Cs2CdBr4 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 8-coordinate geometry to one Br(1), two equivalent Br(3), two equivalent Br(4), and three equivalent Br(2) atoms. In the second Cs site, Cs(2) is bonded in a 8-coordinate geometry to two equivalent Br(1), two equivalent Br(2), two equivalent Br(3), and two equivalent Br(4) atoms. Cd(1) is bonded in a tetrahedral geometry to one Br(1), one Br(2), one Br(3), and one Br(4) atom. There are four inequivalent Br sites. In the first Br site, Br(1) is bonded in a distorted see-saw-like geometry to one Cs(1), two equivalent Cs(2), and one Cd(1) atom. In the second Br site, Br(2) is bonded in a 1-coordinate geometry to two equivalent Cs(2), three equivalent Cs(1), and one Cd(1) atom. In the third Br site, Br(3) is bonded to two equivalent Cs(1), two equivalent Cs(2), and one Cd(1) atom to form a mixture of distorted corner and edge-sharing BrCs4Cd trigonal bipyramids. In the fourth Br site, Br(4) is bonded in a 5-coordinate geometry to two equivalent Cs(1), two equivalent Cs(2), and one Cd(1) atom.
Cs2CdBr4 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 8-coordinate geometry to one Br(1), two equivalent Br(3), two equivalent Br(4), and three equivalent Br(2) atoms. The Cs(1)-Br(1) bond length is 3.64 Å. There is one shorter (3.71 Å) and one longer (3.81 Å) Cs(1)-Br(3) bond length. There is one shorter (3.84 Å) and one longer (3.91 Å) Cs(1)-Br(4) bond length. There are a spread of Cs(1)-Br(2) bond distances ranging from 3.76-4.26 Å. In the second Cs site, Cs(2) is bonded in a 8-coordinate geometry to two equivalent Br(1), two equivalent Br(2), two equivalent Br(3), and two equivalent Br(4) atoms. There is one shorter (3.67 Å) and one longer (3.92 Å) Cs(2)-Br(1) bond length. There is one shorter (3.75 Å) and one longer (3.76 Å) Cs(2)-Br(2) bond length. There is one shorter (3.71 Å) and one longer (3.72 Å) Cs(2)-Br(3) bond length. There is one shorter (3.62 Å) and one longer (3.69 Å) Cs(2)-Br(4) bond length. Cd(1) is bonded in a tetrahedral geometry to one Br(1), one Br(2), one Br(3), and one Br(4) atom. The Cd(1)-Br(1) bond length is 2.59 Å. The Cd(1)-Br(2) bond length is 2.62 Å. The Cd(1)-Br(3) bond length is 2.62 Å. The Cd(1)-Br(4) bond length is 2.61 Å. There are four inequivalent Br sites. In the first Br site, Br(1) is bonded in a distorted see-saw-like geometry to one Cs(1), two equivalent Cs(2), and one Cd(1) atom. In the second Br site, Br(2) is bonded in a 1-coordinate geometry to two equivalent Cs(2), three equivalent Cs(1), and one Cd(1) atom. In the third Br site, Br(3) is bonded to two equivalent Cs(1), two equivalent Cs(2), and one Cd(1) atom to form a mixture of distorted corner and edge-sharing BrCs4Cd trigonal bipyramids. In the fourth Br site, Br(4) is bonded in a 5-coordinate geometry to two equivalent Cs(1), two equivalent Cs(2), and one Cd(1) atom.