Ni3BO5 crystallizes in the orthorhombic Pbam space group. There are four inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form a mixture of corner and edge-sharing NiO6 octahedra. The corner-sharing octahedral tilt angles are 61°. In the second Ni site, Ni(2) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent O(4) atoms to form a mixture of corner and edge-sharing NiO6 octahedra. The corner-sharing octahedral tilt angles range from 17-62°. In the third Ni site, Ni(3) is bonded to two equivalent O(5) and four equivalent O(4) atoms to form a mixture of corner and edge-sharing NiO6 octahedra. The corner-sharing octahedral tilt angles are 17°. In the fourth Ni site, Ni(4) is bonded to one O(2), one O(4), two equivalent O(3), and two equivalent O(5) atoms to form a mixture of corner and edge-sharing NiO6 octahedra. The corner-sharing octahedral tilt angles range from 61-62°. B(1) is bonded in a trigonal planar geometry to one O(1), one O(3), and one O(5) atom. There are five inequivalent O sites. In the first O site, O(5) is bonded in a 4-coordinate geometry to one Ni(3), two equivalent Ni(4), and one B(1) atom. In the second O site, O(1) is bonded in a rectangular see-saw-like geometry to one Ni(2), two equivalent Ni(1), and one B(1) atom. In the third O site, O(2) is bonded to one Ni(1), one Ni(4), and two equivalent Ni(2) atoms to form ONi4 tetrahedra that share corners with three equivalent O(4)Ni5 square pyramids, corners with three equivalent O(2)Ni4 tetrahedra, and  an edgeedge with one O(4)Ni5 square pyramid. In the fourth O site, O(3) is bonded in a 4-coordinate geometry to one Ni(2), two equivalent Ni(4), and one B(1) atom. In the fifth O site, O(4) is bonded to one Ni(4), two equivalent Ni(2), and two equivalent Ni(3) atoms to form ONi5 square pyramids that share corners with two equivalent O(4)Ni5 square pyramids, corners with three equivalent O(2)Ni4 tetrahedra, edges with three equivalent O(4)Ni5 square pyramids, and  an edgeedge with one O(2)Ni4 tetrahedra.
Ni3BO5 crystallizes in the orthorhombic Pbam space group. There are four inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form a mixture of corner and edge-sharing NiO6 octahedra. The corner-sharing octahedral tilt angles are 61°. Both Ni(1)-O(2) bond lengths are 2.01 Å. All Ni(1)-O(1) bond lengths are 2.05 Å. In the second Ni site, Ni(2) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent O(4) atoms to form a mixture of corner and edge-sharing NiO6 octahedra. The corner-sharing octahedral tilt angles range from 17-62°. The Ni(2)-O(1) bond length is 2.06 Å. The Ni(2)-O(3) bond length is 2.08 Å. Both Ni(2)-O(2) bond lengths are 1.92 Å. Both Ni(2)-O(4) bond lengths are 2.01 Å. In the third Ni site, Ni(3) is bonded to two equivalent O(5) and four equivalent O(4) atoms to form a mixture of corner and edge-sharing NiO6 octahedra. The corner-sharing octahedral tilt angles are 17°. Both Ni(3)-O(5) bond lengths are 2.04 Å. All Ni(3)-O(4) bond lengths are 2.04 Å. In the fourth Ni site, Ni(4) is bonded to one O(2), one O(4), two equivalent O(3), and two equivalent O(5) atoms to form a mixture of corner and edge-sharing NiO6 octahedra. The corner-sharing octahedral tilt angles range from 61-62°. The Ni(4)-O(2) bond length is 1.93 Å. The Ni(4)-O(4) bond length is 2.00 Å. Both Ni(4)-O(3) bond lengths are 2.06 Å. Both Ni(4)-O(5) bond lengths are 2.08 Å. 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 1.37 Å. The B(1)-O(3) bond length is 1.38 Å. The B(1)-O(5) bond length is 1.38 Å. There are five inequivalent O sites. In the first O site, O(5) is bonded in a 4-coordinate geometry to one Ni(3), two equivalent Ni(4), and one B(1) atom. In the second O site, O(1) is bonded in a rectangular see-saw-like geometry to one Ni(2), two equivalent Ni(1), and one B(1) atom. In the third O site, O(2) is bonded to one Ni(1), one Ni(4), and two equivalent Ni(2) atoms to form ONi4 tetrahedra that share corners with three equivalent O(4)Ni5 square pyramids, corners with three equivalent O(2)Ni4 tetrahedra, and  an edgeedge with one O(4)Ni5 square pyramid. In the fourth O site, O(3) is bonded in a 4-coordinate geometry to one Ni(2), two equivalent Ni(4), and one B(1) atom. In the fifth O site, O(4) is bonded to one Ni(4), two equivalent Ni(2), and two equivalent Ni(3) atoms to form ONi5 square pyramids that share corners with two equivalent O(4)Ni5 square pyramids, corners with three equivalent O(2)Ni4 tetrahedra, edges with three equivalent O(4)Ni5 square pyramids, and  an edgeedge with one O(2)Ni4 tetrahedra.