Li3NiF6 crystallizes in the orthorhombic Pna2_1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(2), one F(4), one F(5), one F(6), and two equivalent F(1) atoms to form distorted LiF6 octahedra that share  a cornercorner with one Li(2)F6 octahedra, corners with two equivalent Li(1)F6 octahedra, corners with four equivalent Ni(1)F6 octahedra,  an edgeedge with one Ni(1)F6 octahedra, edges with two equivalent Li(2)F6 octahedra, and  a faceface with one Li(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 39-57°. In the second Li site, Li(2) is bonded to one F(2), one F(4), one F(5), one F(6), and two equivalent F(1) atoms to form distorted LiF6 octahedra that share  a cornercorner with one Li(1)F6 octahedra, corners with two equivalent Li(2)F6 octahedra, corners with two equivalent Ni(1)F6 octahedra, edges with two equivalent Li(1)F6 octahedra, edges with two equivalent Ni(1)F6 octahedra, and  a faceface with one Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 44-57°. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one F(2), one F(4), one F(5), one F(6), and two equivalent F(3) atoms. Ni(1) is bonded to one F(1), one F(2), one F(3), one F(4), one F(5), and one F(6) atom to form NiF6 octahedra that share corners with two equivalent Li(2)F6 octahedra, corners with four equivalent Li(1)F6 octahedra,  an edgeedge with one Li(1)F6 octahedra, and edges with two equivalent Li(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 39-57°. There are six inequivalent F sites. In the first F site, F(5) is bonded to one Li(1), one Li(2), one Li(3), and one Ni(1) atom to form distorted FLi3Ni trigonal pyramids that share corners with three equivalent F(1)Li4Ni trigonal bipyramids, corners with two equivalent F(2)Li3Ni trigonal pyramids, corners with two equivalent F(6)Li3Ni trigonal pyramids,  an edgeedge with one F(1)Li4Ni trigonal bipyramid,  an edgeedge with one F(2)Li3Ni trigonal pyramid, and  an edgeedge with one F(6)Li3Ni trigonal pyramid. In the second F site, F(6) is bonded to one Li(1), one Li(2), one Li(3), and one Ni(1) atom to form distorted FLi3Ni trigonal pyramids that share  a cornercorner with one F(1)Li4Ni trigonal bipyramid, corners with two equivalent F(2)Li3Ni trigonal pyramids, corners with two equivalent F(5)Li3Ni trigonal pyramids, edges with two equivalent F(1)Li4Ni trigonal bipyramids,  an edgeedge with one F(2)Li3Ni trigonal pyramid, and  an edgeedge with one F(5)Li3Ni trigonal pyramid. In the third F site, F(1) is bonded to two equivalent Li(1), two equivalent Li(2), and one Ni(1) atom to form distorted FLi4Ni trigonal bipyramids that share  a cornercorner with one F(2)Li3Ni trigonal pyramid,  a cornercorner with one F(6)Li3Ni trigonal pyramid, corners with three equivalent F(5)Li3Ni trigonal pyramids, edges with two equivalent F(1)Li4Ni trigonal bipyramids,  an edgeedge with one F(5)Li3Ni trigonal pyramid, edges with two equivalent F(2)Li3Ni trigonal pyramids, and edges with two equivalent F(6)Li3Ni trigonal pyramids. In the fourth F site, F(2) is bonded to one Li(1), one Li(2), one Li(3), and one Ni(1) atom to form FLi3Ni trigonal pyramids that share  a cornercorner with one F(1)Li4Ni trigonal bipyramid, corners with two equivalent F(5)Li3Ni trigonal pyramids, corners with two equivalent F(6)Li3Ni trigonal pyramids, edges with two equivalent F(1)Li4Ni trigonal bipyramids,  an edgeedge with one F(5)Li3Ni trigonal pyramid, and  an edgeedge with one F(6)Li3Ni trigonal pyramid. In the fifth F site, F(3) is bonded in a trigonal planar geometry to two equivalent Li(3) and one Ni(1) atom. In the sixth F site, F(4) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one Li(3), and one Ni(1) atom.
