V6Si5 crystallizes in the orthorhombic Ibam space group. There are three inequivalent V sites. In the first V site, V(1) is bonded in a 8-coordinate geometry to two equivalent V(1), two equivalent Si(3), and four equivalent Si(2) atoms. In the second V site, V(2) is bonded to one Si(3), two equivalent Si(1), and four equivalent Si(2) atoms to form a mixture of distorted edge, face, and corner-sharing VSi7 pentagonal bipyramids. In the third V site, V(3) is bonded in a 7-coordinate geometry to one Si(2), two equivalent Si(1), and four equivalent Si(3) atoms. There are three inequivalent Si sites. In the first Si site, Si(1) is bonded in a 10-coordinate geometry to four equivalent V(2), four equivalent V(3), and two equivalent Si(1) atoms. In the second Si site, Si(2) is bonded in a 9-coordinate geometry to one V(3), four equivalent V(1), and four equivalent V(2) atoms. In the third Si site, Si(3) is bonded in a 10-coordinate geometry to one V(2), two equivalent V(1), four equivalent V(3), and three equivalent Si(3) atoms.
V6Si5 crystallizes in the orthorhombic Ibam space group. There are three inequivalent V sites. In the first V site, V(1) is bonded in a 8-coordinate geometry to two equivalent V(1), two equivalent Si(3), and four equivalent Si(2) atoms. Both V(1)-V(1) bond lengths are 2.40 Å. Both V(1)-Si(3) bond lengths are 2.43 Å. There are two shorter (2.46 Å) and two longer (2.55 Å) V(1)-Si(2) bond lengths. In the second V site, V(2) is bonded to one Si(3), two equivalent Si(1), and four equivalent Si(2) atoms to form a mixture of distorted edge, face, and corner-sharing VSi7 pentagonal bipyramids. The V(2)-Si(3) bond length is 2.54 Å. Both V(2)-Si(1) bond lengths are 2.71 Å. There are a spread of V(2)-Si(2) bond distances ranging from 2.61-2.73 Å. In the third V site, V(3) is bonded in a 7-coordinate geometry to one Si(2), two equivalent Si(1), and four equivalent Si(3) atoms. The V(3)-Si(2) bond length is 2.39 Å. Both V(3)-Si(1) bond lengths are 2.46 Å. There are a spread of V(3)-Si(3) bond distances ranging from 2.35-2.67 Å. There are three inequivalent Si sites. In the first Si site, Si(1) is bonded in a 10-coordinate geometry to four equivalent V(2), four equivalent V(3), and two equivalent Si(1) atoms. Both Si(1)-Si(1) bond lengths are 2.40 Å. In the second Si site, Si(2) is bonded in a 9-coordinate geometry to one V(3), four equivalent V(1), and four equivalent V(2) atoms. In the third Si site, Si(3) is bonded in a 10-coordinate geometry to one V(2), two equivalent V(1), four equivalent V(3), and three equivalent Si(3) atoms. There is one shorter (2.41 Å) and two longer (2.75 Å) Si(3)-Si(3) bond lengths.