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MgBr2 is trigonal omega structured and crystallizes in the trigonal P-3m1 space group. The structure is two-dimensional and consists of one MgBr2 sheet oriented in the (0, 0, 1) direction. Mg2+ is bonded to six equivalent Br1- atoms to form edge-sharing MgBr6 octahedra. All Mg–Br bond lengths are 2.70 Å. Br1- is bonded in a distorted T-shaped geometry to three equivalent Mg2+ atoms.
(Mg)2MgBr crystallizes in the tetragonal I4/mmm space group. The structure is two-dimensional and consists of two Mg sheets oriented in the (0, 0, 1) direction and two MgBr sheets oriented in the (0, 0, 1) direction. In each Mg sheet, Mg is bonded in a 4-coordinate geometry to four equivalent Mg atoms. All Mg–Mg bond lengths are 3.08 Å. In each MgBr sheet, Mg is bonded in a square co-planar geometry to four equivalent Br atoms. All Mg–Br bond lengths are 3.08 Å. Br is bonded in a square co-planar geometry to four equivalent Mg atoms.
MgBr4(Br)2 crystallizes in the orthorhombic Cmmm space group. The structure is zero-dimensional and consists of four hydrobromic acid molecules and two MgBr4 clusters. In each MgBr4 cluster, Mg is bonded in a distorted rectangular see-saw-like geometry to four equivalent Br atoms. All Mg–Br bond lengths are 2.51 Å. Br is bonded in a single-bond geometry to one Mg atom.