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LiBa2In crystallizes in the orthorhombic Immm space group. The structure is one-dimensional and consists of two LiBa2In ribbons oriented in the (0, 1, 0) direction. Li is bonded in a linear geometry to two equivalent Ba atoms. Both Li–Ba bond lengths are 3.77 Å. Ba is bonded in a linear geometry to one Li and one In atom. The Ba–In bond length is 3.35 Å. In is bonded in a linear geometry to two equivalent Ba atoms.
LiBa3In11 crystallizes in the hexagonal P6_3/mmc space group. The structure is three-dimensional. Li is bonded to twelve In atoms to form face-sharing LiIn12 cuboctahedra. There are six shorter (3.05 Å) and six longer (3.12 Å) Li–In bond lengths. Ba is bonded in a 10-coordinate geometry to fourteen In atoms. There are a spread of Ba–In bond distances ranging from 3.70–4.05 Å. There are three inequivalent In sites. In the first In site, In is bonded in a 11-coordinate geometry to one Li, four equivalent Ba, and six In atoms. There are a spread of In–In bond distances ranging from 2.99–3.33 Å. In the second In site, In is bonded in a 12-coordinate geometry to two equivalent Li, two equivalent Ba, and eight In atoms. Both In–In bond lengths are 3.24 Å. In the third In site, In is bonded in a 9-coordinate geometry to six equivalent Ba and three equivalent In atoms.