahedra; corners with two equivalent Li(1)O2F4 octahedra; corners with two equivalent Li(2)O2F4 octahedra;  an edgeedge with one Li(5,6)F6 octahedra;  an edgeedge with one Li(2)O2F4 octahedra; edges with two equivalent Li(1)O2F4 octahedra; edges with four equivalent Li(3,4)F6 octahedra; and edges with four equivalent Ni(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. In the third Li site, Li(3,4) is bonded to one F(1); one F(2); one F(5); one F(6); and two equivalent F(3,4) atoms to form LiF6 octahedra that share corners with two equivalent Li(3,4)F6 octahedra; corners with two equivalent Li(5,6)F6 octahedra; corners with two equivalent Ni(1)O2F4 octahedra;  an edgeedge with one Ni(1)O2F4 octahedra; edges with two equivalent Li(3,4)F6 octahedra; edges with two equivalent Li(1)O2F4 octahedra; edges with two equivalent Li(2)O2F4 octahedra; and edges with five equivalent Li(5,6)F6 octahedra. The corner-sharing octahedral tilt angles range from 0-3°. In the fourth Li site, Li(5,6) is bonded to one F(6); two equivalent F(3,4); and three equivalent F(5) atoms to form LiF6 octahedra that share corners with two equivalent Li(3,4)F6 octahedra; corners with two equivalent Li(5,6)F6 octahedra; corners with two equivalent Li(2)O2F4 octahedra;  an edgeedge with one Li(1)O2F4 octahedra; edges with five equivalent Li(3,4)F6 octahedra; and edges with six equivalent Li(5,6)F6 octahedra. The corner-sharing octahedral tilt angles range from 2-5°. Ni(1) is bonded to two equivalent O(1), two equivalent F(1), and two equivalent F(2) atoms to form NiO2F4 octahedra that share corners with two equivalent Ni(1)O2F4 octahedra; corners with four equivalent Li(3,4)F6 octahedra; edges with two equivalent Li(3,4)F6 octahedra; edges with two equivalent Ni(1)O2F4 octahedra; edges with four equivalent Li(1)O2F4 octahedra; and edges with four equivalent Li(2)O2F4 octahedra. The corner-sharing octahedra are not tilted. O(1) is bonded to two equivalent Li(1), two equivalent Li(2), and two equivalent Ni(1) atoms to form OLi4Ni2 octahedra that share corners with two equivalent O(1)Li4Ni2 octahedra; corners with four equivalent F(3,4)Li6 octahedra; edges with two equivalent O(1)Li4Ni2 octahedra; edges with two equivalent F(3,4)Li6 octahedra; edges with four equivalent F(1)Li4Ni2 octahedra; and edges with four equivalent F(2)Li4Ni2 octahedra. The corner-sharing octahedral tilt angles range from 0-5°. There are five inequivalent F sites. In the first F site, F(1) is bonded to two equivalent Li(1); two equivalent Li(3,4); and two equivalent Ni(1) atoms to form FLi4Ni2 octahedra that share corners with two equivalent F(1)Li4Ni2 octahedra; corners with two equivalent F(2)Li4Ni2 octahedra; corners with two equivalent F(6)Li6 octahedra;  an edgeedge with one F(1)Li4Ni2 octahedra;  an edgeedge with one F(5)Li6 octahedra; edges with two equivalent F(2)Li4Ni2 octahedra; edges with four equivalent O(1)Li4Ni2 octahedra; and edges with four equivalent F(3,4)Li6 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. In the second F site, F(2) is bonded to two equivalent Li(2); two equivalent Li(3,4); and two equivalent Ni(1) atoms to form FLi4Ni2 octahedra that share corners with two equivalent F(1)Li4Ni2 octahedra; corners with two equivalent F(2)Li4Ni2 octahedra; corners with two equivalent F(5)Li6 octahedra;  an edgeedge with one F(2)Li4Ni2 octahedra;  an edgeedge with one F(6)Li6 octahedra; edges with two equivalent F(1)Li4Ni2 octahedra; edges with four equivalent O(1)Li4Ni2 octahedra; and edges with four equivalent F(3,4)Li6 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. In the third F site, F(3,4) is bonded to one Li(1); one Li(2); two equivalent Li(3,4); and two equivalent Li(5,6) atoms to form FLi6 octahedra that share corners with two equivalent O(1)Li4Ni2 octahedra; corners with two equivalent F(3,4)Li6 octahedra; corners with two equivalent F(5)Li6 octahedra;  an edgeedge with one O(1)Li4Ni2 octahedra; edges with two equivalent F(1)Li4Ni2 octahedra; edges with two equivalent F(2)Li4Ni2 octahedra; edges with two equivalent