Cs2VO4Br5 crystallizes in the monoclinic C2/m space group. Cs(1) is bonded to one Br(3), three equivalent Br(1), and four equivalent Br(2) atoms to form a mixture of distorted edge, face, and corner-sharing CsBr8 hexagonal bipyramids. V(1) is bonded in a distorted square co-planar geometry to four equivalent O(1) and two equivalent Br(1) atoms. O(1) is bonded in a single-bond geometry to one V(1) atom. There are three inequivalent Br sites. In the first Br site, Br(1) is bonded in a 4-coordinate geometry to three equivalent Cs(1) and one V(1) atom. In the second Br site, Br(2) is bonded in a distorted see-saw-like geometry to four equivalent Cs(1) atoms. In the third Br site, Br(3) is bonded in a linear geometry to two equivalent Cs(1) atoms.
Cs2VO4Br5 crystallizes in the monoclinic C2/m space group. Cs(1) is bonded to one Br(3), three equivalent Br(1), and four equivalent Br(2) atoms to form a mixture of distorted edge, face, and corner-sharing CsBr8 hexagonal bipyramids. The Cs(1)-Br(3) bond length is 3.54 Å. There are two shorter (3.69 Å) and one longer (3.82 Å) Cs(1)-Br(1) bond length. There are a spread of Cs(1)-Br(2) bond distances ranging from 3.62-3.71 Å. V(1) is bonded in a distorted square co-planar geometry to four equivalent O(1) and two equivalent Br(1) atoms. All V(1)-O(1) bond lengths are 1.83 Å. Both V(1)-Br(1) bond lengths are 2.59 Å. O(1) is bonded in a single-bond geometry to one V(1) atom. There are three inequivalent Br sites. In the first Br site, Br(1) is bonded in a 4-coordinate geometry to three equivalent Cs(1) and one V(1) atom. In the second Br site, Br(2) is bonded in a distorted see-saw-like geometry to four equivalent Cs(1) atoms. In the third Br site, Br(3) is bonded in a linear geometry to two equivalent Cs(1) atoms.