LaVSb3 crystallizes in the orthorhombic Pbcm space group. La(1) is bonded in a 9-coordinate geometry to one Sb(2), four equivalent Sb(1), and four equivalent Sb(3) atoms. V(1) is bonded to two equivalent Sb(3) and four equivalent Sb(2) atoms to form a mixture of distorted corner, edge, and face-sharing VSb6 octahedra. The corner-sharing octahedral tilt angles are 46°. There are three inequivalent Sb sites. In the first Sb site, Sb(1) is bonded in a 8-coordinate geometry to four equivalent La(1) and four equivalent Sb(1) atoms. In the second Sb site, Sb(2) is bonded in a 6-coordinate geometry to one La(1), four equivalent V(1), and one Sb(3) atom. In the third Sb site, Sb(3) is bonded in a 7-coordinate geometry to four equivalent La(1), two equivalent V(1), and one Sb(2) atom.
LaVSb3 crystallizes in the orthorhombic Pbcm space group. La(1) is bonded in a 9-coordinate geometry to one Sb(2), four equivalent Sb(1), and four equivalent Sb(3) atoms. The La(1)-Sb(2) bond length is 3.35 Å. There are two shorter (3.38 Å) and two longer (3.39 Å) La(1)-Sb(1) bond lengths. There are a spread of La(1)-Sb(3) bond distances ranging from 3.32-3.41 Å. V(1) is bonded to two equivalent Sb(3) and four equivalent Sb(2) atoms to form a mixture of distorted corner, edge, and face-sharing VSb6 octahedra. The corner-sharing octahedral tilt angles are 46°. Both V(1)-Sb(3) bond lengths are 2.75 Å. There are two shorter (2.73 Å) and two longer (2.76 Å) V(1)-Sb(2) bond lengths. There are three inequivalent Sb sites. In the first Sb site, Sb(1) is bonded in a 8-coordinate geometry to four equivalent La(1) and four equivalent Sb(1) atoms. There are two shorter (3.08 Å) and two longer (3.16 Å) Sb(1)-Sb(1) bond lengths. In the second Sb site, Sb(2) is bonded in a 6-coordinate geometry to one La(1), four equivalent V(1), and one Sb(3) atom. The Sb(2)-Sb(3) bond length is 3.24 Å. In the third Sb site, Sb(3) is bonded in a 7-coordinate geometry to four equivalent La(1), two equivalent V(1), and one Sb(2) atom.