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ZnI4(I)2 crystallizes in the orthorhombic Cmmm space group. The structure is zero-dimensional and consists of four hydriodic acid molecules and two ZnI4 clusters. In each ZnI4 cluster, Zn is bonded in a distorted square co-planar geometry to four equivalent I atoms. All Zn–I bond lengths are 2.66 Å. I is bonded in a single-bond geometry to one Zn atom.
ZnI2 is trigonal omega-like structured and crystallizes in the trigonal R-3m space group. The structure is two-dimensional and consists of three ZnI2 sheets oriented in the (0, 0, 1) direction. Zn2+ is bonded to six equivalent I1- atoms to form edge-sharing ZnI6 octahedra. All Zn–I bond lengths are 2.88 Å. I1- is bonded in a distorted T-shaped geometry to three equivalent Zn2+ atoms.