F(3,4)Li6 octahedra; edges with two equivalent F(5)Li6 octahedra; and edges with three equivalent F(6)Li6 octahedra. The corner-sharing octahedral tilt angles range from 2-5°. In the fourth F site, F(5) is bonded to two equivalent Li(3,4) and four equivalent Li(5,6) atoms to form FLi6 octahedra that share corners with two equivalent F(2)Li4Ni2 octahedra; corners with two equivalent F(3,4)Li6 octahedra; corners with two equivalent F(5)Li6 octahedra;  an edgeedge with one F(1)Li4Ni2 octahedra; edges with two equivalent F(5)Li6 octahedra; edges with four equivalent F(6)Li6 octahedra; and edges with five equivalent F(3,4)Li6 octahedra. The corner-sharing octahedral tilt angles range from 2-3°. In the fifth F site, F(6) is bonded to two equivalent Li(3,4) and four equivalent Li(5,6) atoms to form FLi6 octahedra that share corners with two equivalent F(1)Li4Ni2 octahedra; corners with two equivalent F(3,4)Li6 octahedra; corners with two equivalent F(6)Li6 octahedra;  an edgeedge with one F(2)Li4Ni2 octahedra; edges with two equivalent F(6)Li6 octahedra; edges with four equivalent F(5)Li6 octahedra; and edges with five equivalent F(3,4)Li6 octahedra. The corner-sharing octahedral tilt angles range from 2-3°.
Li6NiOF6 is alpha Po-derived structured and crystallizes in the monoclinic C2/m space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1); two equivalent F(1); and two equivalent F(3,4) atoms to form LiO2F4 octahedra that share corners with two equivalent Li(5,6)F6 octahedra; corners with two equivalent Li(1)O2F4 octahedra; corners with two equivalent Li(2)O2F4 octahedra;  an edgeedge with one Li(5,6)F6 octahedra;  an edgeedge with one Li(1)O2F4 octahedra; edges with two equivalent Li(2)O2F4 octahedra; edges with four equivalent Li(3,4)F6 octahedra; and edges with four equivalent Ni(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. Both Li(1)-O(1) bond lengths are 2.04 Å. Both Li(1)-F(1) bond lengths are 2.00 Å. Both Li(1)-F(3,4) bond lengths are 2.22 Å. In the second Li site, Li(2) is bonded to two equivalent O(1); two equivalent F(2); and two equivalent F(3,4) atoms to form LiO2F4 octahedra that share corners with two equivalent Li(5,6)F6 octahedra; corners with two equivalent Li(1)O2F4 octahedra; corners with two equivalent Li(2)O2F4 octahedra;  an edgeedge with one Li(5,6)F6 octahedra;  an edgeedge with one Li(2)O2F4 octahedra; edges with two equivalent Li(1)O2F4 octahedra; edges with four equivalent Li(3,4)F6 octahedra; and edges with four equivalent Ni(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. Both Li(2)-O(1) bond lengths are 2.04 Å. Both Li(2)-F(2) bond lengths are 2.00 Å. Both Li(2)-F(3,4) bond lengths are 2.22 Å. In the third Li site, Li(3,4) is bonded to one F(1); one F(2); one F(5); one F(6); and two equivalent F(3,4) atoms to form LiF6 octahedra that share corners with two equivalent Li(3,4)F6 octahedra; corners with two equivalent Li(5,6)F6 octahedra; corners with two equivalent Ni(1)O2F4 octahedra;  an edgeedge with one Ni(1)O2F4 octahedra; edges with two equivalent Li(3,4)F6 octahedra; edges with two equivalent Li(1)O2F4 octahedra; edges with two equivalent Li(2)O2F4 octahedra; and edges with five equivalent Li(5,6)F6 octahedra. The corner-sharing octahedral tilt angles range from 0-3°. The Li(3,4)-F(1) bond length is 2.14 Å. The Li(3,4)-F(2) bond length is 2.15 Å. The Li(3,4)-F(5) bond length is 2.02 Å. The Li(3,4)-F(6) bond length is 2.02 Å. Both Li(3,4)-F(3,4) bond lengths are 2.00 Å. In the fourth Li site, Li(5,6) is bonded to one F(6); two equivalent F(3,4); and three equivalent F(5) atoms to form LiF6 octahedra that share corners with two equivalent Li(3,4)F6 octahedra; corners with two equivalent Li(5,6)F6 octahedra; corners with two equivalent Li(2)O2F4 octahedra;  an edgeedge with one Li(1)O2F4 octahedra; edges with five equivalent Li(3,4)F6 octahedra; and edges with six equivalent Li(5,6)F6 octahedra. The corner-sharing octahedral tilt angles range from 2-5°. The Li(5,6)-F(6) bond length is 2.10 Å. Both Li(5,6)-F(3,4) bond lengths are 2.04 Å. There