CsAgBr2 crystallizes in the orthorhombic Cmcm space group. Cs(1) is bonded in a body-centered cubic geometry to two equivalent Br(2) and six equivalent Br(1) atoms. Ag(1) is bonded to one Br(1) and four equivalent Br(2) atoms to form a mixture of distorted corner and edge-sharing AgBr5 trigonal bipyramids. There are two inequivalent Br sites. In the first Br site, Br(1) is bonded in a 7-coordinate geometry to six equivalent Cs(1) and one Ag(1) atom. In the second Br site, Br(2) is bonded to two equivalent Cs(1) and four equivalent Ag(1) atoms to form a mixture of distorted corner and edge-sharing BrCs2Ag4 octahedra. The corner-sharing octahedral tilt angles are 19°.
CsAgBr2 crystallizes in the orthorhombic Cmcm space group. Cs(1) is bonded in a body-centered cubic geometry to two equivalent Br(2) and six equivalent Br(1) atoms. Both Cs(1)-Br(2) bond lengths are 3.64 Å. There are four shorter (3.77 Å) and two longer (3.88 Å) Cs(1)-Br(1) bond lengths. Ag(1) is bonded to one Br(1) and four equivalent Br(2) atoms to form a mixture of distorted corner and edge-sharing AgBr5 trigonal bipyramids. The Ag(1)-Br(1) bond length is 2.65 Å. There are two shorter (2.75 Å) and two longer (2.99 Å) Ag(1)-Br(2) bond lengths. There are two inequivalent Br sites. In the first Br site, Br(1) is bonded in a 7-coordinate geometry to six equivalent Cs(1) and one Ag(1) atom. In the second Br site, Br(2) is bonded to two equivalent Cs(1) and four equivalent Ag(1) atoms to form a mixture of distorted corner and edge-sharing BrCs2Ag4 octahedra. The corner-sharing octahedral tilt angles are 19°.