Hf2Cr4Si5 crystallizes in the orthorhombic Ibam space group. Hf(1) is bonded in a 7-coordinate geometry to one Si(3), two equivalent Si(2), and four equivalent Si(1) atoms. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded in a 6-coordinate geometry to two equivalent Si(3) and four equivalent Si(1) atoms. In the second Cr site, Cr(2) is bonded in a 5-coordinate geometry to one Si(1), two equivalent Si(2), and four equivalent Si(3) atoms. There are three inequivalent Si sites. In the first Si site, Si(1) is bonded in a 9-coordinate geometry to four equivalent Hf(1), one Cr(2), and four equivalent Cr(1) atoms. In the second Si site, Si(2) is bonded in a 10-coordinate geometry to four equivalent Hf(1), four equivalent Cr(2), and two equivalent Si(2) atoms. In the third Si site, Si(3) is bonded in a 10-coordinate geometry to one Hf(1), two equivalent Cr(1), four equivalent Cr(2), and three equivalent Si(3) atoms.
Hf2Cr4Si5 crystallizes in the orthorhombic Ibam space group. Hf(1) is bonded in a 7-coordinate geometry to one Si(3), two equivalent Si(2), and four equivalent Si(1) atoms. The Hf(1)-Si(3) bond length is 2.61 Å. Both Hf(1)-Si(2) bond lengths are 2.72 Å. There are a spread of Hf(1)-Si(1) bond distances ranging from 2.68-2.77 Å. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded in a 6-coordinate geometry to two equivalent Si(3) and four equivalent Si(1) atoms. Both Cr(1)-Si(3) bond lengths are 2.44 Å. All Cr(1)-Si(1) bond lengths are 2.52 Å. In the second Cr site, Cr(2) is bonded in a 5-coordinate geometry to one Si(1), two equivalent Si(2), and four equivalent Si(3) atoms. The Cr(2)-Si(1) bond length is 2.39 Å. Both Cr(2)-Si(2) bond lengths are 2.46 Å. There are a spread of Cr(2)-Si(3) bond distances ranging from 2.41-2.77 Å. There are three inequivalent Si sites. In the first Si site, Si(1) is bonded in a 9-coordinate geometry to four equivalent Hf(1), one Cr(2), and four equivalent Cr(1) atoms. In the second Si site, Si(2) is bonded in a 10-coordinate geometry to four equivalent Hf(1), four equivalent Cr(2), and two equivalent Si(2) atoms. Both Si(2)-Si(2) bond lengths are 2.44 Å. In the third Si site, Si(3) is bonded in a 10-coordinate geometry to one Hf(1), two equivalent Cr(1), four equivalent Cr(2), and three equivalent Si(3) atoms. There is one shorter (2.32 Å) and two longer (2.68 Å) Si(3)-Si(3) bond lengths.