CsBrF crystallizes in the tetragonal I4/mmm space group. Cs(1) is bonded to four equivalent Br(1) and five equivalent F(1) atoms to form distorted CsBr4F5 square pyramids that share corners with four equivalent F(1)Cs5Br octahedra, edges with eight equivalent Cs(1)Br4F5 square pyramids, and faces with four equivalent Cs(1)Br4F5 square pyramids. The corner-sharing octahedral tilt angles are 126°. Br(1) is bonded in a 6-coordinate geometry to four equivalent Cs(1), one Br(1), and one F(1) atom. F(1) is bonded to five equivalent Cs(1) and one Br(1) atom to form FCs5Br octahedra that share corners with four equivalent F(1)Cs5Br octahedra, corners with four equivalent Cs(1)Br4F5 square pyramids, and edges with eight equivalent F(1)Cs5Br octahedra. The corner-sharing octahedral tilt angles are 11°.
CsBrF crystallizes in the tetragonal I4/mmm space group. Cs(1) is bonded to four equivalent Br(1) and five equivalent F(1) atoms to form distorted CsBr4F5 square pyramids that share corners with four equivalent F(1)Cs5Br octahedra, edges with eight equivalent Cs(1)Br4F5 square pyramids, and faces with four equivalent Cs(1)Br4F5 square pyramids. The corner-sharing octahedral tilt angles are 126°. All Cs(1)-Br(1) bond lengths are 3.75 Å. There is one shorter (2.93 Å) and four longer (3.06 Å) Cs(1)-F(1) bond lengths. Br(1) is bonded in a 6-coordinate geometry to four equivalent Cs(1), one Br(1), and one F(1) atom. The Br(1)-Br(1) bond length is 2.39 Å. The Br(1)-F(1) bond length is 2.48 Å. F(1) is bonded to five equivalent Cs(1) and one Br(1) atom to form FCs5Br octahedra that share corners with four equivalent F(1)Cs5Br octahedra, corners with four equivalent Cs(1)Br4F5 square pyramids, and edges with eight equivalent F(1)Cs5Br octahedra. The corner-sharing octahedral tilt angles are 11°.