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Fe2B is Khatyrkite structured and crystallizes in the tetragonal I4/mcm space group. The structure is three-dimensional. Fe is bonded in a 4-coordinate geometry to four equivalent B atoms. All Fe–B bond lengths are 2.17 Å. B is bonded in a 10-coordinate geometry to eight equivalent Fe and two equivalent B atoms. Both B–B bond lengths are 2.12 Å.
FeB crystallizes in the orthorhombic Pnma space group. The structure is three-dimensional. Fe3+ is bonded in a 7-coordinate geometry to seven equivalent B3- atoms. There are five shorter (2.14 Å) and two longer (2.15 Å) Fe–B bond lengths. B3- is bonded in a 9-coordinate geometry to seven equivalent Fe3+ and two equivalent B3- atoms. Both B–B bond lengths are 1.79 Å.
Fe2B crystallizes in the tetragonal P4/mmm space group. The structure is three-dimensional. Fe is bonded in a 4-coordinate geometry to four equivalent B atoms. All Fe–B bond lengths are 2.15 Å. B is bonded in a body-centered cubic geometry to eight equivalent Fe atoms.
FeB2 is hexagonal omega structure structured and crystallizes in the hexagonal P6/mmm space group. The structure is three-dimensional. Fe is bonded to twelve equivalent B atoms to form a mixture of edge and face-sharing FeB12 cuboctahedra. All Fe–B bond lengths are 2.22 Å. B is bonded in a 9-coordinate geometry to six equivalent Fe and three equivalent B atoms. All B–B bond lengths are 1.74 Å.
Fe3B is Cementite structured and crystallizes in the orthorhombic Pnma space group. The structure is three-dimensional. there are two inequivalent Fe sites. In the first Fe site, Fe is bonded in a 2-coordinate geometry to three equivalent B atoms. There are two shorter (2.13 Å) and one longer (2.49 Å) Fe–B bond lengths. In the second Fe site, Fe is bonded in a 2-coordinate geometry to three equivalent B atoms. There are a spread of Fe–B bond distances ranging from 2.07–2.28 Å. B is bonded in a 9-coordinate geometry to nine Fe atoms.
FeB crystallizes in the orthorhombic Cmcm space group. The structure is three-dimensional. Fe3+ is bonded in a 7-coordinate geometry to seven equivalent B3- atoms. There are a spread of Fe–B bond distances ranging from 2.14–2.17 Å. B3- is bonded in a 9-coordinate geometry to seven equivalent Fe3+ and two equivalent B3- atoms. Both B–B bond lengths are 1.81 Å.
Fe3B crystallizes in the tetragonal I-4 space group. The structure is three-dimensional. there are three inequivalent Fe sites. In the first Fe site, Fe is bonded in a 2-coordinate geometry to two equivalent B atoms. There are one shorter (2.13 Å) and one longer (2.23 Å) Fe–B bond lengths. In the second Fe site, Fe is bonded in a 3-coordinate geometry to three equivalent B atoms. There are a spread of Fe–B bond distances ranging from 2.12–2.31 Å. In the third Fe site, Fe is bonded in a 4-coordinate geometry to four equivalent B atoms. There are a spread of Fe–B bond distances ranging from 2.18–2.21 Å. B is bonded in a 9-coordinate geometry to nine Fe atoms.