Ni2FeBO5 crystallizes in the orthorhombic Pbam space group. Fe(1) is bonded to one O(3), one O(4), two equivalent O(2), and two equivalent O(5) atoms to form FeO6 octahedra that share corners with two equivalent Ni(2)O6 octahedra, corners with two equivalent Ni(3)O6 octahedra,  an edgeedge with one Ni(2)O6 octahedra, edges with two equivalent Fe(1)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, and edges with two equivalent Ni(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 15-62°. There are three inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to two equivalent O(5) and four equivalent O(4) atoms to form NiO6 octahedra that share corners with two equivalent Ni(3)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, and edges with four equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles are 60°. In the second Ni site, Ni(2) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form NiO6 octahedra that share corners with four equivalent Fe(1)O6 octahedra, edges with two equivalent Fe(1)O6 octahedra, edges with two equivalent Ni(2)O6 octahedra, and edges with four equivalent Ni(3)O6 octahedra. The corner-sharing octahedral tilt angles are 15°. In the third Ni site, Ni(3) is bonded to one O(2), one O(5), two equivalent O(1), and two equivalent O(3) atoms to form NiO6 octahedra that share  a cornercorner with one Ni(1)O6 octahedra, corners with two equivalent Fe(1)O6 octahedra, edges with two equivalent Fe(1)O6 octahedra, edges with two equivalent Ni(2)O6 octahedra, and edges with two equivalent Ni(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 60-62°. B(1) is bonded in a trigonal planar geometry to one O(1), one O(3), and one O(4) atom. There are five inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Ni(2), two equivalent Ni(3), and one B(1) atom. In the second O site, O(2) is bonded to two equivalent Fe(1), one Ni(3), and two equivalent Ni(2) atoms to form OFe2Ni3 square pyramids that share corners with two equivalent O(2)Fe2Ni3 square pyramids, corners with three equivalent O(5)Fe2Ni2 tetrahedra, edges with three equivalent O(2)Fe2Ni3 square pyramids, and  an edgeedge with one O(5)Fe2Ni2 tetrahedra. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Fe(1), two equivalent Ni(3), and one B(1) atom. In the fourth O site, O(4) is bonded in a rectangular see-saw-like geometry to one Fe(1), two equivalent Ni(1), and one B(1) atom. In the fifth O site, O(5) is bonded to two equivalent Fe(1), one Ni(1), and one Ni(3) atom to form OFe2Ni2 tetrahedra that share corners with three equivalent O(2)Fe2Ni3 square pyramids, corners with three equivalent O(5)Fe2Ni2 tetrahedra, and  an edgeedge with one O(2)Fe2Ni3 square pyramid.
Ni2FeBO5 crystallizes in the orthorhombic Pbam space group. Fe(1) is bonded to one O(3), one O(4), two equivalent O(2), and two equivalent O(5) atoms to form FeO6 octahedra that share corners with two equivalent Ni(2)O6 octahedra, corners with two equivalent Ni(3)O6 octahedra,  an edgeedge with one Ni(2)O6 octahedra, edges with two equivalent Fe(1)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, and edges with two equivalent Ni(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 15-62°. The Fe(1)-O(3) bond length is 2.09 Å. The Fe(1)-O(4) bond length is 2.11 Å. Both Fe(1)-O(2) bond lengths are 2.08 Å. Both Fe(1)-O(5) bond lengths are 1.99 Å. There are three inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to two equivalent O(5) and four equivalent O(4) atoms to form NiO6 octahedra that share corners with two equivalent Ni(3)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, and edges with four equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles are 60°. Both Ni(1)-O(5) bond lengths are 2.03 Å. All Ni(1)-O(4) bond lengths are 2.13 Å. In the second Ni site, Ni(2) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form NiO6 octahedra that share corners with four equivalent Fe(1)O6 octahedra, edges with two equivalent Fe(1)O6 octahedra, edges with two equivalent Ni(2)O6 octahedra, and edges with four equivalent Ni(3)O6 octahedra. The corner-sharing octahedral tilt angles are 15°. Both Ni(2)-O(1) bond lengths are 2.10 Å. All Ni(2)-O(2) bond lengths are 2.10 Å. In the third Ni site, Ni(3) is bonded to one O(2), one O(5), two equivalent O(1), and two equivalent O(3) atoms to form NiO6 octahedra that share  a cornercorner with one Ni(1)O6 octahedra, corners with two equivalent Fe(1)O6 octahedra, edges with two equivalent Fe(1)O6 octahedra, edges with two equivalent Ni(2)O6 octahedra, and edges with two equivalent Ni(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 60-62°. The Ni(3)-O(2) bond length is 2.05 Å. The Ni(3)-O(5) bond length is 1.98 Å. Both Ni(3)-O(1) bond lengths are 2.13 Å. Both Ni(3)-O(3) bond lengths are 2.15 Å. B(1) is bonded in a trigonal planar geometry to one O(1), one O(3), and one O(4) atom. The B(1)-O(1) bond length is 1.38 Å. The B(1)-O(3) 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(1) is bonded in a 4-coordinate geometry to one Ni(2), two equivalent Ni(3), and one B(1) atom. In the second O site, O(2) is bonded to two equivalent Fe(1), one Ni(3), and two equivalent Ni(2) atoms to form OFe2Ni3 square pyramids that share corners with two equivalent O(2)Fe2Ni3 square pyramids, corners with three equivalent O(5)Fe2Ni2 tetrahedra, edges with three equivalent O(2)Fe2Ni3 square pyramids, and  an edgeedge with one O(5)Fe2Ni2 tetrahedra. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Fe(1), two equivalent Ni(3), and one B(1) atom. In the fourth O site, O(4) is bonded in a rectangular see-saw-like geometry to one Fe(1), two equivalent Ni(1), and one B(1) atom. In the fifth O site, O(5) is bonded to two equivalent Fe(1), one Ni(1), and one Ni(3) atom to form OFe2Ni2 tetrahedra that share corners with three equivalent O(2)Fe2Ni3 square pyramids, corners with three equivalent O(5)Fe2Ni2 tetrahedra, and  an edgeedge with one O(2)Fe2Ni3 square pyramid.