Na2S2O3 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent S(2), two equivalent O(3), and three equivalent O(2) atoms to form a mixture of distorted corner, face, and edge-sharing NaS2O5 pentagonal bipyramids. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to two equivalent S(2), one O(3), and three equivalent O(1) atoms. There are two inequivalent S sites. In the first S site, S(1) is bonded in a trigonal non-coplanar geometry to one S(2), one O(1), one O(2), and one O(3) atom. In the second S site, S(2) is bonded in a 5-coordinate geometry to two equivalent Na(1), two equivalent Na(2), and one S(1) atom. There are three inequivalent O sites. In the first O site, O(1) is bonded to three equivalent Na(2) and one S(1) atom to form a mixture of distorted corner and edge-sharing ONa3S tetrahedra. In the second O site, O(2) is bonded in a 4-coordinate geometry to three equivalent Na(1) and one S(1) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Na(2), two equivalent Na(1), and one S(1) atom.
Na2S2O3 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent S(2), two equivalent O(3), and three equivalent O(2) atoms to form a mixture of distorted corner, face, and edge-sharing NaS2O5 pentagonal bipyramids. There is one shorter (2.89 Å) and one longer (3.03 Å) Na(1)-S(2) bond length. There is one shorter (2.39 Å) and one longer (2.60 Å) Na(1)-O(3) bond length. There are a spread of Na(1)-O(2) bond distances ranging from 2.46-2.60 Å. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to two equivalent S(2), one O(3), and three equivalent O(1) atoms. There is one shorter (2.89 Å) and one longer (3.07 Å) Na(2)-S(2) bond length. The Na(2)-O(3) bond length is 2.62 Å. There are a spread of Na(2)-O(1) bond distances ranging from 2.39-2.58 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded in a trigonal non-coplanar geometry to one S(2), one O(1), one O(2), and one O(3) atom. The S(1)-S(2) bond length is 2.02 Å. The S(1)-O(1) bond length is 1.50 Å. The S(1)-O(2) bond length is 1.49 Å. The S(1)-O(3) bond length is 1.49 Å. In the second S site, S(2) is bonded in a 5-coordinate geometry to two equivalent Na(1), two equivalent Na(2), and one S(1) atom. There are three inequivalent O sites. In the first O site, O(1) is bonded to three equivalent Na(2) and one S(1) atom to form a mixture of distorted corner and edge-sharing ONa3S tetrahedra. In the second O site, O(2) is bonded in a 4-coordinate geometry to three equivalent Na(1) and one S(1) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Na(2), two equivalent Na(1), and one S(1) atom.