SmVSb3 crystallizes in the orthorhombic Pbcm space group. Sm(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 face, corner, and edge-sharing VSb6 octahedra. The corner-sharing octahedral tilt angles are 47°. There are three inequivalent Sb sites. In the first Sb site, Sb(1) is bonded in a 8-coordinate geometry to four equivalent Sm(1) and four equivalent Sb(1) atoms. In the second Sb site, Sb(2) is bonded in a 5-coordinate geometry to one Sm(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 Sm(1), two equivalent V(1), and one Sb(2) atom.
SmVSb3 crystallizes in the orthorhombic Pbcm space group. Sm(1) is bonded in a 9-coordinate geometry to one Sb(2), four equivalent Sb(1), and four equivalent Sb(3) atoms. The Sm(1)-Sb(2) bond length is 3.26 Å. All Sm(1)-Sb(1) bond lengths are 3.31 Å. There are a spread of Sm(1)-Sb(3) bond distances ranging from 3.23-3.38 Å. V(1) is bonded to two equivalent Sb(3) and four equivalent Sb(2) atoms to form a mixture of distorted face, corner, and edge-sharing VSb6 octahedra. The corner-sharing octahedral tilt angles are 47°. Both V(1)-Sb(3) bond lengths are 2.74 Å. There are two shorter (2.71 Å) and two longer (2.74 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 Sm(1) and four equivalent Sb(1) atoms. There are two shorter (3.02 Å) and two longer (3.14 Å) Sb(1)-Sb(1) bond lengths. In the second Sb site, Sb(2) is bonded in a 5-coordinate geometry to one Sm(1), four equivalent V(1), and one Sb(3) atom. The Sb(2)-Sb(3) bond length is 3.19 Å. In the third Sb site, Sb(3) is bonded in a 7-coordinate geometry to four equivalent Sm(1), two equivalent V(1), and one Sb(2) atom.