LiNaV2O6 crystallizes in the monoclinic C2/c space group. Na(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form NaO6 octahedra that share corners with six equivalent V(1)O4 tetrahedra and edges with two equivalent Na(1)O6 octahedra. Li(1) is bonded in a see-saw-like geometry to two equivalent O(1) and two equivalent O(2) atoms. V(1) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form VO4 tetrahedra that share corners with three equivalent Na(1)O6 octahedra and corners with two equivalent V(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 40-65°. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Na(1), one Li(1), and one V(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Na(1), one Li(1), and one V(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to two equivalent V(1) atoms.
LiNaV2O6 crystallizes in the monoclinic C2/c space group. Na(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form NaO6 octahedra that share corners with six equivalent V(1)O4 tetrahedra and edges with two equivalent Na(1)O6 octahedra. Both Na(1)-O(2) bond lengths are 2.42 Å. There are two shorter (2.37 Å) and two longer (2.57 Å) Na(1)-O(1) bond lengths. Li(1) is bonded in a see-saw-like geometry to two equivalent O(1) and two equivalent O(2) atoms. Both Li(1)-O(1) bond lengths are 1.99 Å. Both Li(1)-O(2) bond lengths are 2.09 Å. V(1) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form VO4 tetrahedra that share corners with three equivalent Na(1)O6 octahedra and corners with two equivalent V(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 40-65°. The V(1)-O(1) bond length is 1.69 Å. The V(1)-O(2) bond length is 1.68 Å. There is one shorter (1.81 Å) and one longer (1.82 Å) V(1)-O(3) bond length. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Na(1), one Li(1), and one V(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Na(1), one Li(1), and one V(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to two equivalent V(1) atoms.