are two shorter (2.00 Å) and one longer (2.11 Å) Li(5,6)-F(5) bond length. Ni(1) is bonded to two equivalent O(1), two equivalent F(1), and two equivalent F(2) atoms to form NiO2F4 octahedra that share corners with two equivalent Ni(1)O2F4 octahedra; corners with four equivalent Li(3,4)F6 octahedra; edges with two equivalent Li(3,4)F6 octahedra; edges with two equivalent Ni(1)O2F4 octahedra; edges with four equivalent Li(1)O2F4 octahedra; and edges with four equivalent Li(2)O2F4 octahedra. The corner-sharing octahedra are not tilted. Both Ni(1)-O(1) bond lengths are 2.00 Å. Both Ni(1)-F(1) bond lengths are 2.14 Å. There is one shorter (2.14 Å) and one longer (2.15 Å) Ni(1)-F(2) bond length. O(1) is bonded to two equivalent Li(1), two equivalent Li(2), and two equivalent Ni(1) atoms to form OLi4Ni2 octahedra that share corners with two equivalent O(1)Li4Ni2 octahedra; corners with four equivalent F(3,4)Li6 octahedra; edges with two equivalent O(1)Li4Ni2 octahedra; edges with two equivalent F(3,4)Li6 octahedra; edges with four equivalent F(1)Li4Ni2 octahedra; and edges with four equivalent F(2)Li4Ni2 octahedra. The corner-sharing octahedral tilt angles range from 0-5°. There are five inequivalent F sites. In the first F site, F(1) is bonded to two equivalent Li(1); two equivalent Li(3,4); and two equivalent Ni(1) atoms to form FLi4Ni2 octahedra that share corners with two equivalent F(1)Li4Ni2 octahedra; corners with two equivalent F(2)Li4Ni2 octahedra; corners with two equivalent F(6)Li6 octahedra;  an edgeedge with one F(1)Li4Ni2 octahedra;  an edgeedge with one F(5)Li6 octahedra; edges with two equivalent F(2)Li4Ni2 octahedra; edges with four equivalent O(1)Li4Ni2 octahedra; and edges with four equivalent F(3,4)Li6 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. In the second F site, F(2) is bonded to two equivalent Li(2); two equivalent Li(3,4); and two equivalent Ni(1) atoms to form FLi4Ni2 octahedra that share corners with two equivalent F(1)Li4Ni2 octahedra; corners with two equivalent F(2)Li4Ni2 octahedra; corners with two equivalent F(5)Li6 octahedra;  an edgeedge with one F(2)Li4Ni2 octahedra;  an edgeedge with one F(6)Li6 octahedra; edges with two equivalent F(1)Li4Ni2 octahedra; edges with four equivalent O(1)Li4Ni2 octahedra; and edges with four equivalent F(3,4)Li6 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. In the third F site, F(3,4) is bonded to one Li(1); one Li(2); two equivalent Li(3,4); and two equivalent Li(5,6) atoms to form FLi6 octahedra that share corners with two equivalent O(1)Li4Ni2 octahedra; corners with two equivalent F(3,4)Li6 octahedra; corners with two equivalent F(5)Li6 octahedra;  an edgeedge with one O(1)Li4Ni2 octahedra; edges with two equivalent F(1)Li4Ni2 octahedra; edges with two equivalent F(2)Li4Ni2 octahedra; edges with two equivalent F(3,4)Li6 octahedra; edges with two equivalent F(5)Li6 octahedra; and edges with three equivalent F(6)Li6 octahedra. The corner-sharing octahedral tilt angles range from 2-5°. In the fourth F site, F(5) is bonded to two equivalent Li(3,4) and four equivalent Li(5,6) atoms to form FLi6 octahedra that share corners with two equivalent F(2)Li4Ni2 octahedra; corners with two equivalent F(3,4)Li6 octahedra; corners with two equivalent F(5)Li6 octahedra;  an edgeedge with one F(1)Li4Ni2 octahedra; edges with two equivalent F(5)Li6 octahedra; edges with four equivalent F(6)Li6 octahedra; and edges with five equivalent F(3,4)Li6 octahedra. The corner-sharing octahedral tilt angles range from 2-3°. In the fifth F site, F(6) is bonded to two equivalent Li(3,4) and four equivalent Li(5,6) atoms to form FLi6 octahedra that share corners with two equivalent F(1)Li4Ni2 octahedra; corners with two equivalent F(3,4)Li6 octahedra; corners with two equivalent F(6)Li6 octahedra;  an edgeedge with one F(2)Li4Ni2 octahedra; edges with two equivalent F(6)Li6 octahedra; edges with four equivalent F(5)Li6 octahedra; and edges with five equivalent F(3,4)Li6 octahedra. The corner-sharing octahedral tilt angles range from 2-3°.