V2B3 crystallizes in the orthorhombic Cmcm space group. There are two inequivalent V sites. In the first V site, V(1) is bonded in a 7-coordinate geometry to two equivalent B(2) and five equivalent B(1) atoms. In the second V site, V(2) is bonded to two equivalent B(1), four equivalent B(2), and six equivalent B(3) atoms to form a mixture of face and edge-sharing VB12 cuboctahedra. There are three inequivalent B sites. In the first B site, B(1) is bonded in a 9-coordinate geometry to two equivalent V(2), five equivalent V(1), and two equivalent B(2) atoms. In the second B site, B(2) is bonded in a 9-coordinate geometry to two equivalent V(1), four equivalent V(2), one B(3), and two equivalent B(1) atoms. In the third B site, B(3) is bonded in a 9-coordinate geometry to six equivalent V(2), one B(2), and two equivalent B(3) atoms.
V2B3 crystallizes in the orthorhombic Cmcm space group. There are two inequivalent V sites. In the first V site, V(1) is bonded in a 7-coordinate geometry to two equivalent B(2) and five equivalent B(1) atoms. Both V(1)-B(2) bond lengths are 2.21 Å. There are four shorter (2.22 Å) and one longer (2.31 Å) V(1)-B(1) bond length. In the second V site, V(2) is bonded to two equivalent B(1), four equivalent B(2), and six equivalent B(3) atoms to form a mixture of face and edge-sharing VB12 cuboctahedra. Both V(2)-B(1) bond lengths are 2.35 Å. All V(2)-B(2) bond lengths are 2.29 Å. There are four shorter (2.29 Å) and two longer (2.30 Å) V(2)-B(3) bond lengths. There are three inequivalent B sites. In the first B site, B(1) is bonded in a 9-coordinate geometry to two equivalent V(2), five equivalent V(1), and two equivalent B(2) atoms. Both B(1)-B(2) bond lengths are 1.76 Å. In the second B site, B(2) is bonded in a 9-coordinate geometry to two equivalent V(1), four equivalent V(2), one B(3), and two equivalent B(1) atoms. The B(2)-B(3) bond length is 1.73 Å. In the third B site, B(3) is bonded in a 9-coordinate geometry to six equivalent V(2), one B(2), and two equivalent B(3) atoms. Both B(3)-B(3) bond lengths are 1.72 Å.