VNi5(BO5)2 crystallizes in the orthorhombic Pmc2_1 space group. V(1) is bonded to one O(4), one O(6), two equivalent O(10), and two equivalent O(8) atoms to form VO6 octahedra that share corners with two equivalent Ni(3)O6 octahedra, corners with two equivalent Ni(4)O6 octahedra,  an edgeedge with one Ni(4)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, and edges with two equivalent Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 16-62°. There are five inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one O(10), one O(9), two equivalent O(3), and two equivalent O(4) atoms to form NiO6 octahedra that share  a cornercorner with one Ni(2)O6 octahedra,  a cornercorner with one Ni(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, and edges with two equivalent Ni(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 58-64°. In the second Ni site, Ni(2) is bonded to one O(8), one O(9), two equivalent O(1), and two equivalent O(6) atoms to form NiO6 octahedra that share  a cornercorner with one Ni(1)O6 octahedra, corners with two equivalent Ni(5)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent Ni(2)O6 octahedra, and edges with two equivalent Ni(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 58-63°. In the third Ni site, Ni(3) is bonded to one O(10), one O(7), two equivalent O(2), and two equivalent O(5) atoms to form NiO6 octahedra that share  a cornercorner with one Ni(1)O6 octahedra, corners with two equivalent V(1)O6 octahedra, edges with two equivalent Ni(3)O6 octahedra, edges with two equivalent Ni(4)O6 octahedra, and edges with two equivalent Ni(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 62-64°. In the fourth Ni site, Ni(4) is bonded to one O(1), one O(2), two equivalent O(7), and two equivalent O(8) atoms to form NiO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent Ni(5)O6 octahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one Ni(5)O6 octahedra, edges with two equivalent Ni(2)O6 octahedra, edges with two equivalent Ni(3)O6 octahedra, and edges with two equivalent Ni(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 16-17°. In the fifth Ni site, Ni(5) is bonded to one O(3), one O(5), two equivalent O(7), and two equivalent O(9) atoms to form a mixture of edge and corner-sharing NiO6 octahedra. The corner-sharing octahedral tilt angles range from 17-63°. There are two inequivalent B sites. In the first B site, B(1) is bonded in a trigonal planar geometry to one O(1), one O(3), and one O(5) atom. In the second B site, B(2) is bonded in a trigonal planar geometry to one O(2), one O(4), and one O(6) atom. There are ten inequivalent O sites. In the first O site, O(9) is bonded to one Ni(1), one Ni(2), and two equivalent Ni(5) atoms to form ONi4 tetrahedra that share  a cornercorner with one O(8)V2Ni3 square pyramid, corners with two equivalent O(7)Ni5 square pyramids,  a cornercorner with one O(10)V2Ni2 tetrahedra, corners with two equivalent O(9)Ni4 tetrahedra, and  an edgeedge with one O(7)Ni5 square pyramid. In the second O site, O(10) is bonded to two equivalent V(1), one Ni(1), and one Ni(3) atom to form OV2Ni2 tetrahedra that share  a cornercorner with one O(7)Ni5 square pyramid, corners with two equivalent O(8)V2Ni3 square pyramids,  a cornercorner with one O(9)Ni4 tetrahedra, corners with two equivalent O(10)V2Ni2 tetrahedra, and  an edgeedge with one O(8)V2Ni3 square pyramid. In the third O site, O(1) is bonded in a 4-coordinate geometry to one Ni(4), two equivalent Ni(2), and one B(1) atom. In the fourth O site, O(2) is bonded in a rectangular see-saw-like geometry to one Ni(4), two equivalent Ni(3), and one B(2) atom. In the fifth O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Ni(5), two