AgCu2PbBiS4 crystallizes in the orthorhombic Pnma space group. Ag(1) is bonded in a 7-coordinate geometry to one Cu(2), two equivalent Cu(1), one S(3), one S(4), and two equivalent S(1) atoms. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a distorted linear geometry to two equivalent Ag(1), one S(1), one S(3), and two equivalent S(2) atoms. In the second Cu site, Cu(2) is bonded in a 3-coordinate geometry to one Ag(1), one Pb(1), one S(2), and two equivalent S(3) atoms. Pb(1) is bonded to one Cu(2), one S(2), two equivalent S(1), and two equivalent S(4) atoms to form PbCuS5 octahedra that share corners with four equivalent Bi(1)S6 octahedra, edges with two equivalent Pb(1)CuS5 octahedra, and edges with three equivalent Bi(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 6-70°. Bi(1) is bonded to one S(1), two equivalent S(2), and three equivalent S(4) atoms to form BiS6 octahedra that share corners with four equivalent Pb(1)CuS5 octahedra, edges with three equivalent Pb(1)CuS5 octahedra, and edges with four equivalent Bi(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 6-70°. There are four inequivalent S sites. In the first S site, S(4) is bonded to one Ag(1), two equivalent Pb(1), and three equivalent Bi(1) atoms to form edge-sharing SAgBi3Pb2 octahedra. In the second S site, S(1) is bonded in a 6-coordinate geometry to two equivalent Ag(1), one Cu(1), two equivalent Pb(1), and one Bi(1) atom. In the third S site, S(2) is bonded in a 6-coordinate geometry to one Cu(2), two equivalent Cu(1), one Pb(1), and two equivalent Bi(1) atoms. In the fourth S site, S(3) is bonded in a 4-coordinate geometry to one Ag(1), one Cu(1), and two equivalent Cu(2) atoms.
AgCu2PbBiS4 crystallizes in the orthorhombic Pnma space group. Ag(1) is bonded in a 7-coordinate geometry to one Cu(2), two equivalent Cu(1), one S(3), one S(4), and two equivalent S(1) atoms. The Ag(1)-Cu(2) bond length is 3.03 Å. Both Ag(1)-Cu(1) bond lengths are 2.71 Å. The Ag(1)-S(3) bond length is 2.52 Å. The Ag(1)-S(4) bond length is 3.08 Å. Both Ag(1)-S(1) bond lengths are 2.70 Å. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a distorted linear geometry to two equivalent Ag(1), one S(1), one S(3), and two equivalent S(2) atoms. The Cu(1)-S(1) bond length is 2.20 Å. The Cu(1)-S(3) bond length is 2.24 Å. Both Cu(1)-S(2) bond lengths are 3.07 Å. In the second Cu site, Cu(2) is bonded in a 3-coordinate geometry to one Ag(1), one Pb(1), one S(2), and two equivalent S(3) atoms. The Cu(2)-Pb(1) bond length is 3.00 Å. The Cu(2)-S(2) bond length is 2.34 Å. Both Cu(2)-S(3) bond lengths are 2.28 Å. Pb(1) is bonded to one Cu(2), one S(2), two equivalent S(1), and two equivalent S(4) atoms to form PbCuS5 octahedra that share corners with four equivalent Bi(1)S6 octahedra, edges with two equivalent Pb(1)CuS5 octahedra, and edges with three equivalent Bi(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 6-70°. The Pb(1)-S(2) bond length is 2.92 Å. Both Pb(1)-S(1) bond lengths are 3.02 Å. Both Pb(1)-S(4) bond lengths are 3.09 Å. Bi(1) is bonded to one S(1), two equivalent S(2), and three equivalent S(4) atoms to form BiS6 octahedra that share corners with four equivalent Pb(1)CuS5 octahedra, edges with three equivalent Pb(1)CuS5 octahedra, and edges with four equivalent Bi(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 6-70°. The Bi(1)-S(1) bond length is 2.93 Å. Both Bi(1)-S(2) bond lengths are 2.78 Å. There is one shorter (2.76 Å) and two longer (2.96 Å) Bi(1)-S(4) bond lengths. There are four inequivalent S sites. In the first S site, S(4) is bonded to one Ag(1), two equivalent Pb(1), and three equivalent Bi(1) atoms to form edge-sharing SAgBi3Pb2 octahedra. In the second S site, S(1) is bonded in a 6-coordinate geometry to two equivalent Ag(1), one Cu(1), two equivalent Pb(1), and one Bi(1) atom. In the third S site, S(2) is bonded in a 6-coordinate geometry to one Cu(2), two equivalent Cu(1), one Pb(1), and two equivalent Bi(1) atoms. In the fourth S site, S(3) is bonded in a 4-coordinate geometry to one Ag(1), one Cu(1), and two equivalent Cu(2) atoms.