Zr5Ge4 crystallizes in the tetragonal P4_12_12 space group. There are three inequivalent Zr sites. In the first Zr site, Zr(1) is bonded to two equivalent Ge(1) and four equivalent Ge(2) atoms to form corner-sharing ZrGe6 octahedra. The corner-sharing octahedral tilt angles are 52°. In the second Zr site, Zr(2) is bonded in a 7-coordinate geometry to three equivalent Ge(2) and four equivalent Ge(1) atoms. In the third Zr site, Zr(3) is bonded in a 6-coordinate geometry to three equivalent Ge(1) and three equivalent Ge(2) atoms. There are two inequivalent Ge sites. In the first Ge site, Ge(1) is bonded in a 9-coordinate geometry to one Zr(1), three equivalent Zr(3), four equivalent Zr(2), and one Ge(2) atom. In the second Ge site, Ge(2) is bonded in a 9-coordinate geometry to two equivalent Zr(1), three equivalent Zr(2), three equivalent Zr(3), and one Ge(1) atom.
Zr5Ge4 crystallizes in the tetragonal P4_12_12 space group. There are three inequivalent Zr sites. In the first Zr site, Zr(1) is bonded to two equivalent Ge(1) and four equivalent Ge(2) atoms to form corner-sharing ZrGe6 octahedra. The corner-sharing octahedral tilt angles are 52°. Both Zr(1)-Ge(1) bond lengths are 2.90 Å. There are two shorter (2.78 Å) and two longer (2.81 Å) Zr(1)-Ge(2) bond lengths. In the second Zr site, Zr(2) is bonded in a 7-coordinate geometry to three equivalent Ge(2) and four equivalent Ge(1) atoms. There are a spread of Zr(2)-Ge(2) bond distances ranging from 2.85-3.15 Å. There are a spread of Zr(2)-Ge(1) bond distances ranging from 2.79-3.12 Å. In the third Zr site, Zr(3) is bonded in a 6-coordinate geometry to three equivalent Ge(1) and three equivalent Ge(2) atoms. There are a spread of Zr(3)-Ge(1) bond distances ranging from 2.66-2.86 Å. There are a spread of Zr(3)-Ge(2) bond distances ranging from 2.71-2.78 Å. There are two inequivalent Ge sites. In the first Ge site, Ge(1) is bonded in a 9-coordinate geometry to one Zr(1), three equivalent Zr(3), four equivalent Zr(2), and one Ge(2) atom. The Ge(1)-Ge(2) bond length is 2.71 Å. In the second Ge site, Ge(2) is bonded in a 9-coordinate geometry to two equivalent Zr(1), three equivalent Zr(2), three equivalent Zr(3), and one Ge(1) atom.