YbPS4 crystallizes in the monoclinic C2/c space group. There are three inequivalent Yb sites. In the first Yb site, Yb(1) is bonded in a 7-coordinate geometry to one S(1), one S(2), one S(3), one S(4), one S(5), one S(6), and one S(7) atom. In the second Yb site, Yb(2) is bonded to two equivalent S(3), two equivalent S(5), and two equivalent S(8) atoms to form YbS6 octahedra that share corners with two equivalent P(2)S4 tetrahedra. In the third Yb site, Yb(3) is bonded in a 6-coordinate geometry to two equivalent S(4), two equivalent S(6), and two equivalent S(7) atoms. There are two inequivalent P sites. In the first P site, P(1) is bonded in a trigonal planar geometry to one S(1), one S(3), and one S(7) atom. In the second P site, P(2) is bonded to one S(2), one S(4), one S(5), and one S(6) atom to form PS4 tetrahedra that share  a cornercorner with one Yb(2)S6 octahedra. The corner-sharing octahedral tilt angles are 75°. There are eight inequivalent S sites. In the first S site, S(1) is bonded in a 2-coordinate geometry to one Yb(1) and one P(1) atom. In the second S site, S(2) is bonded in a 3-coordinate geometry to one Yb(1), one P(2), and one S(8) atom. In the third S site, S(3) is bonded in a distorted trigonal planar geometry to one Yb(1), one Yb(2), and one P(1) atom. In the fourth S site, S(4) is bonded in a distorted T-shaped geometry to one Yb(1), one Yb(3), and one P(2) atom. In the fifth S site, S(5) is bonded in a distorted T-shaped geometry to one Yb(1), one Yb(2), and one P(2) atom. In the sixth S site, S(6) is bonded in a distorted T-shaped geometry to one Yb(1), one Yb(3), and one P(2) atom. In the seventh S site, S(7) is bonded in a T-shaped geometry to one Yb(1), one Yb(3), and one P(1) atom. In the eighth S site, S(8) is bonded in a distorted water-like geometry to one Yb(2) and one S(2) atom.
YbPS4 crystallizes in the monoclinic C2/c space group. There are three inequivalent Yb sites. In the first Yb site, Yb(1) is bonded in a 7-coordinate geometry to one S(1), one S(2), one S(3), one S(4), one S(5), one S(6), and one S(7) atom. The Yb(1)-S(1) bond length is 3.04 Å. The Yb(1)-S(2) bond length is 3.16 Å. The Yb(1)-S(3) bond length is 2.93 Å. The Yb(1)-S(4) bond length is 2.89 Å. The Yb(1)-S(5) bond length is 2.87 Å. The Yb(1)-S(6) bond length is 2.79 Å. The Yb(1)-S(7) bond length is 3.07 Å. In the second Yb site, Yb(2) is bonded to two equivalent S(3), two equivalent S(5), and two equivalent S(8) atoms to form YbS6 octahedra that share corners with two equivalent P(2)S4 tetrahedra. Both Yb(2)-S(3) bond lengths are 2.97 Å. Both Yb(2)-S(5) bond lengths are 2.91 Å. Both Yb(2)-S(8) bond lengths are 2.77 Å. In the third Yb site, Yb(3) is bonded in a 6-coordinate geometry to two equivalent S(4), two equivalent S(6), and two equivalent S(7) atoms. Both Yb(3)-S(4) bond lengths are 2.91 Å. Both Yb(3)-S(6) bond lengths are 2.82 Å. Both Yb(3)-S(7) bond lengths are 3.09 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded in a trigonal planar geometry to one S(1), one S(3), and one S(7) atom. The P(1)-S(1) bond length is 1.94 Å. The P(1)-S(3) bond length is 1.98 Å. The P(1)-S(7) bond length is 1.96 Å. In the second P site, P(2) is bonded to one S(2), one S(4), one S(5), and one S(6) atom to form PS4 tetrahedra that share  a cornercorner with one Yb(2)S6 octahedra. The corner-sharing octahedral tilt angles are 75°. The P(2)-S(2) bond length is 2.14 Å. The P(2)-S(4) bond length is 2.04 Å. The P(2)-S(5) bond length is 2.04 Å. The P(2)-S(6) bond length is 2.05 Å. There are eight inequivalent S sites. In the first S site, S(1) is bonded in a 2-coordinate geometry to one Yb(1) and one P(1) atom. In the second S site, S(2) is bonded in a 3-coordinate geometry to one Yb(1), one P(2), and one S(8) atom. The S(2)-S(8) bond length is 2.05 Å. In the third S site, S(3) is bonded in a distorted trigonal planar geometry to one Yb(1), one Yb(2), and one P(1) atom. In the fourth S site, S(4) is bonded in a distorted T-shaped geometry to one Yb(1), one Yb(3), and one P(2) atom. In the fifth S site, S(5) is bonded in a distorted T-shaped geometry to one Yb(1), one Yb(2), and one P(2) atom. In the sixth S site, S(6) is bonded in a distorted T-shaped geometry to one Yb(1), one Yb(3), and one P(2) atom. In the seventh S site, S(7) is bonded in a T-shaped geometry to one Yb(1), one Yb(3), and one P(1) atom. In the eighth S site, S(8) is bonded in a distorted water-like geometry to one Yb(2) and one S(2) atom.