CsGdCdTe3 crystallizes in the orthorhombic Cmcm space group. Cs(1) is bonded in a 8-coordinate geometry to two equivalent Te(2) and six equivalent Te(1) atoms. Gd(1) is bonded to two equivalent Te(2) and four equivalent Te(1) atoms to form GdTe6 octahedra that share corners with two equivalent Gd(1)Te6 octahedra, edges with two equivalent Gd(1)Te6 octahedra, and edges with four equivalent Cd(1)Te4 tetrahedra. The corner-sharing octahedral tilt angles are 40°. Cd(1) is bonded to two equivalent Te(1) and two equivalent Te(2) atoms to form CdTe4 tetrahedra that share corners with two equivalent Cd(1)Te4 tetrahedra and edges with four equivalent Gd(1)Te6 octahedra. There are two inequivalent Te sites. In the first Te site, Te(1) is bonded in a 6-coordinate geometry to three equivalent Cs(1), two equivalent Gd(1), and one Cd(1) atom. In the second Te site, Te(2) is bonded in a 6-coordinate geometry to two equivalent Cs(1), two equivalent Gd(1), and two equivalent Cd(1) atoms.
CsGdCdTe3 crystallizes in the orthorhombic Cmcm space group. Cs(1) is bonded in a 8-coordinate geometry to two equivalent Te(2) and six equivalent Te(1) atoms. Both Cs(1)-Te(2) bond lengths are 3.90 Å. There are four shorter (4.01 Å) and two longer (4.15 Å) Cs(1)-Te(1) bond lengths. Gd(1) is bonded to two equivalent Te(2) and four equivalent Te(1) atoms to form GdTe6 octahedra that share corners with two equivalent Gd(1)Te6 octahedra, edges with two equivalent Gd(1)Te6 octahedra, and edges with four equivalent Cd(1)Te4 tetrahedra. The corner-sharing octahedral tilt angles are 40°. Both Gd(1)-Te(2) bond lengths are 3.18 Å. All Gd(1)-Te(1) bond lengths are 3.17 Å. Cd(1) is bonded to two equivalent Te(1) and two equivalent Te(2) atoms to form CdTe4 tetrahedra that share corners with two equivalent Cd(1)Te4 tetrahedra and edges with four equivalent Gd(1)Te6 octahedra. Both Cd(1)-Te(1) bond lengths are 2.81 Å. Both Cd(1)-Te(2) bond lengths are 2.91 Å. There are two inequivalent Te sites. In the first Te site, Te(1) is bonded in a 6-coordinate geometry to three equivalent Cs(1), two equivalent Gd(1), and one Cd(1) atom. In the second Te site, Te(2) is bonded in a 6-coordinate geometry to two equivalent Cs(1), two equivalent Gd(1), and two equivalent Cd(1) atoms.