Li3NiO2F crystallizes in the orthorhombic Pnnm space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), two equivalent O(2), and one F(1) atom to form distorted LiO3F trigonal pyramids that share  a cornercorner with one Li(3)O3F trigonal pyramid, corners with two equivalent Li(1)O3F trigonal pyramids, corners with five equivalent Li(2)O2F2 trigonal pyramids, and edges with two equivalent Li(3)O3F trigonal pyramids. In the second Li site, Li(2) is bonded to one O(1), one O(2), and two equivalent F(1) atoms to form distorted LiO2F2 trigonal pyramids that share  a cornercorner with one Li(3)O3F trigonal pyramid, corners with two equivalent Li(2)O2F2 trigonal pyramids, corners with five equivalent Li(1)O3F trigonal pyramids, and edges with two equivalent Li(3)O3F trigonal pyramids. In the third Li site, Li(3) is bonded to one O(2), two equivalent O(1), and one F(1) atom to form distorted LiO3F trigonal pyramids that share  a cornercorner with one Li(2)O2F2 trigonal pyramid,  a cornercorner with one Li(1)O3F trigonal pyramid, corners with two equivalent Li(3)O3F trigonal pyramids, edges with two equivalent Li(2)O2F2 trigonal pyramids, and edges with two equivalent Li(1)O3F trigonal pyramids. Ni(1) is bonded in a rectangular see-saw-like geometry to one O(2), two equivalent O(1), and one F(1) atom. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), two equivalent Li(3), and two equivalent Ni(1) atoms to form distorted OLi4Ni2 octahedra that share corners with two equivalent O(1)Li4Ni2 octahedra,  a cornercorner with one O(2)Li4Ni trigonal bipyramid,  a cornercorner with one F(1)Li4Ni trigonal bipyramid,  an edgeedge with one O(1)Li4Ni2 octahedra, edges with three equivalent O(2)Li4Ni trigonal bipyramids, and edges with three equivalent F(1)Li4Ni trigonal bipyramids. The corner-sharing octahedral tilt angles are 44°. In the second O site, O(2) is bonded to one Li(2), one Li(3), two equivalent Li(1), and one Ni(1) atom to form distorted OLi4Ni trigonal bipyramids that share  a cornercorner with one O(1)Li4Ni2 octahedra, corners with two equivalent O(2)Li4Ni trigonal bipyramids, corners with four equivalent F(1)Li4Ni trigonal bipyramids, edges with three equivalent O(1)Li4Ni2 octahedra, and  an edgeedge with one F(1)Li4Ni trigonal bipyramid. The corner-sharing octahedral tilt angles are 9°. F(1) is bonded to one Li(1), one Li(3), two equivalent Li(2), and one Ni(1) atom to form distorted FLi4Ni trigonal bipyramids that share  a cornercorner with one O(1)Li4Ni2 octahedra, corners with two equivalent F(1)Li4Ni trigonal bipyramids, corners with four equivalent O(2)Li4Ni trigonal bipyramids, edges with three equivalent O(1)Li4Ni2 octahedra, and  an edgeedge with one O(2)Li4Ni trigonal bipyramid. The corner-sharing octahedral tilt angles are 4°.
Li3NiO2F crystallizes in the orthorhombic Pnnm space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), two equivalent O(2), and one F(1) atom to form distorted LiO3F trigonal pyramids that share  a cornercorner with one Li(3)O3F trigonal pyramid, corners with two equivalent Li(1)O3F trigonal pyramids, corners with five equivalent Li(2)O2F2 trigonal pyramids, and edges with two equivalent Li(3)O3F trigonal pyramids. The Li(1)-O(1) bond length is 2.16 Å. Both Li(1)-O(2) bond lengths are 1.93 Å. The Li(1)-F(1) bond length is 1.88 Å. In the second Li site, Li(2) is bonded to one O(1), one O(2), and two equivalent F(1) atoms to form distorted LiO2F2 trigonal pyramids that share  a cornercorner with one Li(3)O3F trigonal pyramid, corners with two equivalent Li(2)O2F2 trigonal pyramids, corners with five equivalent Li(1)O3F trigonal pyramids, and edges with two equivalent Li(3)O3F trigonal pyramids. The Li(2)-O(1) bond length is 2.19 Å. The Li(2)-O(2) bond length is 1.91 Å. Both Li(2)-F(1) bond lengths are 1.96 Å. In the third Li site, Li(3) is bonded to one O(2), two equivalent O(1), and one F(1) atom to form distorted LiO3F trigonal pyramids that share  a cornercorner with one Li(2)O2F2 trigonal pyramid,  a cornercorner with one Li(1)O3F trigonal pyramid, corners with two equivalent Li(3)O3F trigonal pyramids, edges with two equivalent Li(2)O2F2 trigonal pyramids, and edges with two equivalent Li(1)O3F trigonal pyramids. The Li(3)-O(2) bond length is 1.98 Å. Both Li(3)-O(1) bond lengths are 1.95 Å. The Li(3)-F(1) bond length is 1.93 Å. Ni(1) is bonded in a rectangular see-saw-like geometry to one O(2), two equivalent O(1), and one F(1) atom. The Ni(1)-O(2) bond length is 1.87 Å. There is one shorter (1.90 Å) and one longer (2.05 Å) Ni(1)-O(1) bond length. The Ni(1)-F(1) bond length is 2.33 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), two equivalent Li(3), and two equivalent Ni(1) atoms to form distorted OLi4Ni2 octahedra that share corners with two equivalent O(1)Li4Ni2 octahedra,  a cornercorner with one O(2)Li4Ni trigonal bipyramid,  a cornercorner with one F(1)Li4Ni trigonal bipyramid,  an edgeedge with one O(1)Li4Ni2 octahedra, edges with three equivalent O(2)Li4Ni trigonal bipyramids, and edges with three equivalent F(1)Li4Ni trigonal bipyramids. The corner-sharing octahedral tilt angles are 44°. In the second O site, O(2) is bonded to one Li(2), one Li(3), two equivalent Li(1), and one Ni(1) atom to form distorted OLi4Ni trigonal bipyramids that share  a cornercorner with one O(1)Li4Ni2 octahedra, corners with two equivalent O(2)Li4Ni trigonal bipyramids, corners with four equivalent F(1)Li4Ni trigonal bipyramids, edges with three equivalent O(1)Li4Ni2 octahedra, and  an edgeedge with one F(1)Li4Ni trigonal bipyramid. The corner-sharing octahedral tilt angles are 9°. F(1) is bonded to one Li(1), one Li(3), two equivalent Li(2), and one Ni(1) atom to form distorted FLi4Ni trigonal bipyramids that share  a cornercorner with one O(1)Li4Ni2 octahedra, corners with two equivalent F(1)Li4Ni trigonal bipyramids, corners with four equivalent O(2)Li4Ni trigonal bipyramids, edges with three equivalent O(1)Li4Ni2 octahedra, and  an edgeedge with one O(2)Li4Ni trigonal bipyramid. The corner-sharing octahedral tilt angles are 4°.