Dy5Bi3 crystallizes in the orthorhombic Pnma space group. There are four inequivalent Dy sites. In the first Dy site, Dy(1) is bonded in a 5-coordinate geometry to two equivalent Bi(1) and three equivalent Bi(2) atoms. In the second Dy site, Dy(2) is bonded in a 6-coordinate geometry to two equivalent Bi(1) and four equivalent Bi(2) atoms. In the third Dy site, Dy(3) is bonded to one Bi(1) and four equivalent Bi(2) atoms to form distorted edge-sharing DyBi5 square pyramids. In the fourth Dy site, Dy(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 Dy(3), one Dy(4), two equivalent Dy(2), and four equivalent Dy(1) atoms. In the second Bi site, Bi(2) is bonded in a 9-coordinate geometry to two equivalent Dy(2), two equivalent Dy(3), two equivalent Dy(4), and three equivalent Dy(1) atoms.
Dy5Bi3 crystallizes in the orthorhombic Pnma space group. There are four inequivalent Dy sites. In the first Dy site, Dy(1) is bonded in a 5-coordinate geometry to two equivalent Bi(1) and three equivalent Bi(2) atoms. There is one shorter (3.07 Å) and one longer (3.18 Å) Dy(1)-Bi(1) bond length. There are a spread of Dy(1)-Bi(2) bond distances ranging from 3.35-3.58 Å. In the second Dy site, Dy(2) is bonded in a 6-coordinate geometry to two equivalent Bi(1) and four equivalent Bi(2) atoms. There is one shorter (3.11 Å) and one longer (3.52 Å) Dy(2)-Bi(1) bond length. There are two shorter (3.22 Å) and two longer (3.34 Å) Dy(2)-Bi(2) bond lengths. In the third Dy site, Dy(3) is bonded to one Bi(1) and four equivalent Bi(2) atoms to form distorted edge-sharing DyBi5 square pyramids. The Dy(3)-Bi(1) bond length is 3.16 Å. There are two shorter (3.20 Å) and two longer (3.22 Å) Dy(3)-Bi(2) bond lengths. In the fourth Dy site, Dy(4) is bonded in a 5-coordinate geometry to one Bi(1) and four equivalent Bi(2) atoms. The Dy(4)-Bi(1) bond length is 3.06 Å. There are two shorter (3.27 Å) and two longer (3.35 Å) Dy(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 Dy(3), one Dy(4), two equivalent Dy(2), and four equivalent Dy(1) atoms. In the second Bi site, Bi(2) is bonded in a 9-coordinate geometry to two equivalent Dy(2), two equivalent Dy(3), two equivalent Dy(4), and three equivalent Dy(1) atoms.