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GaF3 crystallizes in the trigonal R-3c space group. The structure is three-dimensional. Ga3+ is bonded to six equivalent F1- atoms to form corner-sharing GaF6 octahedra. The corner-sharing octahedral tilt angles are 34°. All Ga–F bond lengths are 1.92 Å. F1- is bonded in a bent 150 degrees geometry to two equivalent Ga3+ atoms.
GaF3 crystallizes in the monoclinic C2/c space group. The structure is one-dimensional and consists of four fluorine molecules and two GaF ribbons oriented in the (0, 0, 1) direction. In each GaF ribbon, Ga3+ is bonded in a linear geometry to two equivalent F1- atoms. Both Ga–F bond lengths are 2.04 Å. F1- is bonded in an L-shaped geometry to two equivalent Ga3+ atoms.