Ag2Bi2SeS3 is alpha Po-derived structured and crystallizes in the orthorhombic Imm2 space group. There are two inequivalent Ag sites. In the first Ag site, Ag(1) is bonded to one Se(1), one S(2), two equivalent S(1), and two equivalent S(3) atoms to form AgSeS5 octahedra that share corners with two equivalent Bi(1)SeS5 octahedra, corners with four equivalent Ag(1)SeS5 octahedra, edges with four equivalent Ag(2)Se2S4 octahedra, edges with four equivalent Bi(2)Se2S4 octahedra, and edges with four equivalent Bi(1)SeS5 octahedra. The corner-sharing octahedral tilt angles range from 0-4°. In the second Ag site, Ag(2) is bonded to two equivalent Se(1), one S(1), one S(3), and two equivalent S(2) atoms to form AgSe2S4 octahedra that share corners with two equivalent Bi(2)Se2S4 octahedra, corners with four equivalent Ag(2)Se2S4 octahedra, edges with four equivalent Ag(1)SeS5 octahedra, edges with four equivalent Bi(2)Se2S4 octahedra, and edges with four equivalent Bi(1)SeS5 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one Se(1), one S(2), two equivalent S(1), and two equivalent S(3) atoms to form BiSeS5 octahedra that share corners with two equivalent Ag(1)SeS5 octahedra, corners with four equivalent Bi(1)SeS5 octahedra, edges with four equivalent Ag(2)Se2S4 octahedra, edges with four equivalent Ag(1)SeS5 octahedra, and edges with four equivalent Bi(2)Se2S4 octahedra. The corner-sharing octahedral tilt angles range from 0-5°. In the second Bi site, Bi(2) is bonded to two equivalent Se(1), one S(1), one S(3), and two equivalent S(2) atoms to form BiSe2S4 octahedra that share corners with two equivalent Ag(2)Se2S4 octahedra, corners with four equivalent Bi(2)Se2S4 octahedra, edges with four equivalent Ag(2)Se2S4 octahedra, edges with four equivalent Ag(1)SeS5 octahedra, and edges with four equivalent Bi(1)SeS5 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. Se(1) is bonded to one Ag(1), two equivalent Ag(2), one Bi(1), and two equivalent Bi(2) atoms to form SeAg3Bi3 octahedra that share corners with two equivalent S(2)Ag3Bi3 octahedra, corners with four equivalent Se(1)Ag3Bi3 octahedra, edges with four equivalent S(1)Ag3Bi3 octahedra, edges with four equivalent S(2)Ag3Bi3 octahedra, and edges with four equivalent S(3)Ag3Bi3 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. There are three inequivalent S sites. In the first S site, S(1) is bonded to one Ag(2), two equivalent Ag(1), one Bi(2), and two equivalent Bi(1) atoms to form SAg3Bi3 octahedra that share corners with two equivalent S(3)Ag3Bi3 octahedra, corners with four equivalent S(1)Ag3Bi3 octahedra, edges with four equivalent Se(1)Ag3Bi3 octahedra, edges with four equivalent S(2)Ag3Bi3 octahedra, and edges with four equivalent S(3)Ag3Bi3 octahedra. The corner-sharing octahedral tilt angles range from 0-4°. In the second S site, S(2) is bonded to one Ag(1), two equivalent Ag(2), one Bi(1), and two equivalent Bi(2) atoms to form SAg3Bi3 octahedra that share corners with two equivalent Se(1)Ag3Bi3 octahedra, corners with four equivalent S(2)Ag3Bi3 octahedra, edges with four equivalent Se(1)Ag3Bi3 octahedra, edges with four equivalent S(1)Ag3Bi3 octahedra, and edges with four equivalent S(3)Ag3Bi3 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. In the third S site, S(3) is bonded to one Ag(2), two equivalent Ag(1), one Bi(2), and two equivalent Bi(1) atoms to form SAg3Bi3 octahedra that share corners with two equivalent S(1)Ag3Bi3 octahedra, corners with four equivalent S(3)Ag3Bi3 octahedra, edges with four equivalent Se(1)Ag3Bi3 octahedra, edges with four equivalent S(1)Ag3Bi3 octahedra, and edges with four equivalent S(2)Ag3Bi3 octahedra. The corner-sharing octahedral tilt angles range from 0-5°.
