Na3VS3O crystallizes in the orthorhombic Cmc2_1 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent S(1), three equivalent S(2), and one O(1) atom to form distorted NaS5O octahedra that share corners with two equivalent Na(1)S5O octahedra, corners with four equivalent V(1)S3O tetrahedra, edges with two equivalent Na(1)S5O octahedra, and  an edgeedge with one V(1)S3O tetrahedra. The corner-sharing octahedra are not tilted. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one S(2), four equivalent S(1), and one O(1) atom. V(1) is bonded to one S(2), two equivalent S(1), and one O(1) atom to form VS3O tetrahedra that share corners with four equivalent Na(1)S5O octahedra and  an edgeedge with one Na(1)S5O octahedra. The corner-sharing octahedral tilt angles range from 18-75°. There are two inequivalent S sites. In the first S site, S(1) is bonded in a 6-coordinate geometry to one Na(1), four equivalent Na(2), and one V(1) atom. In the second S site, S(2) is bonded to two equivalent Na(2), three equivalent Na(1), and one V(1) atom to form distorted SNa5V octahedra that share corners with two equivalent S(2)Na5V octahedra, corners with four equivalent O(1)Na3V tetrahedra, edges with two equivalent S(2)Na5V octahedra, and  an edgeedge with one O(1)Na3V tetrahedra. The corner-sharing octahedra are not tilted. O(1) is bonded to one Na(1), two equivalent Na(2), and one V(1) atom to form ONa3V tetrahedra that share corners with four equivalent S(2)Na5V octahedra and  an edgeedge with one S(2)Na5V octahedra. The corner-sharing octahedral tilt angles range from 23-69°.
Na3VS3O crystallizes in the orthorhombic Cmc2_1 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent S(1), three equivalent S(2), and one O(1) atom to form distorted NaS5O octahedra that share corners with two equivalent Na(1)S5O octahedra, corners with four equivalent V(1)S3O tetrahedra, edges with two equivalent Na(1)S5O octahedra, and  an edgeedge with one V(1)S3O tetrahedra. The corner-sharing octahedra are not tilted. Both Na(1)-S(1) bond lengths are 3.05 Å. There are a spread of Na(1)-S(2) bond distances ranging from 2.86-3.10 Å. The Na(1)-O(1) bond length is 2.34 Å. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one S(2), four equivalent S(1), and one O(1) atom. The Na(2)-S(2) bond length is 2.87 Å. There are a spread of Na(2)-S(1) bond distances ranging from 2.89-3.25 Å. The Na(2)-O(1) bond length is 2.33 Å. V(1) is bonded to one S(2), two equivalent S(1), and one O(1) atom to form VS3O tetrahedra that share corners with four equivalent Na(1)S5O octahedra and  an edgeedge with one Na(1)S5O octahedra. The corner-sharing octahedral tilt angles range from 18-75°. The V(1)-S(2) bond length is 2.21 Å. Both V(1)-S(1) bond lengths are 2.19 Å. The V(1)-O(1) bond length is 1.70 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded in a 6-coordinate geometry to one Na(1), four equivalent Na(2), and one V(1) atom. In the second S site, S(2) is bonded to two equivalent Na(2), three equivalent Na(1), and one V(1) atom to form distorted SNa5V octahedra that share corners with two equivalent S(2)Na5V octahedra, corners with four equivalent O(1)Na3V tetrahedra, edges with two equivalent S(2)Na5V octahedra, and  an edgeedge with one O(1)Na3V tetrahedra. The corner-sharing octahedra are not tilted. O(1) is bonded to one Na(1), two equivalent Na(2), and one V(1) atom to form ONa3V tetrahedra that share corners with four equivalent S(2)Na5V octahedra and  an edgeedge with one S(2)Na5V octahedra. The corner-sharing octahedral tilt angles range from 23-69°.