Cd3PCl3 crystallizes in the trigonal P-3m1 space group. There are three inequivalent Cd sites. In the first Cd site, Cd(1) is bonded in a distorted rectangular see-saw-like geometry to one P(1) and three equivalent Cl(1) atoms. In the second Cd site, Cd(2) is bonded to two equivalent P(1) and four equivalent Cl(1) atoms to form CdP2Cl4 octahedra that share corners with four equivalent Cd(3)Cl6 octahedra and edges with four equivalent Cd(2)P2Cl4 octahedra. The corner-sharing octahedral tilt angles are 49°. In the third Cd site, Cd(3) is bonded to six equivalent Cl(1) atoms to form corner-sharing CdCl6 octahedra. The corner-sharing octahedral tilt angles are 49°. P(1) is bonded to one Cd(1) and three equivalent Cd(2) atoms to form corner-sharing PCd4 tetrahedra. Cl(1) is bonded in a 4-coordinate geometry to one Cd(1), one Cd(3), and two equivalent Cd(2) atoms.
Cd3PCl3 crystallizes in the trigonal P-3m1 space group. There are three inequivalent Cd sites. In the first Cd site, Cd(1) is bonded in a distorted rectangular see-saw-like geometry to one P(1) and three equivalent Cl(1) atoms. The Cd(1)-P(1) bond length is 2.46 Å. All Cd(1)-Cl(1) bond lengths are 2.63 Å. In the second Cd site, Cd(2) is bonded to two equivalent P(1) and four equivalent Cl(1) atoms to form CdP2Cl4 octahedra that share corners with four equivalent Cd(3)Cl6 octahedra and edges with four equivalent Cd(2)P2Cl4 octahedra. The corner-sharing octahedral tilt angles are 49°. Both Cd(2)-P(1) bond lengths are 2.45 Å. All Cd(2)-Cl(1) bond lengths are 3.10 Å. In the third Cd site, Cd(3) is bonded to six equivalent Cl(1) atoms to form corner-sharing CdCl6 octahedra. The corner-sharing octahedral tilt angles are 49°. All Cd(3)-Cl(1) bond lengths are 2.66 Å. P(1) is bonded to one Cd(1) and three equivalent Cd(2) atoms to form corner-sharing PCd4 tetrahedra. Cl(1) is bonded in a 4-coordinate geometry to one Cd(1), one Cd(3), and two equivalent Cd(2) atoms.