equivalent Ni(1), and one B(1) atom. In the sixth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one V(1), two equivalent Ni(1), and one B(2) atom. In the seventh O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one Ni(5), two equivalent Ni(3), and one B(1) atom. In the eighth O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to one V(1), two equivalent Ni(2), and one B(2) atom. In the ninth O site, O(7) is bonded to one Ni(3), two equivalent Ni(4), and two equivalent Ni(5) atoms to form ONi5 square pyramids that share corners with two equivalent O(8)V2Ni3 square pyramids,  a cornercorner with one O(10)V2Ni2 tetrahedra, corners with two equivalent O(9)Ni4 tetrahedra,  an edgeedge with one O(8)V2Ni3 square pyramid, edges with two equivalent O(7)Ni5 square pyramids, and  an edgeedge with one O(9)Ni4 tetrahedra. In the tenth O site, O(8) is bonded to two equivalent V(1), one Ni(2), and two equivalent Ni(4) atoms to form OV2Ni3 square pyramids that share corners with two equivalent O(7)Ni5 square pyramids,  a cornercorner with one O(9)Ni4 tetrahedra, corners with two equivalent O(10)V2Ni2 tetrahedra,  an edgeedge with one O(7)Ni5 square pyramid, edges with two equivalent O(8)V2Ni3 square pyramids, and  an edgeedge with one O(10)V2Ni2 tetrahedra.
VNi5(BO5)2 crystallizes in the orthorhombic Pmc2_1 space group. V(1) is bonded to one O(4), one O(6), two equivalent O(10), and two equivalent O(8) atoms to form VO6 octahedra that share corners with two equivalent Ni(3)O6 octahedra, corners with two equivalent Ni(4)O6 octahedra,  an edgeedge with one Ni(4)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, and edges with two equivalent Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 16-62°. The V(1)-O(4) bond length is 2.11 Å. The V(1)-O(6) bond length is 2.08 Å. Both V(1)-O(10) bond lengths are 1.94 Å. Both V(1)-O(8) bond lengths are 2.03 Å. There are five inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one O(10), one O(9), two equivalent O(3), and two equivalent O(4) atoms to form NiO6 octahedra that share  a cornercorner with one Ni(2)O6 octahedra,  a cornercorner with one Ni(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, and edges with two equivalent Ni(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 58-64°. The Ni(1)-O(10) bond length is 2.13 Å. The Ni(1)-O(9) bond length is 1.98 Å. Both Ni(1)-O(3) bond lengths are 2.07 Å. Both Ni(1)-O(4) bond lengths are 2.14 Å. In the second Ni site, Ni(2) is bonded to one O(8), one O(9), two equivalent O(1), and two equivalent O(6) atoms to form NiO6 octahedra that share  a cornercorner with one Ni(1)O6 octahedra, corners with two equivalent Ni(5)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent Ni(2)O6 octahedra, and edges with two equivalent Ni(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 58-63°. The Ni(2)-O(8) bond length is 2.10 Å. The Ni(2)-O(9) bond length is 1.93 Å. Both Ni(2)-O(1) bond lengths are 2.11 Å. Both Ni(2)-O(6) bond lengths are 2.19 Å. In the third Ni site, Ni(3) is bonded to one O(10), one O(7), two equivalent O(2), and two equivalent O(5) atoms to form NiO6 octahedra that share  a cornercorner with one Ni(1)O6 octahedra, corners with two equivalent V(1)O6 octahedra, edges with two equivalent Ni(3)O6 octahedra, edges with two equivalent Ni(4)O6 octahedra, and edges with two equivalent Ni(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 62-64°. The Ni(3)-O(10) bond length is 2.05 Å. The Ni(3)-O(7) bond length is 2.00 Å. Both Ni(3)-O(2) bond lengths are 2.13 Å. Both Ni(3)-O(5) bond lengths are 2.09 Å. In the fourth Ni site, Ni(4) is bonded to one O(1), one O(2), two equivalent O(7), and two equivalent O(8) atoms to form