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FeGe2 is Khatyrkite structured and crystallizes in the tetragonal I4/mcm space group. The structure is three-dimensional. Fe is bonded in a 10-coordinate geometry to two equivalent Fe and eight equivalent Ge atoms. Both Fe–Fe bond lengths are 2.47 Å. All Fe–Ge bond lengths are 2.55 Å. Ge is bonded in a 5-coordinate geometry to four equivalent Fe and one Ge atom. The Ge–Ge bond length is 2.63 Å.
FeGe2 crystallizes in the orthorhombic Cmce space group. The structure is three-dimensional. there are two inequivalent Fe sites. In the first Fe site, Fe is bonded in a 8-coordinate geometry to eight Ge atoms. There are a spread of Fe–Ge bond distances ranging from 2.41–2.60 Å. In the second Fe site, Fe is bonded in a 8-coordinate geometry to eight Ge atoms. There are a spread of Fe–Ge bond distances ranging from 2.43–2.53 Å. There are two inequivalent Ge sites. In the first Ge site, Ge is bonded in a 4-coordinate geometry to four Fe and five Ge atoms. There are a spread of Ge–Ge bond distances ranging from 2.64–2.73 Å. In the second Ge site, Ge is bonded in a 4-coordinate geometry to four Fe and five Ge atoms. There are one shorter (2.63 Å) and one longer (2.66 Å) Ge–Ge bond lengths.