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FeBr2 is trigonal omega structured and crystallizes in the trigonal P-3m1 space group. The structure is two-dimensional and consists of one FeBr2 sheet oriented in the (0, 0, 1) direction. Fe2+ is bonded to six equivalent Br1- atoms to form edge-sharing FeBr6 octahedra. All Fe–Br bond lengths are 2.62 Å. Br1- is bonded in a distorted T-shaped geometry to three equivalent Fe2+ atoms.
FeBr3 is Bismuth triodide structured and crystallizes in the trigonal R-3 space group. The structure is two-dimensional and consists of three FeBr3 sheets oriented in the (0, 0, 1) direction. Fe3+ is bonded to six equivalent Br1- atoms to form edge-sharing FeBr6 octahedra. All Fe–Br bond lengths are 2.43 Å. Br1- is bonded in a water-like geometry to two equivalent Fe3+ atoms.