AgBi2Se3Cl crystallizes in the monoclinic P2_1/m space group. Ag(1) is bonded in a 6-coordinate geometry to one Se(2), two equivalent Se(3), and three equivalent Se(1) atoms. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one Se(1), three equivalent Se(2), and two equivalent Cl(1) atoms to form distorted BiSe4Cl2 octahedra that share corners with two equivalent Bi(2)Se5 square pyramids and edges with four equivalent Bi(1)Se4Cl2 octahedra. In the second Bi site, Bi(2) is bonded to two equivalent Se(1) and three equivalent Se(3) atoms to form BiSe5 square pyramids that share corners with two equivalent Bi(1)Se4Cl2 octahedra and edges with four equivalent Bi(2)Se5 square pyramids. The corner-sharing octahedral tilt angles are 77°. There are three inequivalent Se sites. In the first Se site, Se(1) is bonded to three equivalent Ag(1), one Bi(1), and two equivalent Bi(2) atoms to form distorted SeAg3Bi3 octahedra that share corners with four equivalent Se(3)Ag2Bi3 square pyramids, edges with four equivalent Se(1)Ag3Bi3 octahedra, and edges with four equivalent Se(3)Ag2Bi3 square pyramids. In the second Se site, Se(2) is bonded in a rectangular see-saw-like geometry to one Ag(1) and three equivalent Bi(1) atoms. In the third Se site, Se(3) is bonded to two equivalent Ag(1) and three equivalent Bi(2) atoms to form SeAg2Bi3 square pyramids that share corners with four equivalent Se(1)Ag3Bi3 octahedra, edges with four equivalent Se(1)Ag3Bi3 octahedra, and edges with four equivalent Se(3)Ag2Bi3 square pyramids. The corner-sharing octahedral tilt angles range from 13-18°. Cl(1) is bonded in an L-shaped geometry to two equivalent Bi(1) atoms.
AgBi2Se3Cl crystallizes in the monoclinic P2_1/m space group. Ag(1) is bonded in a 6-coordinate geometry to one Se(2), two equivalent Se(3), and three equivalent Se(1) atoms. The Ag(1)-Se(2) bond length is 2.97 Å. Both Ag(1)-Se(3) bond lengths are 2.98 Å. There is one shorter (2.83 Å) and two longer (2.90 Å) Ag(1)-Se(1) bond lengths. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one Se(1), three equivalent Se(2), and two equivalent Cl(1) atoms to form distorted BiSe4Cl2 octahedra that share corners with two equivalent Bi(2)Se5 square pyramids and edges with four equivalent Bi(1)Se4Cl2 octahedra. The Bi(1)-Se(1) bond length is 3.07 Å. There are two shorter (2.83 Å) and one longer (2.97 Å) Bi(1)-Se(2) bond length. Both Bi(1)-Cl(1) bond lengths are 3.03 Å. In the second Bi site, Bi(2) is bonded to two equivalent Se(1) and three equivalent Se(3) atoms to form BiSe5 square pyramids that share corners with two equivalent Bi(1)Se4Cl2 octahedra and edges with four equivalent Bi(2)Se5 square pyramids. The corner-sharing octahedral tilt angles are 77°. Both Bi(2)-Se(1) bond lengths are 3.00 Å. There is one shorter (2.75 Å) and two longer (2.98 Å) Bi(2)-Se(3) bond lengths. There are three inequivalent Se sites. In the first Se site, Se(1) is bonded to three equivalent Ag(1), one Bi(1), and two equivalent Bi(2) atoms to form distorted SeAg3Bi3 octahedra that share corners with four equivalent Se(3)Ag2Bi3 square pyramids, edges with four equivalent Se(1)Ag3Bi3 octahedra, and edges with four equivalent Se(3)Ag2Bi3 square pyramids. In the second Se site, Se(2) is bonded in a rectangular see-saw-like geometry to one Ag(1) and three equivalent Bi(1) atoms. In the third Se site, Se(3) is bonded to two equivalent Ag(1) and three equivalent Bi(2) atoms to form SeAg2Bi3 square pyramids that share corners with four equivalent Se(1)Ag3Bi3 octahedra, edges with four equivalent Se(1)Ag3Bi3 octahedra, and edges with four equivalent Se(3)Ag2Bi3 square pyramids. The corner-sharing octahedral tilt angles range from 13-18°. Cl(1) is bonded in an L-shaped geometry to two equivalent Bi(1) atoms.