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CdCl2 is trigonal omega-like structured and crystallizes in the trigonal R-3m space group. The structure is two-dimensional and consists of three CdCl2 sheets oriented in the (0, 0, 1) direction. Cd2+ is bonded to six equivalent Cl1- atoms to form edge-sharing CdCl6 octahedra. All Cd–Cl bond lengths are 2.68 Å. Cl1- is bonded in a distorted T-shaped geometry to three equivalent Cd2+ atoms.
CdCl2 is trigonal omega-like structured and crystallizes in the triclinic P-1 space group. The structure is two-dimensional and consists of one CdCl2 sheet oriented in the (0, 0, 1) direction. Cd2+ is bonded to six equivalent Cl1- atoms to form edge-sharing CdCl6 octahedra. There are two shorter (2.67 Å) and four longer (2.69 Å) Cd–Cl bond lengths. Cl1- is bonded in a distorted T-shaped geometry to three equivalent Cd2+ atoms.
CdCl4 crystallizes in the orthorhombic Cmce space group. The structure is two-dimensional and consists of two CdCl4 sheets oriented in the (0, 1, 0) direction. Cd is bonded to six Cl atoms to form corner-sharing CdCl6 octahedra. The corner-sharing octahedral tilt angles are 14°. There are two shorter (2.43 Å) and four longer (2.65 Å) Cd–Cl bond lengths. There are two inequivalent Cl sites. In the first Cl site, Cl is bonded in a single-bond geometry to one Cd atom. In the second Cl site, Cl is bonded in a linear geometry to two equivalent Cd atoms.