Na3VO3 crystallizes in the triclinic P-1 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 5-coordinate geometry to one O(1), two equivalent O(2), and two equivalent O(3) atoms. In the second Na site, Na(2) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form NaO4 trigonal pyramids that share corners with five equivalent V(1)O4 tetrahedra and  an edgeedge with one Na(2)O4 trigonal pyramid. In the third Na site, Na(3) is bonded in a 5-coordinate geometry to one O(3), 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 five equivalent Na(2)O4 trigonal pyramids 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 6-coordinate geometry to one Na(1), two equivalent Na(2), two equivalent Na(3), and one V(1) atom. In the second O site, O(2) is bonded to one Na(2), two equivalent Na(1), two equivalent Na(3), and one V(1) atom to form distorted edge-sharing ONa5V octahedra. In the third O site, O(3) is bonded in a 6-coordinate geometry to one Na(2), one Na(3), two equivalent Na(1), and two equivalent V(1) atoms.
Na3VO3 crystallizes in the triclinic P-1 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 5-coordinate geometry to one O(1), two equivalent O(2), and two equivalent O(3) atoms. The Na(1)-O(1) bond length is 2.56 Å. There is one shorter (2.37 Å) and one longer (2.43 Å) Na(1)-O(2) bond length. There is one shorter (2.36 Å) and one longer (2.73 Å) Na(1)-O(3) bond length. In the second Na site, Na(2) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form NaO4 trigonal pyramids that share corners with five equivalent V(1)O4 tetrahedra and  an edgeedge with one Na(2)O4 trigonal pyramid. The Na(2)-O(2) bond length is 2.32 Å. The Na(2)-O(3) bond length is 2.29 Å. There is one shorter (2.29 Å) and one longer (2.48 Å) Na(2)-O(1) bond length. In the third Na site, Na(3) is bonded in a 5-coordinate geometry to one O(3), two equivalent O(1), and two equivalent O(2) atoms. The Na(3)-O(3) bond length is 2.63 Å. There is one shorter (2.32 Å) and one longer (2.75 Å) Na(3)-O(1) bond length. There is one shorter (2.38 Å) and one longer (2.57 Å) Na(3)-O(2) bond length. 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 five equivalent Na(2)O4 trigonal pyramids and  an edgeedge with one V(1)O4 tetrahedra. The V(1)-O(1) bond length is 1.87 Å. The V(1)-O(2) bond length is 1.91 Å. There is one shorter (1.97 Å) and one longer (2.03 Å) V(1)-O(3) bond length. There are three inequivalent O sites. In the first O site, O(1) is bonded in a 6-coordinate geometry to one Na(1), two equivalent Na(2), two equivalent Na(3), and one V(1) atom. In the second O site, O(2) is bonded to one Na(2), two equivalent Na(1), two equivalent Na(3), and one V(1) atom to form distorted edge-sharing ONa5V octahedra. In the third O site, O(3) is bonded in a 6-coordinate geometry to one Na(2), one Na(3), two equivalent Na(1), and two equivalent V(1) atoms.