Ho5Bi3 crystallizes in the orthorhombic Pnma space group. There are four inequivalent Ho sites. In the first Ho site, Ho(1) is bonded in a 5-coordinate geometry to two equivalent Bi(1) and three equivalent Bi(2) atoms. In the second Ho site, Ho(2) is bonded in a 6-coordinate geometry to two equivalent Bi(1) and four equivalent Bi(2) atoms. In the third Ho site, Ho(3) is bonded to one Bi(1) and four equivalent Bi(2) atoms to form distorted edge-sharing HoBi5 square pyramids. In the fourth Ho site, Ho(4) is bonded in a 5-coordinate geometry to one Bi(1) and four equivalent Bi(2) atoms. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 8-coordinate geometry to one Ho(3), one Ho(4), two equivalent Ho(2), and four equivalent Ho(1) atoms. In the second Bi site, Bi(2) is bonded in a 9-coordinate geometry to two equivalent Ho(2), two equivalent Ho(3), two equivalent Ho(4), and three equivalent Ho(1) atoms.
Ho5Bi3 crystallizes in the orthorhombic Pnma space group. There are four inequivalent Ho sites. In the first Ho site, Ho(1) is bonded in a 5-coordinate geometry to two equivalent Bi(1) and three equivalent Bi(2) atoms. There is one shorter (3.06 Å) and one longer (3.16 Å) Ho(1)-Bi(1) bond length. There are a spread of Ho(1)-Bi(2) bond distances ranging from 3.32-3.57 Å. In the second Ho site, Ho(2) is bonded in a 6-coordinate geometry to two equivalent Bi(1) and four equivalent Bi(2) atoms. There is one shorter (3.10 Å) and one longer (3.49 Å) Ho(2)-Bi(1) bond length. There are two shorter (3.20 Å) and two longer (3.33 Å) Ho(2)-Bi(2) bond lengths. In the third Ho site, Ho(3) is bonded to one Bi(1) and four equivalent Bi(2) atoms to form distorted edge-sharing HoBi5 square pyramids. The Ho(3)-Bi(1) bond length is 3.14 Å. There are two shorter (3.18 Å) and two longer (3.21 Å) Ho(3)-Bi(2) bond lengths. In the fourth Ho site, Ho(4) is bonded in a 5-coordinate geometry to one Bi(1) and four equivalent Bi(2) atoms. The Ho(4)-Bi(1) bond length is 3.05 Å. There are two shorter (3.25 Å) and two longer (3.34 Å) Ho(4)-Bi(2) bond lengths. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 8-coordinate geometry to one Ho(3), one Ho(4), two equivalent Ho(2), and four equivalent Ho(1) atoms. In the second Bi site, Bi(2) is bonded in a 9-coordinate geometry to two equivalent Ho(2), two equivalent Ho(3), two equivalent Ho(4), and three equivalent Ho(1) atoms.