Na2S5 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 7-coordinate geometry to one S(2), two equivalent S(1), and four equivalent S(3) atoms. In the second Na site, Na(2) is bonded to two equivalent S(1) and four equivalent S(3) atoms to form NaS6 octahedra that share corners with four equivalent Na(2)S6 octahedra and corners with four equivalent S(1)Na2S2 tetrahedra. The corner-sharing octahedral tilt angles are 68°. There are three inequivalent S sites. In the first S site, S(1) is bonded to one Na(1), one Na(2), one S(2), and one S(3) atom to form distorted SNa2S2 tetrahedra that share corners with two equivalent Na(2)S6 octahedra,  a cornercorner with one S(1)Na2S2 tetrahedra, and  an edgeedge with one S(1)Na2S2 tetrahedra. The corner-sharing octahedral tilt angles range from 71-72°. In the second S site, S(2) is bonded in a distorted trigonal non-coplanar geometry to one Na(1) and two equivalent S(1) atoms. In the third S site, S(3) is bonded in a 5-coordinate geometry to two equivalent Na(1), two equivalent Na(2), and one S(1) atom.
Na2S5 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 7-coordinate geometry to one S(2), two equivalent S(1), and four equivalent S(3) atoms. The Na(1)-S(2) bond length is 2.90 Å. Both Na(1)-S(1) bond lengths are 2.99 Å. There are two shorter (2.85 Å) and two longer (3.00 Å) Na(1)-S(3) bond lengths. In the second Na site, Na(2) is bonded to two equivalent S(1) and four equivalent S(3) atoms to form NaS6 octahedra that share corners with four equivalent Na(2)S6 octahedra and corners with four equivalent S(1)Na2S2 tetrahedra. The corner-sharing octahedral tilt angles are 68°. Both Na(2)-S(1) bond lengths are 3.00 Å. There are two shorter (2.88 Å) and two longer (2.90 Å) Na(2)-S(3) bond lengths. There are three inequivalent S sites. In the first S site, S(1) is bonded to one Na(1), one Na(2), one S(2), and one S(3) atom to form distorted SNa2S2 tetrahedra that share corners with two equivalent Na(2)S6 octahedra,  a cornercorner with one S(1)Na2S2 tetrahedra, and  an edgeedge with one S(1)Na2S2 tetrahedra. The corner-sharing octahedral tilt angles range from 71-72°. The S(1)-S(2) bond length is 2.07 Å. The S(1)-S(3) bond length is 2.06 Å. In the second S site, S(2) is bonded in a distorted trigonal non-coplanar geometry to one Na(1) and two equivalent S(1) atoms. In the third S site, S(3) is bonded in a 5-coordinate geometry to two equivalent Na(1), two equivalent Na(2), and one S(1) atom.