NaPS3 crystallizes in the monoclinic P2_1/m space group. Na(1) is bonded in a 6-coordinate geometry to one S(1), one S(2), one S(4), one S(5), and two equivalent S(3) atoms. There are two inequivalent P sites. In the first P site, P(1) is bonded to one S(3), one S(5), and two equivalent S(1) atoms to form edge-sharing PS4 tetrahedra. In the second P site, P(2) is bonded to one S(2), one S(4), and two equivalent S(1) atoms to form edge-sharing PS4 tetrahedra. There are five inequivalent S sites. In the first S site, S(1) is bonded in a 3-coordinate geometry to one Na(1), one P(1), and one P(2) atom. In the second S site, S(2) is bonded in a 3-coordinate geometry to two equivalent Na(1) and one P(2) atom. In the third S site, S(3) is bonded to four equivalent Na(1) and one P(1) atom to form distorted edge-sharing SNa4P square pyramids. In the fourth S site, S(4) is bonded in a trigonal non-coplanar geometry to two equivalent Na(1) and one P(2) atom. In the fifth S site, S(5) is bonded in a 3-coordinate geometry to two equivalent Na(1) and one P(1) atom.
NaPS3 crystallizes in the monoclinic P2_1/m space group. Na(1) is bonded in a 6-coordinate geometry to one S(1), one S(2), one S(4), one S(5), and two equivalent S(3) atoms. The Na(1)-S(1) bond length is 3.29 Å. The Na(1)-S(2) bond length is 2.96 Å. The Na(1)-S(4) bond length is 2.90 Å. The Na(1)-S(5) bond length is 3.03 Å. There is one shorter (2.92 Å) and one longer (3.32 Å) Na(1)-S(3) bond length. There are two inequivalent P sites. In the first P site, P(1) is bonded to one S(3), one S(5), and two equivalent S(1) atoms to form edge-sharing PS4 tetrahedra. The P(1)-S(3) bond length is 2.00 Å. The P(1)-S(5) bond length is 2.00 Å. Both P(1)-S(1) bond lengths are 2.14 Å. In the second P site, P(2) is bonded to one S(2), one S(4), and two equivalent S(1) atoms to form edge-sharing PS4 tetrahedra. The P(2)-S(2) bond length is 2.00 Å. The P(2)-S(4) bond length is 1.98 Å. Both P(2)-S(1) bond lengths are 2.18 Å. There are five inequivalent S sites. In the first S site, S(1) is bonded in a 3-coordinate geometry to one Na(1), one P(1), and one P(2) atom. In the second S site, S(2) is bonded in a 3-coordinate geometry to two equivalent Na(1) and one P(2) atom. In the third S site, S(3) is bonded to four equivalent Na(1) and one P(1) atom to form distorted edge-sharing SNa4P square pyramids. In the fourth S site, S(4) is bonded in a trigonal non-coplanar geometry to two equivalent Na(1) and one P(2) atom. In the fifth S site, S(5) is bonded in a 3-coordinate geometry to two equivalent Na(1) and one P(1) atom.