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KBrF4 crystallizes in the tetragonal I4/mcm space group. The structure is three-dimensional. K is bonded in a 8-coordinate geometry to eight equivalent F atoms. All K–F bond lengths are 2.79 Å. Br is bonded in a square co-planar geometry to four equivalent F atoms. All Br–F bond lengths are 1.94 Å. F is bonded in a trigonal planar geometry to two equivalent K and one Br atom.
KBrF4 crystallizes in the monoclinic C2/m space group. The structure is three-dimensional. K is bonded in a body-centered cubic geometry to eight F atoms. There are four shorter (2.78 Å) and four longer (2.79 Å) K–F bond lengths. Br is bonded in a 4-coordinate geometry to four F atoms. There are three shorter (2.04 Å) and one longer (2.05 Å) Br–F bond lengths. There are three inequivalent F sites. In the first F site, F is bonded in a distorted trigonal planar geometry to two equivalent K and one Br atom. In the second F site, F is bonded in a distorted trigonal planar geometry to two equivalent K and one Br atom. In the third F site, F is bonded in a distorted trigonal planar geometry to two equivalent K and one Br atom.