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ErFe2 is Cubic Laves structured and crystallizes in the cubic Fd-3m space group. The structure is three-dimensional. Er is bonded in a 12-coordinate geometry to twelve equivalent Fe atoms. All Er–Fe bond lengths are 2.99 Å. Fe is bonded to six equivalent Er and six equivalent Fe atoms to form a mixture of face, edge, and corner-sharing FeEr6Fe6 cuboctahedra. All Fe–Fe bond lengths are 2.55 Å.
ErFe2 is Hexagonal Laves structured and crystallizes in the hexagonal P6_3/mmc space group. The structure is three-dimensional. Er is bonded in a 12-coordinate geometry to twelve Fe atoms. There are a spread of Er–Fe bond distances ranging from 2.99–3.01 Å. There are two inequivalent Fe sites. In the first Fe site, Fe is bonded to six equivalent Er and six equivalent Fe atoms to form a mixture of corner, edge, and face-sharing FeEr6Fe6 cuboctahedra. All Fe–Fe bond lengths are 2.54 Å. In the second Fe site, Fe is bonded to six equivalent Er and six Fe atoms to form a mixture of corner, edge, and face-sharing FeEr6Fe6 cuboctahedra. There are two shorter (2.55 Å) and two longer (2.58 Å) Fe–Fe bond lengths.