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UBr3 crystallizes in the hexagonal P6_3/m space group. The structure is three-dimensional. U3+ is bonded in a 9-coordinate geometry to nine equivalent Br1- atoms. There are six shorter (3.07 Å) and three longer (3.17 Å) U–Br bond lengths. Br1- is bonded in a distorted trigonal non-coplanar geometry to three equivalent U3+ atoms.
Li(UBr3)2Li2UBr6 is trigonal omega-derived structured and crystallizes in the trigonal P-31m space group. The structure is two-dimensional and consists of one Li(UBr3)2 sheet oriented in the (0, 0, 1) direction and one Li2UBr6 sheet oriented in the (0, 0, 1) direction. In the Li(UBr3)2 sheet, Li1+ is bonded to six equivalent Br1- atoms to form LiBr6 octahedra that share edges with six equivalent UBr6 octahedra. All Li–Br bond lengths are 2.83 Å. U3+ is bonded to six equivalent Br1- atoms to form UBr6 octahedra that share edges with three equivalent LiBr6 octahedra and edges with three equivalent UBr6 octahedra. All U–Br bond lengths are 2.95 Å. Br1- is bonded in a 3-coordinate geometry to one Li1+ and two equivalent U3+ atoms. In the Li2UBr6 sheet, Li1+ is bonded to six equivalent Br1- atoms to form LiBr6 octahedra that share edges with three equivalent LiBr6 octahedra and edges with three equivalent UBr6 octahedra. All Li–Br bond lengths are 2.87 Å. U3+ is bonded to six equivalent Br1- atoms to form UBr6 octahedra that share edges with six equivalent LiBr6 octahedra. All U–Br bond lengths are 2.87 Å. Br1- is bonded in a 3-coordinate geometry to two equivalent Li1+ and one U3+ atom.