W5Si3 crystallizes in the tetragonal I4/mcm space group. There are two inequivalent W sites. In the first W site, W(1) is bonded in a 6-coordinate geometry to two equivalent Si(1) and four equivalent Si(2) atoms. In the second W site, W(2) is bonded in a 6-coordinate geometry to two equivalent W(2) and four equivalent Si(2) atoms. There are two inequivalent Si sites. In the first Si site, Si(1) is bonded in a 10-coordinate geometry to eight equivalent W(1) and two equivalent Si(1) atoms. In the second Si site, Si(2) is bonded in a 10-coordinate geometry to two equivalent W(2) and eight equivalent W(1) atoms.
W5Si3 crystallizes in the tetragonal I4/mcm space group. There are two inequivalent W sites. In the first W site, W(1) is bonded in a 6-coordinate geometry to two equivalent Si(1) and four equivalent Si(2) atoms. Both W(1)-Si(1) bond lengths are 2.59 Å. There are a spread of W(1)-Si(2) bond distances ranging from 2.53-2.83 Å. In the second W site, W(2) is bonded in a 6-coordinate geometry to two equivalent W(2) and four equivalent Si(2) atoms. Both W(2)-W(2) bond lengths are 2.47 Å. All W(2)-Si(2) bond lengths are 2.60 Å. There are two inequivalent Si sites. In the first Si site, Si(1) is bonded in a 10-coordinate geometry to eight equivalent W(1) and two equivalent Si(1) atoms. Both Si(1)-Si(1) bond lengths are 2.47 Å. In the second Si site, Si(2) is bonded in a 10-coordinate geometry to two equivalent W(2) and eight equivalent W(1) atoms.