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Li3Re is Uranium Silicide-like structured and crystallizes in the hexagonal P6_3/mmc space group. The structure is three-dimensional. Li is bonded in a distorted see-saw-like geometry to four equivalent Re atoms. There are two shorter (2.71 Å) and two longer (2.73 Å) Li–Re bond lengths. Re is bonded to twelve equivalent Li atoms to form a mixture of face and corner-sharing ReLi12 cuboctahedra.
LiRe3 is alpha bismuth trifluoride structured and crystallizes in the tetragonal I4/mmm space group. The structure is three-dimensional. there are two inequivalent Li sites. In the first Li site, Li is bonded in a distorted body-centered cubic geometry to fourteen Re atoms. There are a spread of Li–Re bond distances ranging from 2.64–3.07 Å. In the second Li site, Li is bonded in a distorted body-centered cubic geometry to fourteen Re atoms. There are a spread of Li–Re bond distances ranging from 2.64–3.07 Å. There are three inequivalent Re sites. In the first Re site, Re is bonded to four Li and four Re atoms to form a mixture of distorted corner, edge, and face-sharing ReLi4Re4 tetrahedra. All Re–Re bond lengths are 2.64 Å. In the second Re site, Re is bonded in a 8-coordinate geometry to six Li and eight equivalent Re atoms. In the third Re site, Re is bonded in a 8-coordinate geometry to six Li and eight equivalent Re atoms.