Cd3PI3 crystallizes in the monoclinic Pm space group. There are three inequivalent Cd sites. In the first Cd site, Cd(1) is bonded to two equivalent P(1), one I(1), and one I(3) atom to form CdP2I2 tetrahedra that share corners with two equivalent Cd(1)P2I2 tetrahedra, corners with four equivalent Cd(2)PI3 tetrahedra, and corners with four equivalent Cd(3)PI3 tetrahedra. In the second Cd site, Cd(2) is bonded to one P(1), one I(2), and two equivalent I(3) atoms to form CdPI3 tetrahedra that share corners with two equivalent Cd(2)PI3 tetrahedra, corners with two equivalent Cd(3)PI3 tetrahedra, and corners with four equivalent Cd(1)P2I2 tetrahedra. In the third Cd site, Cd(3) is bonded to one P(1), one I(2), and two equivalent I(1) atoms to form CdPI3 tetrahedra that share corners with two equivalent Cd(2)PI3 tetrahedra, corners with two equivalent Cd(3)PI3 tetrahedra, and corners with four equivalent Cd(1)P2I2 tetrahedra. P(1) is bonded to one Cd(2), one Cd(3), and two equivalent Cd(1) atoms to form corner-sharing PCd4 tetrahedra. There are three inequivalent I sites. In the first I site, I(1) is bonded in a trigonal non-coplanar geometry to one Cd(1) and two equivalent Cd(3) atoms. In the second I site, I(2) is bonded in a water-like geometry to one Cd(2) and one Cd(3) atom. In the third I site, I(3) is bonded in a trigonal non-coplanar geometry to one Cd(1) and two equivalent Cd(2) atoms.
Cd3PI3 crystallizes in the monoclinic Pm space group. There are three inequivalent Cd sites. In the first Cd site, Cd(1) is bonded to two equivalent P(1), one I(1), and one I(3) atom to form CdP2I2 tetrahedra that share corners with two equivalent Cd(1)P2I2 tetrahedra, corners with four equivalent Cd(2)PI3 tetrahedra, and corners with four equivalent Cd(3)PI3 tetrahedra. Both Cd(1)-P(1) bond lengths are 2.50 Å. The Cd(1)-I(1) bond length is 3.01 Å. The Cd(1)-I(3) bond length is 3.04 Å. In the second Cd site, Cd(2) is bonded to one P(1), one I(2), and two equivalent I(3) atoms to form CdPI3 tetrahedra that share corners with two equivalent Cd(2)PI3 tetrahedra, corners with two equivalent Cd(3)PI3 tetrahedra, and corners with four equivalent Cd(1)P2I2 tetrahedra. The Cd(2)-P(1) bond length is 2.48 Å. The Cd(2)-I(2) bond length is 2.83 Å. Both Cd(2)-I(3) bond lengths are 2.94 Å. In the third Cd site, Cd(3) is bonded to one P(1), one I(2), and two equivalent I(1) atoms to form CdPI3 tetrahedra that share corners with two equivalent Cd(2)PI3 tetrahedra, corners with two equivalent Cd(3)PI3 tetrahedra, and corners with four equivalent Cd(1)P2I2 tetrahedra. The Cd(3)-P(1) bond length is 2.49 Å. The Cd(3)-I(2) bond length is 2.82 Å. Both Cd(3)-I(1) bond lengths are 2.95 Å. P(1) is bonded to one Cd(2), one Cd(3), and two equivalent Cd(1) atoms to form corner-sharing PCd4 tetrahedra. There are three inequivalent I sites. In the first I site, I(1) is bonded in a trigonal non-coplanar geometry to one Cd(1) and two equivalent Cd(3) atoms. In the second I site, I(2) is bonded in a water-like geometry to one Cd(2) and one Cd(3) atom. In the third I site, I(3) is bonded in a trigonal non-coplanar geometry to one Cd(1) and two equivalent Cd(2) atoms.