Na3VO3 is Ilmenite-like structured and crystallizes in the monoclinic C2/c space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded in a 4-coordinate geometry to four equivalent O(2) atoms. In the second Na site, Na(2) is bonded in a distorted rectangular see-saw-like geometry to two equivalent O(2) and two equivalent O(3) atoms. In the third Na site, Na(3) is bonded to one O(1) and three equivalent O(3) atoms to form distorted NaO4 tetrahedra that share corners with two equivalent Na(3)O4 tetrahedra, corners with four equivalent Na(4)O4 tetrahedra, corners with five equivalent V(1)O4 tetrahedra, and edges with two equivalent Na(3)O4 tetrahedra. In the fourth Na site, Na(4) is bonded to one O(1), one O(3), and two equivalent O(2) atoms to form distorted NaO4 tetrahedra that share corners with two equivalent Na(4)O4 tetrahedra, corners with three equivalent V(1)O4 tetrahedra, corners with four equivalent Na(3)O4 tetrahedra, and  an edgeedge with one V(1)O4 tetrahedra. V(1) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form VO4 tetrahedra that share corners with three equivalent Na(4)O4 tetrahedra, corners with five equivalent Na(3)O4 tetrahedra,  an edgeedge with one Na(4)O4 tetrahedra, and  an edgeedge with one V(1)O4 tetrahedra. There are three inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Na(3), one Na(4), and two equivalent V(1) atoms. In the second O site, O(2) is bonded to one Na(2), two equivalent Na(1), two equivalent Na(4), and one V(1) atom to form a mixture of distorted corner and edge-sharing ONa5V octahedra. The corner-sharing octahedral tilt angles are 19°. In the third O site, O(3) is bonded to one Na(2), one Na(4), three equivalent Na(3), and one V(1) atom to form a mixture of distorted corner, face, and edge-sharing ONa5V pentagonal pyramids. The corner-sharing octahedral tilt angles range from 10-57°.
Na3VO3 is Ilmenite-like structured and crystallizes in the monoclinic C2/c space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded in a 4-coordinate geometry to four equivalent O(2) atoms. There are two shorter (2.37 Å) and two longer (2.53 Å) Na(1)-O(2) bond lengths. In the second Na site, Na(2) is bonded in a distorted rectangular see-saw-like geometry to two equivalent O(2) and two equivalent O(3) atoms. Both Na(2)-O(2) bond lengths are 2.30 Å. Both Na(2)-O(3) bond lengths are 2.46 Å. In the third Na site, Na(3) is bonded to one O(1) and three equivalent O(3) atoms to form distorted NaO4 tetrahedra that share corners with two equivalent Na(3)O4 tetrahedra, corners with four equivalent Na(4)O4 tetrahedra, corners with five equivalent V(1)O4 tetrahedra, and edges with two equivalent Na(3)O4 tetrahedra. The Na(3)-O(1) bond length is 2.34 Å. There are a spread of Na(3)-O(3) bond distances ranging from 2.33-2.49 Å. In the fourth Na site, Na(4) is bonded to one O(1), one O(3), and two equivalent O(2) atoms to form distorted NaO4 tetrahedra that share corners with two equivalent Na(4)O4 tetrahedra, corners with three equivalent V(1)O4 tetrahedra, corners with four equivalent Na(3)O4 tetrahedra, and  an edgeedge with one V(1)O4 tetrahedra. The Na(4)-O(1) bond length is 2.37 Å. The Na(4)-O(3) bond length is 2.43 Å. There is one shorter (2.32 Å) and one longer (2.33 Å) Na(4)-O(2) bond length. V(1) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form VO4 tetrahedra that share corners with three equivalent Na(4)O4 tetrahedra, corners with five equivalent Na(3)O4 tetrahedra,  an edgeedge with one Na(4)O4 tetrahedra, and  an edgeedge with one V(1)O4 tetrahedra. The V(1)-O(2) bond length is 1.91 Å. The V(1)-O(3) bond length is 1.91 Å. There is one shorter (1.98 Å) and one longer (2.01 Å) V(1)-O(1) bond length. There are three inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Na(3), one Na(4), and two equivalent V(1) atoms. In the second O site, O(2) is bonded to one Na(2), two equivalent Na(1), two equivalent Na(4), and one V(1) atom to form a mixture of distorted corner and edge-sharing ONa5V octahedra. The corner-sharing octahedral tilt angles are 19°. In the third O site, O(3) is bonded to one Na(2), one Na(4), three equivalent Na(3), and one V(1) atom to form a mixture of distorted corner, face, and edge-sharing ONa5V pentagonal pyramids. The corner-sharing octahedral tilt angles range from 10-57°.