NiO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent Ni(5)O6 octahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one Ni(5)O6 octahedra, edges with two equivalent Ni(2)O6 octahedra, edges with two equivalent Ni(3)O6 octahedra, and edges with two equivalent Ni(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 16-17°. The Ni(4)-O(1) bond length is 2.08 Å. The Ni(4)-O(2) bond length is 2.12 Å. Both Ni(4)-O(7) bond lengths are 2.02 Å. Both Ni(4)-O(8) bond lengths are 2.16 Å. In the fifth Ni site, Ni(5) is bonded to one O(3), one O(5), two equivalent O(7), and two equivalent O(9) atoms to form a mixture of edge and corner-sharing NiO6 octahedra. The corner-sharing octahedral tilt angles range from 17-63°. The Ni(5)-O(3) bond length is 2.13 Å. The Ni(5)-O(5) bond length is 2.13 Å. Both Ni(5)-O(7) bond lengths are 2.08 Å. Both Ni(5)-O(9) bond lengths are 1.97 Å. There are two inequivalent B sites. In the first B site, B(1) is bonded in a trigonal planar geometry to one O(1), one O(3), and one O(5) atom. The B(1)-O(1) bond length is 1.40 Å. The B(1)-O(3) bond length is 1.38 Å. The B(1)-O(5) bond length is 1.38 Å. In the second B site, B(2) is bonded in a trigonal planar geometry to one O(2), one O(4), and one O(6) atom. The B(2)-O(2) bond length is 1.38 Å. The B(2)-O(4) bond length is 1.40 Å. The B(2)-O(6) bond length is 1.40 Å. There are ten inequivalent O sites. In the first O site, O(9) is bonded to one Ni(1), one Ni(2), and two equivalent Ni(5) atoms to form ONi4 tetrahedra that share  a cornercorner with one O(8)V2Ni3 square pyramid, corners with two equivalent O(7)Ni5 square pyramids,  a cornercorner with one O(10)V2Ni2 tetrahedra, corners with two equivalent O(9)Ni4 tetrahedra, and  an edgeedge with one O(7)Ni5 square pyramid. In the second O site, O(10) is bonded to two equivalent V(1), one Ni(1), and one Ni(3) atom to form OV2Ni2 tetrahedra that share  a cornercorner with one O(7)Ni5 square pyramid, corners with two equivalent O(8)V2Ni3 square pyramids,  a cornercorner with one O(9)Ni4 tetrahedra, corners with two equivalent O(10)V2Ni2 tetrahedra, and  an edgeedge with one O(8)V2Ni3 square pyramid. In the third O site, O(1) is bonded in a 4-coordinate geometry to one Ni(4), two equivalent Ni(2), and one B(1) atom. In the fourth O site, O(2) is bonded in a rectangular see-saw-like geometry to one Ni(4), two equivalent Ni(3), and one B(2) atom. In the fifth O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Ni(5), two equivalent Ni(1), and one B(1) atom. In the sixth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one V(1), two equivalent Ni(1), and one B(2) atom. In the seventh O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one Ni(5), two equivalent Ni(3), and one B(1) atom. In the eighth O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to one V(1), two equivalent Ni(2), and one B(2) atom. In the ninth O site, O(7) is bonded to one Ni(3), two equivalent Ni(4), and two equivalent Ni(5) atoms to form ONi5 square pyramids that share corners with two equivalent O(8)V2Ni3 square pyramids,  a cornercorner with one O(10)V2Ni2 tetrahedra, corners with two equivalent O(9)Ni4 tetrahedra,  an edgeedge with one O(8)V2Ni3 square pyramid, edges with two equivalent O(7)Ni5 square pyramids, and  an edgeedge with one O(9)Ni4 tetrahedra. In the tenth O site, O(8) is bonded to two equivalent V(1), one Ni(2), and two equivalent Ni(4) atoms to form OV2Ni3 square pyramids that share corners with two equivalent O(7)Ni5 square pyramids,  a cornercorner with one O(9)Ni4 tetrahedra, corners with two equivalent O(10)V2Ni2 tetrahedra,  an edgeedge with one O(7)Ni5 square pyramid, edges with two equivalent O(8)V2Ni3 square pyramids, and  an edgeedge with one O(10)V2Ni2 tetrahedra.