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ZnBr4(Br)2 crystallizes in the orthorhombic Cmmm space group. The structure is zero-dimensional and consists of four hydrobromic acid molecules and two ZnBr4 clusters. In each ZnBr4 cluster, Zn is bonded in a distorted rectangular see-saw-like geometry to four equivalent Br atoms. All Zn–Br bond lengths are 2.45 Å. Br is bonded in a single-bond geometry to one Zn atom.
ZnBr2 is trigonal omega-like structured and crystallizes in the trigonal R-3m space group. The structure is two-dimensional and consists of three ZnBr2 sheets oriented in the (0, 0, 1) direction. Zn2+ is bonded to six equivalent Br1- atoms to form edge-sharing ZnBr6 octahedra. All Zn–Br bond lengths are 2.65 Å. Br1- is bonded in a distorted T-shaped geometry to three equivalent Zn2+ atoms.