V3BO5 crystallizes in the orthorhombic Pbam space group. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(3), one O(5), two equivalent O(2), and two equivalent O(4) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles are 63°. In the second V site, V(2) is bonded to two equivalent O(3) and four equivalent O(1) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles are 63°. In the third V site, V(3) is bonded to one O(1), one O(4), two equivalent O(3), and two equivalent O(5) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 17-63°. In the fourth V site, V(4) is bonded to two equivalent O(2) and four equivalent O(5) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles are 17°. B(1) is bonded in a trigonal planar geometry to one O(1), one O(2), and one O(4) atom. There are five inequivalent O sites. In the first O site, O(5) is bonded to one V(1), two equivalent V(3), and two equivalent V(4) atoms to form OV5 square pyramids that share corners with two equivalent O(5)V5 square pyramids, corners with three equivalent O(3)V4 tetrahedra, edges with three equivalent O(5)V5 square pyramids, and  an edgeedge with one O(3)V4 tetrahedra. In the second O site, O(1) is bonded in a rectangular see-saw-like geometry to one V(3), two equivalent V(2), and one B(1) atom. In the third O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one V(4), two equivalent V(1), and one B(1) atom. In the fourth O site, O(3) is bonded to one V(1), one V(2), and two equivalent V(3) atoms to form OV4 tetrahedra that share corners with three equivalent O(5)V5 square pyramids, corners with three equivalent O(3)V4 tetrahedra, and  an edgeedge with one O(5)V5 square pyramid. In the fifth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one V(3), two equivalent V(1), and one B(1) atom.
V3BO5 crystallizes in the orthorhombic Pbam space group. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(3), one O(5), two equivalent O(2), and two equivalent O(4) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles are 63°. The V(1)-O(3) bond length is 2.07 Å. The V(1)-O(5) bond length is 2.14 Å. Both V(1)-O(2) bond lengths are 2.21 Å. Both V(1)-O(4) bond lengths are 2.23 Å. In the second V site, V(2) is bonded to two equivalent O(3) and four equivalent O(1) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles are 63°. Both V(2)-O(3) bond lengths are 2.09 Å. All V(2)-O(1) bond lengths are 2.21 Å. In the third V site, V(3) is bonded to one O(1), one O(4), two equivalent O(3), and two equivalent O(5) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 17-63°. The V(3)-O(1) bond length is 2.18 Å. The V(3)-O(4) bond length is 2.18 Å. Both V(3)-O(3) bond lengths are 2.01 Å. Both V(3)-O(5) bond lengths are 2.12 Å. In the fourth V site, V(4) is bonded to two equivalent O(2) and four equivalent O(5) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles are 17°. Both V(4)-O(2) bond lengths are 2.19 Å. All V(4)-O(5) bond lengths are 2.14 Å. B(1) is bonded in a trigonal planar geometry to one O(1), one O(2), and one O(4) atom. The B(1)-O(1) bond length is 1.40 Å. The B(1)-O(2) bond length is 1.39 Å. The B(1)-O(4) bond length is 1.40 Å. There are five inequivalent O sites. In the first O site, O(5) is bonded to one V(1), two equivalent V(3), and two equivalent V(4) atoms to form OV5 square pyramids that share corners with two equivalent O(5)V5 square pyramids, corners with three equivalent O(3)V4 tetrahedra, edges with three equivalent O(5)V5 square pyramids, and  an edgeedge with one O(3)V4 tetrahedra. In the second O site, O(1) is bonded in a rectangular see-saw-like geometry to one V(3), two equivalent V(2), and one B(1) atom. In the third O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one V(4), two equivalent V(1), and one B(1) atom. In the fourth O site, O(3) is bonded to one V(1), one V(2), and two equivalent V(3) atoms to form OV4 tetrahedra that share corners with three equivalent O(5)V5 square pyramids, corners with three equivalent O(3)V4 tetrahedra, and  an edgeedge with one O(5)V5 square pyramid. In the fifth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one V(3), two equivalent V(1), and one B(1) atom.