Yb5Sb3 crystallizes in the orthorhombic Pnma space group. There are four inequivalent Yb sites. In the first Yb site, Yb(1) is bonded to one Sb(2) and four equivalent Sb(1) atoms to form distorted edge-sharing YbSb5 square pyramids. In the second Yb site, Yb(2) is bonded in a 5-coordinate geometry to one Sb(2) and four equivalent Sb(1) atoms. In the third Yb site, Yb(3) is bonded in a 5-coordinate geometry to two equivalent Sb(2) and four equivalent Sb(1) atoms. In the fourth Yb site, Yb(4) is bonded in a 5-coordinate geometry to two equivalent Sb(2) and three equivalent Sb(1) atoms. There are two inequivalent Sb sites. In the first Sb site, Sb(1) is bonded in a 9-coordinate geometry to two equivalent Yb(1), two equivalent Yb(2), two equivalent Yb(3), and three equivalent Yb(4) atoms. In the second Sb site, Sb(2) is bonded in a 8-coordinate geometry to one Yb(1), one Yb(2), two equivalent Yb(3), and four equivalent Yb(4) atoms.
Yb5Sb3 crystallizes in the orthorhombic Pnma space group. There are four inequivalent Yb sites. In the first Yb site, Yb(1) is bonded to one Sb(2) and four equivalent Sb(1) atoms to form distorted edge-sharing YbSb5 square pyramids. The Yb(1)-Sb(2) bond length is 3.18 Å. There are two shorter (3.23 Å) and two longer (3.24 Å) Yb(1)-Sb(1) bond lengths. In the second Yb site, Yb(2) is bonded in a 5-coordinate geometry to one Sb(2) and four equivalent Sb(1) atoms. The Yb(2)-Sb(2) bond length is 3.05 Å. There are two shorter (3.26 Å) and two longer (3.39 Å) Yb(2)-Sb(1) bond lengths. In the third Yb site, Yb(3) is bonded in a 5-coordinate geometry to two equivalent Sb(2) and four equivalent Sb(1) atoms. There is one shorter (3.15 Å) and one longer (3.70 Å) Yb(3)-Sb(2) bond length. There are two shorter (3.27 Å) and two longer (3.32 Å) Yb(3)-Sb(1) bond lengths. In the fourth Yb site, Yb(4) is bonded in a 5-coordinate geometry to two equivalent Sb(2) and three equivalent Sb(1) atoms. There is one shorter (3.02 Å) and one longer (3.19 Å) Yb(4)-Sb(2) bond length. There are a spread of Yb(4)-Sb(1) bond distances ranging from 3.28-3.63 Å. There are two inequivalent Sb sites. In the first Sb site, Sb(1) is bonded in a 9-coordinate geometry to two equivalent Yb(1), two equivalent Yb(2), two equivalent Yb(3), and three equivalent Yb(4) atoms. In the second Sb site, Sb(2) is bonded in a 8-coordinate geometry to one Yb(1), one Yb(2), two equivalent Yb(3), and four equivalent Yb(4) atoms.