CdBiSe2Br crystallizes in the orthorhombic Pnma space group. Cd(1) is bonded to two equivalent Se(1), two equivalent Se(2), and two equivalent Br(1) atoms to form CdSe4Br2 octahedra that share corners with two equivalent Cd(1)Se4Br2 octahedra, corners with four equivalent Bi(1)Se5 square pyramids, edges with two equivalent Cd(1)Se4Br2 octahedra, and edges with three equivalent Bi(1)Se5 square pyramids. The corner-sharing octahedral tilt angles are 46°. Bi(1) is bonded to two equivalent Se(1) and three equivalent Se(2) atoms to form BiSe5 square pyramids that share corners with four equivalent Cd(1)Se4Br2 octahedra, edges with three equivalent Cd(1)Se4Br2 octahedra, and edges with four equivalent Bi(1)Se5 square pyramids. The corner-sharing octahedral tilt angles range from 14-66°. There are two inequivalent Se sites. In the first Se site, Se(1) is bonded in a rectangular see-saw-like geometry to two equivalent Cd(1) and two equivalent Bi(1) atoms. In the second Se site, Se(2) is bonded to two equivalent Cd(1) and three equivalent Bi(1) atoms to form edge-sharing SeCd2Bi3 square pyramids. Br(1) is bonded in an L-shaped geometry to two equivalent Cd(1) atoms.
CdBiSe2Br crystallizes in the orthorhombic Pnma space group. Cd(1) is bonded to two equivalent Se(1), two equivalent Se(2), and two equivalent Br(1) atoms to form CdSe4Br2 octahedra that share corners with two equivalent Cd(1)Se4Br2 octahedra, corners with four equivalent Bi(1)Se5 square pyramids, edges with two equivalent Cd(1)Se4Br2 octahedra, and edges with three equivalent Bi(1)Se5 square pyramids. The corner-sharing octahedral tilt angles are 46°. There is one shorter (2.75 Å) and one longer (2.76 Å) Cd(1)-Se(1) bond length. Both Cd(1)-Se(2) bond lengths are 2.93 Å. Both Cd(1)-Br(1) bond lengths are 2.79 Å. Bi(1) is bonded to two equivalent Se(1) and three equivalent Se(2) atoms to form BiSe5 square pyramids that share corners with four equivalent Cd(1)Se4Br2 octahedra, edges with three equivalent Cd(1)Se4Br2 octahedra, and edges with four equivalent Bi(1)Se5 square pyramids. The corner-sharing octahedral tilt angles range from 14-66°. Both Bi(1)-Se(1) bond lengths are 2.84 Å. There is one shorter (2.72 Å) and two longer (3.12 Å) Bi(1)-Se(2) bond lengths. There are two inequivalent Se sites. In the first Se site, Se(1) is bonded in a rectangular see-saw-like geometry to two equivalent Cd(1) and two equivalent Bi(1) atoms. In the second Se site, Se(2) is bonded to two equivalent Cd(1) and three equivalent Bi(1) atoms to form edge-sharing SeCd2Bi3 square pyramids. Br(1) is bonded in an L-shaped geometry to two equivalent Cd(1) atoms.