Ag2BiSbSe4 is alpha Po-derived structured and crystallizes in the tetragonal I-4m2 space group. There are two inequivalent Ag sites. In the first Ag site, Ag(1) is bonded to two equivalent Se(2) and four Se(1,1) atoms to form AgSe6 octahedra that share corners with two equivalent Sb(1)Se6 octahedra, corners with four equivalent Ag(1)Se6 octahedra, edges with four equivalent Ag(2)Se6 octahedra, edges with four equivalent Bi(1)Se6 octahedra, and edges with four equivalent Sb(1)Se6 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the second Ag site, Ag(2) is bonded to two Se(1,1) and four Se(2,2) atoms to form AgSe6 octahedra that share corners with two equivalent Bi(1)Se6 octahedra, corners with four equivalent Ag(2)Se6 octahedra, edges with four equivalent Ag(1)Se6 octahedra, edges with four equivalent Bi(1)Se6 octahedra, and edges with four equivalent Sb(1)Se6 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. Bi(1) is bonded to two Se(1,1) and four Se(2,2) atoms to form BiSe6 octahedra that share corners with two equivalent Ag(2)Se6 octahedra, corners with four equivalent Bi(1)Se6 octahedra, edges with four equivalent Ag(1)Se6 octahedra, edges with four equivalent Ag(2)Se6 octahedra, and edges with four equivalent Sb(1)Se6 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. Sb(1) is bonded to two equivalent Se(2) and four Se(1,1) atoms to form SbSe6 octahedra that share corners with two equivalent Ag(1)Se6 octahedra, corners with four equivalent Sb(1)Se6 octahedra, edges with four equivalent Ag(1)Se6 octahedra, edges with four equivalent Ag(2)Se6 octahedra, and edges with four equivalent Bi(1)Se6 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. There are four inequivalent Se sites. In the first Se site, Se(1) is bonded to one Ag(2), two equivalent Ag(1), one Bi(1), and two equivalent Sb(1) atoms to form SeAg3BiSb2 octahedra that share corners with six Se(1,1)Ag3BiSb2 octahedra; edges with four equivalent Se(1)Ag3BiSb2 octahedra; and edges with eight Se(2,2)Ag3Bi2Sb octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the second Se site, Se(2) is bonded to one Ag(1), two equivalent Ag(2), two equivalent Bi(1), and one Sb(1) atom to form SeAg3Bi2Sb octahedra that share corners with six equivalent Se(2)Ag3Bi2Sb octahedra; edges with four equivalent Se(2)Ag3Bi2Sb octahedra; and edges with eight Se(1,1)Ag3BiSb2 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. In the third Se site, Se(1) is bonded to one Ag(2), two equivalent Ag(1), one Bi(1), and two equivalent Sb(1) atoms to form SeAg3BiSb2 octahedra that share corners with six Se(1,1)Ag3BiSb2 octahedra; edges with four equivalent Se(1)Ag3BiSb2 octahedra; and edges with eight Se(2,2)Ag3Bi2Sb octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the fourth Se site, Se(2) is bonded to one Ag(1), two equivalent Ag(2), two equivalent Bi(1), and one Sb(1) atom to form SeAg3Bi2Sb octahedra that share corners with six equivalent Se(2)Ag3Bi2Sb octahedra; edges with four equivalent Se(2)Ag3Bi2Sb octahedra; and edges with eight Se(1,1)Ag3BiSb2 octahedra. The corner-sharing octahedral tilt angles range from 0-2°.
Ag2BiSbSe4 is alpha Po-derived structured and crystallizes in the tetragonal I-4m2 space group. There are two inequivalent Ag sites. In the first Ag site, Ag(1) is bonded to two equivalent Se(2) and four Se(1,1) atoms to form AgSe6 octahedra that share corners with two equivalent Sb(1)Se6 octahedra, corners with four equivalent Ag(1)Se6 octahedra, edges with four equivalent Ag(2)Se6 octahedra, edges with four equivalent Bi(1)Se6 octahedra, and edges with four equivalent Sb(1)Se6 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. Both Ag(1)-Se(2) bond lengths are 2.99 Å. All Ag(1)-Se(1,1) bond lengths are 2.92 Å. In the second Ag site, Ag(2) is bonded to two Se(1,1) and four Se(2,2) atoms to form AgSe6 octahedra that share corners with two equivalent Bi(1)Se6 octahedra, corners with four equivalent Ag(2)Se6 octahedra, edges with four equivalent Ag(1)Se6 octahedra, edges with four equivalent Bi(1)Se6 octahedra, and edges with four equivalent Sb(1)Se6 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. Both Ag(2)-Se(1,1) bond lengths are 2.91 Å. All Ag(2)-Se(2,2) bond lengths are 2.92 Å. Bi(1) is bonded to two Se(1,1) and four Se(2,2) atoms to form BiSe6 octahedra that share corners with two equivalent Ag(2)Se6 octahedra, corners with four equivalent Bi(1)Se6 octahedra, edges with four equivalent Ag(1)Se6 octahedra, edges with four equivalent Ag(2)Se6 octahedra, and edges with four equivalent Sb(1)Se6 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. Both Bi(1)-Se(1,1) bond lengths are 2.96 Å. All Bi(1)-Se(2,2) bond lengths are 2.92 Å. Sb(1) is bonded to two equivalent Se(2) and four Se(1,1) atoms to form SbSe6 octahedra that share corners with two equivalent Ag(1)Se6 octahedra, corners with four equivalent Sb(1)Se6 octahedra, edges with four equivalent Ag(1)Se6 octahedra, edges with four equivalent Ag(2)Se6 octahedra, and edges with four equivalent Bi(1)Se6 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. Both Sb(1)-Se(2) bond lengths are 2.87 Å. All Sb(1)-Se(1,1) bond lengths are 2.92 Å. There are four inequivalent Se sites. In the first Se site, Se(1) is bonded to one Ag(2), two equivalent Ag(1), one Bi(1), and two equivalent Sb(1) atoms to form SeAg3BiSb2 octahedra that share corners with six Se(1,1)Ag3BiSb2 octahedra; edges with four equivalent Se(1)Ag3BiSb2 octahedra; and edges with eight Se(2,2)Ag3Bi2Sb octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the second Se site, Se(2) is bonded to one Ag(1), two equivalent Ag(2), two equivalent Bi(1), and one Sb(1) atom to form SeAg3Bi2Sb octahedra that share corners with six equivalent Se(2)Ag3Bi2Sb octahedra; edges with four equivalent Se(2)Ag3Bi2Sb octahedra; and edges with eight Se(1,1)Ag3BiSb2 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. The Se(2)-Ag(1) bond length is 2.99 Å. In the third Se site, Se(1) is bonded to one Ag(2), two equivalent Ag(1), one Bi(1), and two equivalent Sb(1) atoms to form SeAg3BiSb2 octahedra that share corners with six Se(1,1)Ag3BiSb2 octahedra; edges with four equivalent Se(1)Ag3BiSb2 octahedra; and edges with eight Se(2,2)Ag3Bi2Sb octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the fourth Se site, Se(2) is bonded to one Ag(1), two equivalent Ag(2), two equivalent Bi(1), and one Sb(1) atom to form SeAg3Bi2Sb octahedra that share corners with six equivalent Se(2)Ag3Bi2Sb octahedra; edges with four equivalent Se(2)Ag3Bi2Sb octahedra; and edges with eight Se(1,1)Ag3BiSb2 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. The Se(2)-Sb(1) bond length is 2.87 Å.