Na(VS2)2 crystallizes in the monoclinic Pm space group. Na(1) is bonded in a 6-coordinate geometry to one S(3), one S(4), two equivalent S(1), and two equivalent S(2) atoms. There are two inequivalent V sites. In the first V site, V(1) is bonded to one S(1), one S(2), two equivalent S(3), and two equivalent S(4) atoms to form edge-sharing VS6 octahedra. In the second V site, V(2) is bonded to one S(3), one S(4), two equivalent S(1), and two equivalent S(2) atoms to form edge-sharing VS6 octahedra. There are four inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Na(1), one V(1), and two equivalent V(2) atoms to form a mixture of corner and edge-sharing SNa2V3 square pyramids. In the second S site, S(2) is bonded to two equivalent Na(1), one V(1), and two equivalent V(2) atoms to form a mixture of distorted corner and edge-sharing SNa2V3 trigonal bipyramids. In the third S site, S(3) is bonded in a rectangular see-saw-like geometry to one Na(1), one V(2), and two equivalent V(1) atoms. In the fourth S site, S(4) is bonded in a rectangular see-saw-like geometry to one Na(1), one V(2), and two equivalent V(1) atoms.
Na(VS2)2 crystallizes in the monoclinic Pm space group. Na(1) is bonded in a 6-coordinate geometry to one S(3), one S(4), two equivalent S(1), and two equivalent S(2) atoms. The Na(1)-S(3) bond length is 2.94 Å. The Na(1)-S(4) bond length is 2.84 Å. Both Na(1)-S(1) bond lengths are 2.82 Å. Both Na(1)-S(2) bond lengths are 2.89 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one S(1), one S(2), two equivalent S(3), and two equivalent S(4) atoms to form edge-sharing VS6 octahedra. The V(1)-S(1) bond length is 2.43 Å. The V(1)-S(2) bond length is 2.34 Å. Both V(1)-S(3) bond lengths are 2.43 Å. Both V(1)-S(4) bond lengths are 2.40 Å. In the second V site, V(2) is bonded to one S(3), one S(4), two equivalent S(1), and two equivalent S(2) atoms to form edge-sharing VS6 octahedra. The V(2)-S(3) bond length is 2.31 Å. The V(2)-S(4) bond length is 2.43 Å. Both V(2)-S(1) bond lengths are 2.42 Å. Both V(2)-S(2) bond lengths are 2.43 Å. There are four inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Na(1), one V(1), and two equivalent V(2) atoms to form a mixture of corner and edge-sharing SNa2V3 square pyramids. In the second S site, S(2) is bonded to two equivalent Na(1), one V(1), and two equivalent V(2) atoms to form a mixture of distorted corner and edge-sharing SNa2V3 trigonal bipyramids. In the third S site, S(3) is bonded in a rectangular see-saw-like geometry to one Na(1), one V(2), and two equivalent V(1) atoms. In the fourth S site, S(4) is bonded in a rectangular see-saw-like geometry to one Na(1), one V(2), and two equivalent V(1) atoms.