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Ti2B is Khatyrkite structured and crystallizes in the tetragonal I4/mcm space group. The structure is three-dimensional. Ti is bonded in a 4-coordinate geometry to four equivalent B atoms. All Ti–B bond lengths are 2.42 Å. B is bonded in a 10-coordinate geometry to eight equivalent Ti atoms.
Ti2B crystallizes in the tetragonal I4/mcm space group. The structure is three-dimensional. Ti is bonded in a distorted bent 150 degrees geometry to two equivalent B atoms. Both Ti–B bond lengths are 2.36 Å. B is bonded to four equivalent Ti and two equivalent B atoms to form corner-sharing BTi4B2 octahedra. The corner-sharing octahedra tilt angles range from 0–40°. Both B–B bond lengths are 1.98 Å.