Zr5Si3 crystallizes in the monoclinic Pm space group. There are five inequivalent Zr sites. In the first Zr site, Zr(1) is bonded in a 6-coordinate geometry to two equivalent Si(1), two equivalent Si(2), and two equivalent Si(3) atoms. In the second Zr site, Zr(2) is bonded in a 4-coordinate geometry to two equivalent Si(2) and two equivalent Si(3) atoms. In the third Zr site, Zr(3) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Si(1) and two equivalent Si(3) atoms. In the fourth Zr site, Zr(4) is bonded in a 4-coordinate geometry to two equivalent Si(1) and two equivalent Si(2) atoms. In the fifth Zr site, Zr(5) is bonded in a distorted T-shaped geometry to one Si(1), one Si(2), and one Si(3) atom. There are three inequivalent Si sites. In the first Si site, Si(1) is bonded to one Zr(5), two equivalent Zr(1), two equivalent Zr(3), and two equivalent Zr(4) atoms to form distorted face-sharing SiZr7 pentagonal bipyramids. In the second Si site, Si(2) is bonded in a 8-coordinate geometry to one Zr(5), two equivalent Zr(1), two equivalent Zr(2), two equivalent Zr(4), and one Si(3) atom. In the third Si site, Si(3) is bonded in a 8-coordinate geometry to one Zr(5), two equivalent Zr(1), two equivalent Zr(2), two equivalent Zr(3), and one Si(2) atom.
Zr5Si3 crystallizes in the monoclinic Pm space group. There are five inequivalent Zr sites. In the first Zr site, Zr(1) is bonded in a 6-coordinate geometry to two equivalent Si(1), two equivalent Si(2), and two equivalent Si(3) atoms. Both Zr(1)-Si(1) bond lengths are 2.73 Å. Both Zr(1)-Si(2) bond lengths are 2.88 Å. Both Zr(1)-Si(3) bond lengths are 2.74 Å. In the second Zr site, Zr(2) is bonded in a 4-coordinate geometry to two equivalent Si(2) and two equivalent Si(3) atoms. Both Zr(2)-Si(2) bond lengths are 2.79 Å. Both Zr(2)-Si(3) bond lengths are 2.77 Å. In the third Zr site, Zr(3) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Si(1) and two equivalent Si(3) atoms. Both Zr(3)-Si(1) bond lengths are 2.74 Å. Both Zr(3)-Si(3) bond lengths are 2.64 Å. In the fourth Zr site, Zr(4) is bonded in a 4-coordinate geometry to two equivalent Si(1) and two equivalent Si(2) atoms. Both Zr(4)-Si(1) bond lengths are 2.70 Å. Both Zr(4)-Si(2) bond lengths are 2.71 Å. In the fifth Zr site, Zr(5) is bonded in a distorted T-shaped geometry to one Si(1), one Si(2), and one Si(3) atom. The Zr(5)-Si(1) bond length is 2.77 Å. The Zr(5)-Si(2) bond length is 2.80 Å. The Zr(5)-Si(3) bond length is 2.79 Å. There are three inequivalent Si sites. In the first Si site, Si(1) is bonded to one Zr(5), two equivalent Zr(1), two equivalent Zr(3), and two equivalent Zr(4) atoms to form distorted face-sharing SiZr7 pentagonal bipyramids. In the second Si site, Si(2) is bonded in a 8-coordinate geometry to one Zr(5), two equivalent Zr(1), two equivalent Zr(2), two equivalent Zr(4), and one Si(3) atom. The Si(2)-Si(3) bond length is 2.36 Å. In the third Si site, Si(3) is bonded in a 8-coordinate geometry to one Zr(5), two equivalent Zr(1), two equivalent Zr(2), two equivalent Zr(3), and one Si(2) atom.