NaSS crystallizes in the tetragonal I-42d space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to two equivalent S(2) and four equivalent S(1) atoms. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to two equivalent S(2) and four equivalent S(1) atoms. There are two inequivalent S sites. In the first S site, S(1) is bonded in a 5-coordinate geometry to two equivalent Na(1), two equivalent Na(2), and one S(2) atom. In the second S site, S(2) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one S(1), and one S(2) atom.
NaSS crystallizes in the tetragonal I-42d space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to two equivalent S(2) and four equivalent S(1) atoms. Both Na(1)-S(2) bond lengths are 3.19 Å. There are two shorter (2.81 Å) and two longer (2.83 Å) Na(1)-S(1) bond lengths. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to two equivalent S(2) and four equivalent S(1) atoms. Both Na(2)-S(2) bond lengths are 3.04 Å. There are two shorter (2.87 Å) and two longer (3.05 Å) Na(2)-S(1) bond lengths. There are two inequivalent S sites. In the first S site, S(1) is bonded in a 5-coordinate geometry to two equivalent Na(1), two equivalent Na(2), and one S(2) atom. The S(1)-S(2) bond length is 2.07 Å. In the second S site, S(2) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one S(1), and one S(2) atom. The S(2)-S(2) bond length is 2.05 Å.