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Fe2C crystallizes in the hexagonal P6/mmm space group. The structure is two-dimensional and consists of one Fe2C sheet oriented in the (0, 0, 1) direction. Fe2+ is bonded in a distorted trigonal planar geometry to three equivalent C4- atoms. All Fe–C bond lengths are 2.14 Å. C4- is bonded in a hexagonal planar geometry to six equivalent Fe2+ atoms.
Fe2C is zeta iron carbide structured and crystallizes in the orthorhombic Pnnm space group. The structure is three-dimensional. Fe2+ is bonded in a distorted trigonal planar geometry to three equivalent C4- atoms. There is two shorter (1.92 Å) and one longer (1.94 Å) Fe–C bond length. C4- is bonded to six equivalent Fe2+ atoms to form a mixture of corner and edge-sharing CFe6 octahedra. The corner-sharing octahedral tilt angles are 51°.