Zr5Sb3 crystallizes in the orthorhombic Pnma space group. There are four inequivalent Zr sites. In the first Zr site, Zr(1) is bonded to one Sb(1) and four equivalent Sb(2) atoms to form distorted ZrSb5 square pyramids that share corners with four equivalent Zr(2)Sb6 octahedra, edges with two equivalent Zr(1)Sb5 square pyramids, and faces with two equivalent Zr(2)Sb6 octahedra. The corner-sharing octahedral tilt angles range from 35-47°. In the second Zr site, Zr(2) is bonded to two equivalent Sb(1) and four equivalent Sb(2) atoms to form distorted ZrSb6 octahedra that share corners with six equivalent Zr(2)Sb6 octahedra, corners with four equivalent Zr(1)Sb5 square pyramids, and faces with two equivalent Zr(1)Sb5 square pyramids. The corner-sharing octahedral tilt angles range from 30-48°. In the third Zr site, Zr(3) is bonded in a 5-coordinate geometry to one Sb(1) and four equivalent Sb(2) atoms. In the fourth Zr site, Zr(4) is bonded in a 5-coordinate geometry to two equivalent Sb(1) and three equivalent Sb(2) atoms. There are two inequivalent Sb sites. In the first Sb site, Sb(1) is bonded in a 8-coordinate geometry to one Zr(1), one Zr(3), two equivalent Zr(2), and four equivalent Zr(4) atoms. In the second Sb site, Sb(2) is bonded in a 9-coordinate geometry to two equivalent Zr(1), two equivalent Zr(2), two equivalent Zr(3), and three equivalent Zr(4) atoms.
Zr5Sb3 crystallizes in the orthorhombic Pnma space group. There are four inequivalent Zr sites. In the first Zr site, Zr(1) is bonded to one Sb(1) and four equivalent Sb(2) atoms to form distorted ZrSb5 square pyramids that share corners with four equivalent Zr(2)Sb6 octahedra, edges with two equivalent Zr(1)Sb5 square pyramids, and faces with two equivalent Zr(2)Sb6 octahedra. The corner-sharing octahedral tilt angles range from 35-47°. The Zr(1)-Sb(1) bond length is 2.93 Å. There are two shorter (2.98 Å) and two longer (2.99 Å) Zr(1)-Sb(2) bond lengths. In the second Zr site, Zr(2) is bonded to two equivalent Sb(1) and four equivalent Sb(2) atoms to form distorted ZrSb6 octahedra that share corners with six equivalent Zr(2)Sb6 octahedra, corners with four equivalent Zr(1)Sb5 square pyramids, and faces with two equivalent Zr(1)Sb5 square pyramids. The corner-sharing octahedral tilt angles range from 30-48°. There is one shorter (2.89 Å) and one longer (3.15 Å) Zr(2)-Sb(1) bond length. There are two shorter (3.01 Å) and two longer (3.04 Å) Zr(2)-Sb(2) bond lengths. In the third Zr site, Zr(3) is bonded in a 5-coordinate geometry to one Sb(1) and four equivalent Sb(2) atoms. The Zr(3)-Sb(1) bond length is 2.83 Å. There are two shorter (2.95 Å) and two longer (3.15 Å) Zr(3)-Sb(2) bond lengths. In the fourth Zr site, Zr(4) is bonded in a 5-coordinate geometry to two equivalent Sb(1) and three equivalent Sb(2) atoms. There is one shorter (2.85 Å) and one longer (2.92 Å) Zr(4)-Sb(1) bond length. There are a spread of Zr(4)-Sb(2) bond distances ranging from 3.11-3.15 Å. There are two inequivalent Sb sites. In the first Sb site, Sb(1) is bonded in a 8-coordinate geometry to one Zr(1), one Zr(3), two equivalent Zr(2), and four equivalent Zr(4) atoms. In the second Sb site, Sb(2) is bonded in a 9-coordinate geometry to two equivalent Zr(1), two equivalent Zr(2), two equivalent Zr(3), and three equivalent Zr(4) atoms.