Ni(PO3)3 crystallizes in the orthorhombic Pbcm space group. Ni(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form NiO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra and corners with four equivalent P(2)O4 tetrahedra. There are two inequivalent P sites. In the first P site, P(1) is bonded to two equivalent O(1) and two equivalent O(5) atoms to form PO4 tetrahedra that share corners with two equivalent Ni(1)O6 octahedra and corners with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 46°. In the second P site, P(2) is bonded to one O(2), one O(3), one O(4), and one O(5) atom to form PO4 tetrahedra that share corners with two equivalent Ni(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 45-51°. There are five inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 120 degrees geometry to one Ni(1) and one P(1) atom. In the second O site, O(2) is bonded in a bent 120 degrees geometry to one Ni(1) and one P(2) atom. In the third O site, O(3) is bonded in a distorted bent 150 degrees geometry to one Ni(1) and one P(2) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to two equivalent P(2) atoms. In the fifth O site, O(5) is bonded in a bent 120 degrees geometry to one P(1) and one P(2) atom.
Ni(PO3)3 crystallizes in the orthorhombic Pbcm space group. Ni(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form NiO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra and corners with four equivalent P(2)O4 tetrahedra. Both Ni(1)-O(1) bond lengths are 1.97 Å. Both Ni(1)-O(2) bond lengths are 2.03 Å. Both Ni(1)-O(3) bond lengths are 1.95 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to two equivalent O(1) and two equivalent O(5) atoms to form PO4 tetrahedra that share corners with two equivalent Ni(1)O6 octahedra and corners with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 46°. Both P(1)-O(1) bond lengths are 1.50 Å. Both P(1)-O(5) bond lengths are 1.60 Å. In the second P site, P(2) is bonded to one O(2), one O(3), one O(4), and one O(5) atom to form PO4 tetrahedra that share corners with two equivalent Ni(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 45-51°. The P(2)-O(2) bond length is 1.50 Å. The P(2)-O(3) bond length is 1.51 Å. The P(2)-O(4) bond length is 1.59 Å. The P(2)-O(5) bond length is 1.61 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 120 degrees geometry to one Ni(1) and one P(1) atom. In the second O site, O(2) is bonded in a bent 120 degrees geometry to one Ni(1) and one P(2) atom. In the third O site, O(3) is bonded in a distorted bent 150 degrees geometry to one Ni(1) and one P(2) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to two equivalent P(2) atoms. In the fifth O site, O(5) is bonded in a bent 120 degrees geometry to one P(1) and one P(2) atom.