NaV3O6 is Ilmenite-like structured and crystallizes in the monoclinic C2 space group. Na(1) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms. There are three inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 16-18°. In the second V site, V(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles are 16°. In the third V site, V(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form a mixture of distorted corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles are 18°. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), one V(1), one V(2), and one V(3) atom to form a mixture of distorted corner and edge-sharing ONaV3 tetrahedra. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one V(1), one V(2), and one V(3) atom. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Na(1), one V(1), one V(2), and one V(3) atom.
NaV3O6 is Ilmenite-like structured and crystallizes in the monoclinic C2 space group. Na(1) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms. Both Na(1)-O(1) bond lengths are 2.12 Å. Both Na(1)-O(2) bond lengths are 2.61 Å. Both Na(1)-O(3) bond lengths are 2.29 Å. There are three inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 16-18°. Both V(1)-O(1) bond lengths are 1.97 Å. Both V(1)-O(2) bond lengths are 2.09 Å. Both V(1)-O(3) bond lengths are 2.12 Å. In the second V site, V(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles are 16°. Both V(2)-O(1) bond lengths are 1.97 Å. Both V(2)-O(2) bond lengths are 1.93 Å. Both V(2)-O(3) bond lengths are 2.03 Å. In the third V site, V(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form a mixture of distorted corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles are 18°. Both V(3)-O(1) bond lengths are 2.00 Å. Both V(3)-O(2) bond lengths are 2.06 Å. Both V(3)-O(3) bond lengths are 1.92 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), one V(1), one V(2), and one V(3) atom to form a mixture of distorted corner and edge-sharing ONaV3 tetrahedra. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one V(1), one V(2), and one V(3) atom. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Na(1), one V(1), one V(2), and one V(3) atom.