Ag2Bi2SeS3 is alpha Po-derived structured and crystallizes in the orthorhombic Imm2 space group. There are two inequivalent Ag sites. In the first Ag site, Ag(1) is bonded to one Se(1), one S(2), two equivalent S(1), and two equivalent S(3) atoms to form AgSeS5 octahedra that share corners with two equivalent Bi(1)SeS5 octahedra, corners with four equivalent Ag(1)SeS5 octahedra, edges with four equivalent Ag(2)Se2S4 octahedra, edges with four equivalent Bi(2)Se2S4 octahedra, and edges with four equivalent Bi(1)SeS5 octahedra. The corner-sharing octahedral tilt angles range from 0-4°. The Ag(1)-Se(1) bond length is 2.92 Å. The Ag(1)-S(2) bond length is 2.87 Å. Both Ag(1)-S(1) bond lengths are 2.89 Å. Both Ag(1)-S(3) bond lengths are 2.82 Å. In the second Ag site, Ag(2) is bonded to two equivalent Se(1), one S(1), one S(3), and two equivalent S(2) atoms to form AgSe2S4 octahedra that share corners with two equivalent Bi(2)Se2S4 octahedra, corners with four equivalent Ag(2)Se2S4 octahedra, edges with four equivalent Ag(1)SeS5 octahedra, edges with four equivalent Bi(2)Se2S4 octahedra, and edges with four equivalent Bi(1)SeS5 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. Both Ag(2)-Se(1) bond lengths are 2.82 Å. The Ag(2)-S(1) bond length is 2.95 Å. The Ag(2)-S(3) bond length is 2.95 Å. Both Ag(2)-S(2) bond lengths are 2.89 Å. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one Se(1), one S(2), two equivalent S(1), and two equivalent S(3) atoms to form BiSeS5 octahedra that share corners with two equivalent Ag(1)SeS5 octahedra, corners with four equivalent Bi(1)SeS5 octahedra, edges with four equivalent Ag(2)Se2S4 octahedra, edges with four equivalent Ag(1)SeS5 octahedra, and edges with four equivalent Bi(2)Se2S4 octahedra. The corner-sharing octahedral tilt angles range from 0-5°. The Bi(1)-Se(1) bond length is 2.98 Å. The Bi(1)-S(2) bond length is 2.79 Å. Both Bi(1)-S(1) bond lengths are 2.82 Å. Both Bi(1)-S(3) bond lengths are 2.89 Å. In the second Bi site, Bi(2) is bonded to two equivalent Se(1), one S(1), one S(3), and two equivalent S(2) atoms to form BiSe2S4 octahedra that share corners with two equivalent Ag(2)Se2S4 octahedra, corners with four equivalent Bi(2)Se2S4 octahedra, edges with four equivalent Ag(2)Se2S4 octahedra, edges with four equivalent Ag(1)SeS5 octahedra, and edges with four equivalent Bi(1)SeS5 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. Both Bi(2)-Se(1) bond lengths are 2.89 Å. The Bi(2)-S(1) bond length is 2.85 Å. The Bi(2)-S(3) bond length is 2.82 Å. Both Bi(2)-S(2) bond lengths are 2.83 Å. Se(1) is bonded to one Ag(1), two equivalent Ag(2), one Bi(1), and two equivalent Bi(2) atoms to form SeAg3Bi3 octahedra that share corners with two equivalent S(2)Ag3Bi3 octahedra, corners with four equivalent Se(1)Ag3Bi3 octahedra, edges with four equivalent S(1)Ag3Bi3 octahedra, edges with four equivalent S(2)Ag3Bi3 octahedra, and edges with four equivalent S(3)Ag3Bi3 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. There are three inequivalent S sites. In the first S site, S(1) is bonded to one Ag(2), two equivalent Ag(1), one Bi(2), and two equivalent Bi(1) atoms to form SAg3Bi3 octahedra that share corners with two equivalent S(3)Ag3Bi3 octahedra, corners with four equivalent S(1)Ag3Bi3 octahedra, edges with four equivalent Se(1)Ag3Bi3 octahedra, edges with four equivalent S(2)Ag3Bi3 octahedra, and edges with four equivalent S(3)Ag3Bi3 octahedra. The corner-sharing octahedral tilt angles range from 0-4°. In the second S site, S(2) is bonded to one Ag(1), two equivalent Ag(2), one Bi(1), and two equivalent Bi(2) atoms to form SAg3Bi3 octahedra that share corners with two equivalent Se(1)Ag3Bi3 octahedra, corners with four equivalent S(2)Ag3Bi3 octahedra, edges with four equivalent Se(1)Ag3Bi3 octahedra, edges with four equivalent S(1)Ag3Bi3 octahedra, and edges with four equivalent S(3)Ag3Bi3 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. In the third S site, S(3) is bonded to one Ag(2), two equivalent Ag(1), one Bi(2), and two equivalent Bi(1) atoms to form SAg3Bi3 octahedra that share corners with two equivalent S(1)Ag3Bi3 octahedra, corners with four equivalent S(3)Ag3Bi3 octahedra, edges with four equivalent Se(1)Ag3Bi3 octahedra, edges with four equivalent S(1)Ag3Bi3 octahedra, and edges with four equivalent S(2)Ag3Bi3 octahedra. The corner-sharing octahedral tilt angles range from 0-5°.