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V2GeC is H-Phase structured and crystallizes in the hexagonal P6_3/mmc space group. The structure is three-dimensional. V is bonded in a 6-coordinate geometry to three equivalent Ge and three equivalent C atoms. All V–Ge bond lengths are 2.63 Å. All V–C bond lengths are 2.04 Å. Ge is bonded in a 12-coordinate geometry to six equivalent V atoms. C is bonded to six equivalent V atoms to form edge-sharing CV6 octahedra.
V3GeC crystallizes in the orthorhombic Cmcm space group. The structure is three-dimensional. there are two inequivalent V sites. In the first V site, V is bonded in a distorted bent 150 degrees geometry to two equivalent Ge and two equivalent C atoms. Both V–Ge bond lengths are 2.57 Å. Both V–C bond lengths are 2.01 Å. In the second V site, V is bonded in a 2-coordinate geometry to three equivalent Ge and two equivalent C atoms. There are two shorter (2.55 Å) and one longer (2.62 Å) V–Ge bond lengths. Both V–C bond lengths are 2.04 Å. Ge is bonded in a 9-coordinate geometry to eight V atoms. C is bonded to six V atoms to form a mixture of edge and corner-sharing CV6 octahedra. The corner-sharing octahedral tilt angles are 23°.