BiPS4 crystallizes in the orthorhombic Ibca space group. The structure consists of a BiPS4 framework. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 4-coordinate geometry to two equivalent S(1) and two equivalent S(4) atoms. In the second Bi site, Bi(2) is bonded to two equivalent S(2), two equivalent S(3), and two equivalent S(4) atoms to form distorted BiS6 pentagonal pyramids that share corners with two equivalent P(2)S4 tetrahedra and edges with two equivalent P(1)S4 tetrahedra. There are two inequivalent P sites. In the first P site, P(1) is bonded to two equivalent S(2) and two equivalent S(3) atoms to form PS4 tetrahedra that share edges with two equivalent Bi(2)S6 pentagonal pyramids. In the second P site, P(2) is bonded to two equivalent S(1) and two equivalent S(4) atoms to form PS4 tetrahedra that share corners with two equivalent Bi(2)S6 pentagonal pyramids. There are four inequivalent S sites. In the first S site, S(1) is bonded in an L-shaped geometry to one Bi(1) and one P(2) atom. In the second S site, S(2) is bonded in a distorted L-shaped geometry to one Bi(2) and one P(1) atom. In the third S site, S(3) is bonded in a 2-coordinate geometry to one Bi(2) and one P(1) atom. In the fourth S site, S(4) is bonded in a 3-coordinate geometry to one Bi(1), one Bi(2), and one P(2) atom.
BiPS4 crystallizes in the orthorhombic Ibca space group. The structure consists of a BiPS4 framework. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 4-coordinate geometry to two equivalent S(1) and two equivalent S(4) atoms. Both Bi(1)-S(1) bond lengths are 2.72 Å. Both Bi(1)-S(4) bond lengths are 2.85 Å. In the second Bi site, Bi(2) is bonded to two equivalent S(2), two equivalent S(3), and two equivalent S(4) atoms to form distorted BiS6 pentagonal pyramids that share corners with two equivalent P(2)S4 tetrahedra and edges with two equivalent P(1)S4 tetrahedra. Both Bi(2)-S(2) bond lengths are 2.77 Å. Both Bi(2)-S(3) bond lengths are 2.81 Å. Both Bi(2)-S(4) bond lengths are 3.01 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to two equivalent S(2) and two equivalent S(3) atoms to form PS4 tetrahedra that share edges with two equivalent Bi(2)S6 pentagonal pyramids. Both P(1)-S(2) bond lengths are 2.05 Å. Both P(1)-S(3) bond lengths are 2.03 Å. In the second P site, P(2) is bonded to two equivalent S(1) and two equivalent S(4) atoms to form PS4 tetrahedra that share corners with two equivalent Bi(2)S6 pentagonal pyramids. Both P(2)-S(1) bond lengths are 2.04 Å. Both P(2)-S(4) bond lengths are 2.04 Å. There are four inequivalent S sites. In the first S site, S(1) is bonded in an L-shaped geometry to one Bi(1) and one P(2) atom. In the second S site, S(2) is bonded in a distorted L-shaped geometry to one Bi(2) and one P(1) atom. In the third S site, S(3) is bonded in a 2-coordinate geometry to one Bi(2) and one P(1) atom. In the fourth S site, S(4) is bonded in a 3-coordinate geometry to one Bi(1), one Bi(2), and one P(2) atom.