Li3NiF6 crystallizes in the orthorhombic Pna2_1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(2), one F(4), one F(5), one F(6), and two equivalent F(1) atoms to form distorted LiF6 octahedra that share  a cornercorner with one Li(2)F6 octahedra, corners with two equivalent Li(1)F6 octahedra, corners with four equivalent Ni(1)F6 octahedra,  an edgeedge with one Ni(1)F6 octahedra, edges with two equivalent Li(2)F6 octahedra, and  a faceface with one Li(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 39-57°. The Li(1)-F(2) bond length is 2.04 Å. The Li(1)-F(4) bond length is 1.88 Å. The Li(1)-F(5) bond length is 1.99 Å. The Li(1)-F(6) bond length is 1.88 Å. There is one shorter (2.06 Å) and one longer (2.25 Å) Li(1)-F(1) bond length. In the second Li site, Li(2) is bonded to one F(2), one F(4), one F(5), one F(6), and two equivalent F(1) atoms to form distorted LiF6 octahedra that share  a cornercorner with one Li(1)F6 octahedra, corners with two equivalent Li(2)F6 octahedra, corners with two equivalent Ni(1)F6 octahedra, edges with two equivalent Li(1)F6 octahedra, edges with two equivalent Ni(1)F6 octahedra, and  a faceface with one Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 44-57°. The Li(2)-F(2) bond length is 1.91 Å. The Li(2)-F(4) bond length is 1.97 Å. The Li(2)-F(5) bond length is 1.89 Å. The Li(2)-F(6) bond length is 2.15 Å. There is one shorter (2.04 Å) and one longer (2.07 Å) Li(2)-F(1) bond length. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one F(2), one F(4), one F(5), one F(6), and two equivalent F(3) atoms. The Li(3)-F(2) bond length is 1.99 Å. The Li(3)-F(4) bond length is 2.36 Å. The Li(3)-F(5) bond length is 2.10 Å. The Li(3)-F(6) bond length is 2.00 Å. There is one shorter (1.86 Å) and one longer (1.92 Å) Li(3)-F(3) bond length. Ni(1) is bonded to one F(1), one F(2), one F(3), one F(4), one F(5), and one F(6) atom to form NiF6 octahedra that share corners with two equivalent Li(2)F6 octahedra, corners with four equivalent Li(1)F6 octahedra,  an edgeedge with one Li(1)F6 octahedra, and edges with two equivalent Li(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 39-57°. The Ni(1)-F(1) bond length is 1.95 Å. The Ni(1)-F(2) bond length is 1.91 Å. The Ni(1)-F(3) bond length is 1.87 Å. The Ni(1)-F(4) bond length is 1.89 Å. The Ni(1)-F(5) bond length is 1.91 Å. The Ni(1)-F(6) bond length is 1.90 Å. There are six inequivalent F sites. In the first F site, F(5) is bonded to one Li(1), one Li(2), one Li(3), and one Ni(1) atom to form distorted FLi3Ni trigonal pyramids that share corners with three equivalent F(1)Li4Ni trigonal bipyramids, corners with two equivalent F(2)Li3Ni trigonal pyramids, corners with two equivalent F(6)Li3Ni trigonal pyramids,  an edgeedge with one F(1)Li4Ni trigonal bipyramid,  an edgeedge with one F(2)Li3Ni trigonal pyramid, and  an edgeedge with one F(6)Li3Ni trigonal pyramid. In the second F site, F(6) is bonded to one Li(1), one Li(2), one Li(3), and one Ni(1) atom to form distorted FLi3Ni trigonal pyramids that share  a cornercorner with one F(1)Li4Ni trigonal bipyramid, corners with two equivalent F(2)Li3Ni trigonal pyramids, corners with two equivalent F(5)Li3Ni trigonal pyramids, edges with two equivalent F(1)Li4Ni trigonal bipyramids,  an edgeedge with one F(2)Li3Ni trigonal pyramid, and  an edgeedge with one F(5)Li3Ni trigonal pyramid. In the third F site, F(1) is bonded to two equivalent Li(1), two equivalent Li(2), and one Ni(1) atom to form distorted FLi4Ni trigonal bipyramids that share  a cornercorner with one F(2)Li3Ni trigonal pyramid,  a cornercorner with one F(6)Li3Ni trigonal pyramid, corners with three equivalent F(5)Li3Ni trigonal pyramids, edges with two equivalent F(1)Li4Ni trigonal bipyramids,  an edgeedge with one F(5)Li3Ni trigonal pyramid, edges with two equivalent F(2)Li3Ni trigonal pyramids, and edges with two equivalent F(6)Li3Ni trigonal pyramids. In the fourth F site, F(2) is bonded to one Li(1), one Li(2), one Li(3), and one Ni(1) atom to form FLi3Ni trigonal pyramids that share  a cornercorner with one F(1)Li4Ni trigonal bipyramid, corners with two equivalent F(5)Li3Ni trigonal pyramids, corners with two equivalent F(6)Li3Ni trigonal pyramids, edges with two equivalent F(1)Li4Ni trigonal bipyramids,  an edgeedge with one F(5)Li3Ni trigonal pyramid, and  an edgeedge with one F(6)Li3Ni trigonal pyramid. In the fifth F site, F(3) is bonded in a trigonal planar geometry to two equivalent Li(3) and one Ni(1) atom. In the sixth F site, F(4) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one Li(3), and one Ni(1) atom.