Ni2BBi(PO5)2 crystallizes in the monoclinic P2_1/m space group. Ni(1) is bonded to one O(1), one O(2), one O(4), one O(5), and two equivalent O(6) atoms to form distorted NiO6 octahedra that share corners with two equivalent B(1)O4 tetrahedra, corners with four equivalent P(1)O4 tetrahedra, edges with two equivalent Ni(1)O6 octahedra, and edges with two equivalent Bi(1)O6 pentagonal pyramids. B(1) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form BO4 tetrahedra that share corners with four equivalent Ni(1)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, and  an edgeedge with one Bi(1)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 54-57°. Bi(1) is bonded to one O(1), one O(2), two equivalent O(4), and two equivalent O(5) atoms to form distorted BiO6 pentagonal pyramids that share corners with four equivalent P(1)O4 tetrahedra, edges with four equivalent Ni(1)O6 octahedra, and  an edgeedge with one B(1)O4 tetrahedra. P(1) is bonded to one O(3), one O(4), one O(5), and one O(6) atom to form PO4 tetrahedra that share corners with four equivalent Ni(1)O6 octahedra, corners with two equivalent Bi(1)O6 pentagonal pyramids, and  a cornercorner with one B(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 45-56°. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to two equivalent Ni(1), one B(1), and one Bi(1) atom. In the second O site, O(2) is bonded in a distorted single-bond geometry to two equivalent Ni(1), one B(1), and one Bi(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one B(1) and one P(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Ni(1), one Bi(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Ni(1), one Bi(1), and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to two equivalent Ni(1) and one P(1) atom.
Ni2BBi(PO5)2 crystallizes in the monoclinic P2_1/m space group. Ni(1) is bonded to one O(1), one O(2), one O(4), one O(5), and two equivalent O(6) atoms to form distorted NiO6 octahedra that share corners with two equivalent B(1)O4 tetrahedra, corners with four equivalent P(1)O4 tetrahedra, edges with two equivalent Ni(1)O6 octahedra, and edges with two equivalent Bi(1)O6 pentagonal pyramids. The Ni(1)-O(1) bond length is 2.06 Å. The Ni(1)-O(2) bond length is 2.23 Å. The Ni(1)-O(4) bond length is 2.12 Å. The Ni(1)-O(5) bond length is 2.17 Å. There is one shorter (2.07 Å) and one longer (2.11 Å) Ni(1)-O(6) bond length. B(1) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form BO4 tetrahedra that share corners with four equivalent Ni(1)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, and  an edgeedge with one Bi(1)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 54-57°. The B(1)-O(1) bond length is 1.48 Å. The B(1)-O(2) bond length is 1.49 Å. Both B(1)-O(3) bond lengths are 1.48 Å. Bi(1) is bonded to one O(1), one O(2), two equivalent O(4), and two equivalent O(5) atoms to form distorted BiO6 pentagonal pyramids that share corners with four equivalent P(1)O4 tetrahedra, edges with four equivalent Ni(1)O6 octahedra, and  an edgeedge with one B(1)O4 tetrahedra. The Bi(1)-O(1) bond length is 2.35 Å. The Bi(1)-O(2) bond length is 2.17 Å. Both Bi(1)-O(4) bond lengths are 2.41 Å. Both Bi(1)-O(5) bond lengths are 2.48 Å. P(1) is bonded to one O(3), one O(4), one O(5), and one O(6) atom to form PO4 tetrahedra that share corners with four equivalent Ni(1)O6 octahedra, corners with two equivalent Bi(1)O6 pentagonal pyramids, and  a cornercorner with one B(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 45-56°. The P(1)-O(3) bond length is 1.56 Å. The P(1)-O(4) bond length is 1.56 Å. The P(1)-O(5) bond length is 1.54 Å. The P(1)-O(6) bond length is 1.55 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to two equivalent Ni(1), one B(1), and one Bi(1) atom. In the second O site, O(2) is bonded in a distorted single-bond geometry to two equivalent Ni(1), one B(1), and one Bi(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one B(1) and one P(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Ni(1), one Bi(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Ni(1), one Bi(1), and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to two equivalent Ni(1) and one P(1) atom.