Rb2ZnBr4 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 7-coordinate geometry to one Br(1), two equivalent Br(2), two equivalent Br(3), and two equivalent Br(4) atoms. In the second Rb site, Rb(2) is bonded in a 9-coordinate geometry to two equivalent Br(2), two equivalent Br(3), two equivalent Br(4), and three equivalent Br(1) atoms. Zn(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 1-coordinate geometry to one Rb(1), three equivalent Rb(2), and one Zn(1) atom. In the second Br site, Br(2) is bonded in a 1-coordinate geometry to two equivalent Rb(1), two equivalent Rb(2), and one Zn(1) atom. In the third Br site, Br(3) is bonded to two equivalent Rb(1), two equivalent Rb(2), and one Zn(1) atom to form a mixture of distorted edge and corner-sharing BrRb4Zn trigonal bipyramids. In the fourth Br site, Br(4) is bonded in a 5-coordinate geometry to two equivalent Rb(1), two equivalent Rb(2), and one Zn(1) atom.
Rb2ZnBr4 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 7-coordinate geometry to one Br(1), two equivalent Br(2), two equivalent Br(3), and two equivalent Br(4) atoms. The Rb(1)-Br(1) bond length is 3.51 Å. There is one shorter (3.56 Å) and one longer (3.91 Å) Rb(1)-Br(2) bond length. There is one shorter (3.55 Å) and one longer (3.60 Å) Rb(1)-Br(3) bond length. There is one shorter (3.74 Å) and one longer (3.78 Å) Rb(1)-Br(4) bond length. In the second Rb site, Rb(2) is bonded in a 9-coordinate geometry to two equivalent Br(2), two equivalent Br(3), two equivalent Br(4), and three equivalent Br(1) atoms. There is one shorter (3.49 Å) and one longer (3.62 Å) Rb(2)-Br(2) bond length. There is one shorter (3.53 Å) and one longer (3.59 Å) Rb(2)-Br(3) bond length. There is one shorter (3.49 Å) and one longer (3.50 Å) Rb(2)-Br(4) bond length. There are a spread of Rb(2)-Br(1) bond distances ranging from 3.45-4.02 Å. Zn(1) is bonded in a tetrahedral geometry to one Br(1), one Br(2), one Br(3), and one Br(4) atom. The Zn(1)-Br(1) bond length is 2.39 Å. The Zn(1)-Br(2) bond length is 2.42 Å. The Zn(1)-Br(3) bond length is 2.42 Å. The Zn(1)-Br(4) bond length is 2.41 Å. There are four inequivalent Br sites. In the first Br site, Br(1) is bonded in a 1-coordinate geometry to one Rb(1), three equivalent Rb(2), and one Zn(1) atom. In the second Br site, Br(2) is bonded in a 1-coordinate geometry to two equivalent Rb(1), two equivalent Rb(2), and one Zn(1) atom. In the third Br site, Br(3) is bonded to two equivalent Rb(1), two equivalent Rb(2), and one Zn(1) atom to form a mixture of distorted edge and corner-sharing BrRb4Zn trigonal bipyramids. In the fourth Br site, Br(4) is bonded in a 5-coordinate geometry to two equivalent Rb(1), two equivalent Rb(2), and one Zn(1) atom.