Rh5B4 crystallizes in the hexagonal P6_3/mmc space group. There are three inequivalent Rh sites. In the first Rh site, Rh(1) is bonded in a 6-coordinate geometry to three equivalent B(1) and three equivalent B(2) atoms. In the second Rh site, Rh(2) is bonded in a distorted trigonal non-coplanar geometry to four equivalent B(1) atoms. In the third Rh site, Rh(3) is bonded in a 6-coordinate geometry to six equivalent B(2) atoms. There are two inequivalent B sites. In the first B site, B(1) is bonded in a 8-coordinate geometry to three equivalent Rh(1), four equivalent Rh(2), and one B(2) atom. In the second B site, B(2) is bonded in a 8-coordinate geometry to three equivalent Rh(1), three equivalent Rh(3), one B(1), and one B(2) atom.
Rh5B4 crystallizes in the hexagonal P6_3/mmc space group. There are three inequivalent Rh sites. In the first Rh site, Rh(1) is bonded in a 6-coordinate geometry to three equivalent B(1) and three equivalent B(2) atoms. All Rh(1)-B(1) bond lengths are 2.29 Å. All Rh(1)-B(2) bond lengths are 2.16 Å. In the second Rh site, Rh(2) is bonded in a distorted trigonal non-coplanar geometry to four equivalent B(1) atoms. There are three shorter (2.07 Å) and one longer (2.71 Å) Rh(2)-B(1) bond length. In the third Rh site, Rh(3) is bonded in a 6-coordinate geometry to six equivalent B(2) atoms. All Rh(3)-B(2) bond lengths are 2.21 Å. There are two inequivalent B sites. In the first B site, B(1) is bonded in a 8-coordinate geometry to three equivalent Rh(1), four equivalent Rh(2), and one B(2) atom. The B(1)-B(2) bond length is 2.24 Å. In the second B site, B(2) is bonded in a 8-coordinate geometry to three equivalent Rh(1), three equivalent Rh(3), one B(1), and one B(2) atom. The B(2)-B(2) bond length is 2.18 Å.