PbBi2S4 crystallizes in the orthorhombic Pnma space group. Pb(1) is bonded in a 5-coordinate geometry to one S(4), two equivalent S(1), and two equivalent S(2) atoms. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 7-coordinate geometry to one S(1), one S(4), two equivalent S(2), and three equivalent S(3) atoms. In the second Bi site, Bi(2) is bonded to one S(2), two equivalent S(4), and three equivalent S(1) atoms to form edge-sharing BiS6 octahedra. There are four inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Pb(1), one Bi(1), and three equivalent Bi(2) atoms to form SBi4Pb2 octahedra that share corners with three equivalent S(4)Bi3Pb trigonal pyramids, edges with four equivalent S(1)Bi4Pb2 octahedra, and edges with three equivalent S(4)Bi3Pb trigonal pyramids. In the second S site, S(2) is bonded in a 5-coordinate geometry to two equivalent Pb(1), one Bi(2), and two equivalent Bi(1) atoms. In the third S site, S(3) is bonded in a 3-coordinate geometry to three equivalent Bi(1) atoms. In the fourth S site, S(4) is bonded to one Pb(1), one Bi(1), and two equivalent Bi(2) atoms to form SBi3Pb trigonal pyramids that share corners with three equivalent S(1)Bi4Pb2 octahedra, corners with two equivalent S(4)Bi3Pb trigonal pyramids, and edges with three equivalent S(1)Bi4Pb2 octahedra. The corner-sharing octahedral tilt angles range from 4-40°.
PbBi2S4 crystallizes in the orthorhombic Pnma space group. Pb(1) is bonded in a 5-coordinate geometry to one S(4), two equivalent S(1), and two equivalent S(2) atoms. The Pb(1)-S(4) bond length is 2.86 Å. Both Pb(1)-S(1) bond lengths are 3.08 Å. Both Pb(1)-S(2) bond lengths are 3.00 Å. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 7-coordinate geometry to one S(1), one S(4), two equivalent S(2), and three equivalent S(3) atoms. The Bi(1)-S(1) bond length is 3.22 Å. The Bi(1)-S(4) bond length is 2.97 Å. Both Bi(1)-S(2) bond lengths are 3.02 Å. There are two shorter (2.77 Å) and one longer (2.82 Å) Bi(1)-S(3) bond length. In the second Bi site, Bi(2) is bonded to one S(2), two equivalent S(4), and three equivalent S(1) atoms to form edge-sharing BiS6 octahedra. The Bi(2)-S(2) bond length is 2.68 Å. Both Bi(2)-S(4) bond lengths are 2.76 Å. There are two shorter (2.96 Å) and one longer (3.09 Å) Bi(2)-S(1) bond length. There are four inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Pb(1), one Bi(1), and three equivalent Bi(2) atoms to form SBi4Pb2 octahedra that share corners with three equivalent S(4)Bi3Pb trigonal pyramids, edges with four equivalent S(1)Bi4Pb2 octahedra, and edges with three equivalent S(4)Bi3Pb trigonal pyramids. In the second S site, S(2) is bonded in a 5-coordinate geometry to two equivalent Pb(1), one Bi(2), and two equivalent Bi(1) atoms. In the third S site, S(3) is bonded in a 3-coordinate geometry to three equivalent Bi(1) atoms. In the fourth S site, S(4) is bonded to one Pb(1), one Bi(1), and two equivalent Bi(2) atoms to form SBi3Pb trigonal pyramids that share corners with three equivalent S(1)Bi4Pb2 octahedra, corners with two equivalent S(4)Bi3Pb trigonal pyramids, and edges with three equivalent S(1)Bi4Pb2 octahedra. The corner-sharing octahedral tilt angles range from 4-40°.