V5SiB2 crystallizes in the tetragonal I4/mcm space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to three equivalent B(1) and two equivalent Si(1) atoms to form a mixture of distorted edge, face, and corner-sharing VSi2B3 trigonal bipyramids. In the second V site, V(2) is bonded in a distorted square co-planar geometry to four equivalent B(1) and two equivalent Si(1) atoms. B(1) is bonded in a 9-coordinate geometry to two equivalent V(2), six equivalent V(1), and one B(1) atom. Si(1) is bonded in a 10-coordinate geometry to two equivalent V(2) and eight equivalent V(1) atoms.
V5SiB2 crystallizes in the tetragonal I4/mcm space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to three equivalent B(1) and two equivalent Si(1) atoms to form a mixture of distorted edge, face, and corner-sharing VSi2B3 trigonal bipyramids. There are two shorter (2.22 Å) and one longer (2.29 Å) V(1)-B(1) bond length. Both V(1)-Si(1) bond lengths are 2.46 Å. In the second V site, V(2) is bonded in a distorted square co-planar geometry to four equivalent B(1) and two equivalent Si(1) atoms. All V(2)-B(1) bond lengths are 2.31 Å. Both V(2)-Si(1) bond lengths are 2.68 Å. B(1) is bonded in a 9-coordinate geometry to two equivalent V(2), six equivalent V(1), and one B(1) atom. The B(1)-B(1) bond length is 1.88 Å. Si(1) is bonded in a 10-coordinate geometry to two equivalent V(2) and eight equivalent V(1) atoms.