Hf3Si2 crystallizes in the tetragonal P4/mbm space group. There are two inequivalent Hf sites. In the first Hf site, Hf(1) is bonded in a 6-coordinate geometry to six equivalent Si(1) atoms. In the second Hf site, Hf(2) is bonded in a square co-planar geometry to four equivalent Si(1) atoms. Si(1) is bonded in a 9-coordinate geometry to two equivalent Hf(2), six equivalent Hf(1), and one Si(1) atom.
Hf3Si2 crystallizes in the tetragonal P4/mbm space group. There are two inequivalent Hf sites. In the first Hf site, Hf(1) is bonded in a 6-coordinate geometry to six equivalent Si(1) atoms. There are two shorter (2.72 Å) and four longer (2.79 Å) Hf(1)-Si(1) bond lengths. In the second Hf site, Hf(2) is bonded in a square co-planar geometry to four equivalent Si(1) atoms. All Hf(2)-Si(1) bond lengths are 2.77 Å. Si(1) is bonded in a 9-coordinate geometry to two equivalent Hf(2), six equivalent Hf(1), and one Si(1) atom. The Si(1)-Si(1) bond length is 2.44 Å.