Li8NbO6 crystallizes in the triclinic P-1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form LiO4 tetrahedra that share corners with two equivalent Nb(1)O6 octahedra, corners with three equivalent Li(2)O4 tetrahedra, corners with three equivalent Li(3)O4 tetrahedra,  an edgeedge with one Nb(1)O6 octahedra,  an edgeedge with one Li(1)O4 tetrahedra,  an edgeedge with one Li(2)O4 tetrahedra, and  an edgeedge with one Li(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 17-52°. In the second Li site, Li(2) is bonded to one O(1), one O(3), and two equivalent O(2) atoms to form LiO4 tetrahedra that share corners with two equivalent Nb(1)O6 octahedra, corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Li(3)O4 tetrahedra,  an edgeedge with one Nb(1)O6 octahedra,  an edgeedge with one Li(1)O4 tetrahedra,  an edgeedge with one Li(2)O4 tetrahedra, and  an edgeedge with one Li(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 22-55°. In the third Li site, Li(3) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form LiO4 tetrahedra that share corners with two equivalent Nb(1)O6 octahedra, corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Li(2)O4 tetrahedra,  an edgeedge with one Nb(1)O6 octahedra,  an edgeedge with one Li(1)O4 tetrahedra,  an edgeedge with one Li(2)O4 tetrahedra, and  an edgeedge with one Li(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 17-56°. In the fourth Li site, Li(4) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms. Nb(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form NbO6 octahedra that share corners with four equivalent Li(1)O4 tetrahedra, corners with four equivalent Li(2)O4 tetrahedra, corners with four equivalent Li(3)O4 tetrahedra, edges with two equivalent Li(1)O4 tetrahedra, edges with two equivalent Li(2)O4 tetrahedra, and edges with two equivalent Li(3)O4 tetrahedra. There are three inequivalent O sites. In the first O site, O(1) is bonded in a 7-coordinate geometry to one Li(2), one Li(3), two equivalent Li(1), two equivalent Li(4), and one Nb(1) atom. In the second O site, O(2) is bonded in a 7-coordinate geometry to one Li(1), one Li(3), two equivalent Li(2), two equivalent Li(4), and one Nb(1) atom. In the third O site, O(3) is bonded in a 7-coordinate geometry to one Li(1), one Li(2), two equivalent Li(3), two equivalent Li(4), and one Nb(1) atom.
Li8NbO6 crystallizes in the triclinic P-1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form LiO4 tetrahedra that share corners with two equivalent Nb(1)O6 octahedra, corners with three equivalent Li(2)O4 tetrahedra, corners with three equivalent Li(3)O4 tetrahedra,  an edgeedge with one Nb(1)O6 octahedra,  an edgeedge with one Li(1)O4 tetrahedra,  an edgeedge with one Li(2)O4 tetrahedra, and  an edgeedge with one Li(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 17-52°. The Li(1)-O(2) bond length is 1.97 Å. The Li(1)-O(3) bond length is 1.90 Å. There is one shorter (1.98 Å) and one longer (2.04 Å) Li(1)-O(1) bond length. In the second Li site, Li(2) is bonded to one O(1), one O(3), and two equivalent O(2) atoms to form LiO4 tetrahedra that share corners with two equivalent Nb(1)O6 octahedra, corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Li(3)O4 tetrahedra,  an edgeedge with one Nb(1)O6 octahedra,  an edgeedge with one Li(1)O4 tetrahedra,  an edgeedge with one Li(2)O4 tetrahedra, and  an edgeedge with one Li(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 22-55°. The Li(2)-O(1) bond length is 1.92 Å. The Li(2)-O(3) bond length is 1.99 Å. There is one shorter (1.94 Å) and one longer (2.08 Å) Li(2)-O(2) bond length. In the third Li site, Li(3) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form LiO4 tetrahedra that share corners with two equivalent Nb(1)O6 octahedra, corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Li(2)O4 tetrahedra,  an edgeedge with one Nb(1)O6 octahedra,  an edgeedge with one Li(1)O4 tetrahedra,  an edgeedge with one Li(2)O4 tetrahedra, and  an edgeedge with one Li(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 17-56°. The Li(3)-O(1) bond length is 2.01 Å. The Li(3)-O(2) bond length is 1.89 Å. There is one shorter (1.93 Å) and one longer (2.04 Å) Li(3)-O(3) bond length. In the fourth Li site, Li(4) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms. There is one shorter (2.24 Å) and one longer (2.55 Å) Li(4)-O(1) bond length. There is one shorter (2.10 Å) and one longer (2.35 Å) Li(4)-O(2) bond length. There is one shorter (2.13 Å) and one longer (2.36 Å) Li(4)-O(3) bond length. Nb(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form NbO6 octahedra that share corners with four equivalent Li(1)O4 tetrahedra, corners with four equivalent Li(2)O4 tetrahedra, corners with four equivalent Li(3)O4 tetrahedra, edges with two equivalent Li(1)O4 tetrahedra, edges with two equivalent Li(2)O4 tetrahedra, and edges with two equivalent Li(3)O4 tetrahedra. Both Nb(1)-O(1) bond lengths are 2.05 Å. Both Nb(1)-O(2) bond lengths are 2.16 Å. Both Nb(1)-O(3) bond lengths are 2.16 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a 7-coordinate geometry to one Li(2), one Li(3), two equivalent Li(1), two equivalent Li(4), and one Nb(1) atom. In the second O site, O(2) is bonded in a 7-coordinate geometry to one Li(1), one Li(3), two equivalent Li(2), two equivalent Li(4), and one Nb(1) atom. In the third O site, O(3) is bonded in a 7-coordinate geometry to one Li(1), one Li(2), two equivalent Li(3), two equivalent Li(4), and one Nb(1) atom.