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PCl4ICl2 is beta-prime cadmium gold structured and crystallizes in the tetragonal P-42_1m space group. The structure is zero-dimensional and consists of two [pcl4]+1 molecules and two ICl2 clusters. In each ICl2 cluster, I is bonded in a linear geometry to two equivalent Cl atoms. Both I–Cl bond lengths are 2.58 Å. Cl is bonded in a single-bond geometry to one I atom.
PCl4ICl4 crystallizes in the orthorhombic Imma space group. The structure is zero-dimensional and consists of eight [pcl4]+1 molecules and eight ICl4 clusters. In each ICl4 cluster, I5+ is bonded in a rectangular see-saw-like geometry to four Cl1- atoms. There are two shorter (2.52 Å) and two longer (2.54 Å) I–Cl bond lengths. There are two inequivalent Cl1- sites. In the first Cl1- site, Cl1- is bonded in a single-bond geometry to one I5+ atom. In the second Cl1- site, Cl1- is bonded in a single-bond geometry to one I5+ atom.