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LaBr3 crystallizes in the hexagonal P6_3/m space group. The structure is three-dimensional. La3+ is bonded in a 9-coordinate geometry to nine equivalent Br1- atoms. There are six shorter (3.11 Å) and three longer (3.21 Å) La–Br bond lengths. Br1- is bonded in a trigonal non-coplanar geometry to three equivalent La3+ atoms.
LaBr crystallizes in the trigonal R-3m space group. The structure is two-dimensional and consists of six LaBr sheets oriented in the (0, 0, 1) direction. La is bonded in a 3-coordinate geometry to three equivalent Br atoms. All La–Br bond lengths are 3.07 Å. Br is bonded in a distorted T-shaped geometry to three equivalent La atoms.
La2Br5 crystallizes in the monoclinic P2_1/m space group. The structure is three-dimensional. there are two inequivalent La+2.50+ sites. In the first La+2.50+ site, La+2.50+ is bonded in a 8-coordinate geometry to eight Br1- atoms. There are a spread of La–Br bond distances ranging from 3.06–3.56 Å. In the second La+2.50+ site, La+2.50+ is bonded to seven Br1- atoms to form distorted edge-sharing LaBr7 pentagonal bipyramids. There are a spread of La–Br bond distances ranging from 3.03–3.16 Å. There are five inequivalent Br1- sites. In the first Br1- site, Br1- is bonded in a 3-coordinate geometry to three La+2.50+ atoms. In the second Br1- site, Br1- is bonded in a distorted trigonal non-coplanar geometry to three equivalent La+2.50+ atoms. In the third Br1- site, Br1- is bonded in a distorted trigonal non-coplanar geometry to three equivalent La+2.50+ atoms. In the fourth Br1- site, Br1- is bonded in a distorted T-shaped geometry to three La+2.50+ atoms. In the fifth Br1- site, Br1- is bonded in a distorted L-shaped geometry to three La+2.50+ atoms.
LaBr2 is Molybdenite-like structured and crystallizes in the hexagonal P6_3/mmc space group. The structure is two-dimensional and consists of two LaBr2 sheets oriented in the (0, 0, 1) direction. La2+ is bonded to six equivalent Br1- atoms to form distorted edge-sharing LaBr6 pentagonal pyramids. All La–Br bond lengths are 3.07 Å. Br1- is bonded in a distorted T-shaped geometry to three equivalent La2+ atoms.