(RhBi4)3(Br)2 crystallizes in the orthorhombic Fddd space group. The structure consists of sixteen hydrogen bromide atoms inside a RhBi4 framework. In the RhBi4 framework, there are two inequivalent Rh sites. In the first Rh site, Rh(1) is bonded in a body-centered cubic geometry to two equivalent Bi(1), two equivalent Bi(3), and four equivalent Bi(2) atoms. In the second Rh site, Rh(2) is bonded in a 8-coordinate geometry to four equivalent Bi(1) and four equivalent Bi(3) atoms. There are three inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a distorted water-like geometry to one Rh(1) and one Rh(2) atom. In the second Bi site, Bi(2) is bonded in a distorted water-like geometry to two equivalent Rh(1) atoms. In the third Bi site, Bi(3) is bonded in a distorted water-like geometry to one Rh(1) and one Rh(2) atom.
(RhBi4)3(Br)2 crystallizes in the orthorhombic Fddd space group. The structure consists of sixteen hydrogen bromide atoms inside a RhBi4 framework. In the RhBi4 framework, there are two inequivalent Rh sites. In the first Rh site, Rh(1) is bonded in a body-centered cubic geometry to two equivalent Bi(1), two equivalent Bi(3), and four equivalent Bi(2) atoms. Both Rh(1)-Bi(1) bond lengths are 2.95 Å. Both Rh(1)-Bi(3) bond lengths are 2.88 Å. There are two shorter (2.87 Å) and two longer (2.89 Å) Rh(1)-Bi(2) bond lengths. In the second Rh site, Rh(2) is bonded in a 8-coordinate geometry to four equivalent Bi(1) and four equivalent Bi(3) atoms. All Rh(2)-Bi(1) bond lengths are 2.88 Å. All Rh(2)-Bi(3) bond lengths are 2.87 Å. There are three inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a distorted water-like geometry to one Rh(1) and one Rh(2) atom. In the second Bi site, Bi(2) is bonded in a distorted water-like geometry to two equivalent Rh(1) atoms. In the third Bi site, Bi(3) is bonded in a distorted water-like geometry to one Rh(1) and one Rh(2) atom.