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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.
ZnBr2 crystallizes in the tetragonal I4_1/acd space group. The structure is three-dimensional and consists of two ZnBr2 frameworks. Zn2+ is bonded to four Br1- atoms to form corner-sharing ZnBr4 tetrahedra. There are a spread of Zn–Br bond distances ranging from 2.44–2.46 Å. There are three inequivalent Br1- sites. In the first Br1- site, Br1- is bonded in a water-like geometry to two equivalent Zn2+ atoms. In the second Br1- site, Br1- is bonded in a bent 120 degrees geometry to two equivalent Zn2+ atoms. In the third Br1- site, Br1- is bonded in a water-like geometry to two equivalent Zn2+ atoms.