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CsBr is Tetraauricupride structured and crystallizes in the cubic Pm-3m space group. The structure is three-dimensional. Cs1+ is bonded in a body-centered cubic geometry to eight equivalent Br1- atoms. All Cs–Br bond lengths are 3.80 Å. Br1- is bonded in a body-centered cubic geometry to eight equivalent Cs1+ atoms.
CsBr3 crystallizes in the orthorhombic Pnma space group. The structure is three-dimensional. Cs is bonded in a 10-coordinate geometry to ten Br atoms. There are a spread of Cs–Br bond distances ranging from 3.69–4.29 Å. There are three inequivalent Br sites. In the first Br site, Br is bonded in a 5-coordinate geometry to four equivalent Cs and one Br atom. The Br–Br bond length is 2.66 Å. In the second Br site, Br is bonded to four equivalent Cs and one Br atom to form distorted BrCs4Br trigonal bipyramids that share corners with six equivalent BrCs2Br2 tetrahedra, corners with eight equivalent BrCs4Br trigonal bipyramids, an edgeedge with one BrCs2Br2 tetrahedra, and edges with two equivalent BrCs4Br trigonal bipyramids. The Br–Br bond length is 2.52 Å. In the third Br site, Br is bonded to two equivalent Cs and two Br atoms to form distorted BrCs2Br2 tetrahedra that share corners with two equivalent BrCs2Br2 tetrahedra, corners with six equivalent BrCs4Br trigonal bipyramids, and an edgeedge with one BrCs4Br trigonal bipyramid.
CsBr is Halite, Rock Salt structured and crystallizes in the cubic Fm-3m space group. The structure is three-dimensional. Cs1+ is bonded to six equivalent Br1- atoms to form a mixture of edge and corner-sharing CsBr6 octahedra. The corner-sharing octahedral tilt angles are 0°. All Cs–Br bond lengths are 3.70 Å. Br1- is bonded to six equivalent Cs1+ atoms to form a mixture of edge and corner-sharing BrCs6 octahedra. The corner-sharing octahedral tilt angles are 0°.