P2NbS8 crystallizes in the tetragonal P-4n2 space group. Nb(1) is bonded in a 8-coordinate geometry to two equivalent S(2), two equivalent S(4), and four equivalent S(1) atoms. P(1) is bonded to one S(2), one S(4), and two equivalent S(3) atoms to form corner-sharing PS4 tetrahedra. There are four inequivalent S sites. In the first S site, S(4) is bonded in an L-shaped geometry to one Nb(1) and one P(1) atom. In the second S site, S(1) is bonded in a 3-coordinate geometry to two equivalent Nb(1) and one S(1) atom. In the third S site, S(2) is bonded in an L-shaped geometry to one Nb(1) and one P(1) atom. In the fourth S site, S(3) is bonded in a water-like geometry to two equivalent P(1) atoms.
P2NbS8 crystallizes in the tetragonal P-4n2 space group. Nb(1) is bonded in a 8-coordinate geometry to two equivalent S(2), two equivalent S(4), and four equivalent S(1) atoms. Both Nb(1)-S(2) bond lengths are 2.71 Å. Both Nb(1)-S(4) bond lengths are 2.63 Å. There are two shorter (2.52 Å) and two longer (2.53 Å) Nb(1)-S(1) bond lengths. P(1) is bonded to one S(2), one S(4), and two equivalent S(3) atoms to form corner-sharing PS4 tetrahedra. The P(1)-S(2) bond length is 1.99 Å. The P(1)-S(4) bond length is 2.01 Å. Both P(1)-S(3) bond lengths are 2.14 Å. There are four inequivalent S sites. In the first S site, S(4) is bonded in an L-shaped geometry to one Nb(1) and one P(1) atom. In the second S site, S(1) is bonded in a 3-coordinate geometry to two equivalent Nb(1) and one S(1) atom. The S(1)-S(1) bond length is 2.02 Å. In the third S site, S(2) is bonded in an L-shaped geometry to one Nb(1) and one P(1) atom. In the fourth S site, S(3) is bonded in a water-like geometry to two equivalent P(1) atoms.