V3B4 crystallizes in the orthorhombic Immm space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to four equivalent B(1) and eight equivalent B(2) atoms to form a mixture of face and edge-sharing VB12 cuboctahedra. In the second V site, V(2) is bonded in a 7-coordinate geometry to two equivalent B(2) and five equivalent B(1) atoms. There are two inequivalent B sites. In the first B site, B(1) is bonded in a 9-coordinate geometry to two equivalent V(1), five equivalent V(2), and two equivalent B(2) atoms. In the second B site, B(2) is bonded in a 9-coordinate geometry to two equivalent V(2), four equivalent V(1), one B(2), and two equivalent B(1) atoms.
V3B4 crystallizes in the orthorhombic Immm space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to four equivalent B(1) and eight equivalent B(2) atoms to form a mixture of face and edge-sharing VB12 cuboctahedra. All V(1)-B(1) bond lengths are 2.35 Å. All V(1)-B(2) bond lengths are 2.29 Å. In the second V site, V(2) is bonded in a 7-coordinate geometry to two equivalent B(2) and five equivalent B(1) atoms. Both V(2)-B(2) bond lengths are 2.21 Å. There are four shorter (2.23 Å) and one longer (2.31 Å) V(2)-B(1) bond length. There are two inequivalent B sites. In the first B site, B(1) is bonded in a 9-coordinate geometry to two equivalent V(1), five equivalent V(2), 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(2), four equivalent V(1), one B(2), and two equivalent B(1) atoms. The B(2)-B(2) bond length is 1.73 Å.