Li2Ni(PO3)4 crystallizes in the monoclinic Cc space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one O(3), one O(5), one O(7), and one O(8) atom. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(10), one O(4), one O(5), and one O(9) atom. Ni(1) is bonded to one O(1), one O(12), one O(3), one O(4), one O(8), and one O(9) atom to form NiO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(4)O4 tetrahedra. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), one O(6), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Ni(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 50-59°. In the second P site, P(2) is bonded to one O(10), one O(2), one O(4), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one Ni(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 44°. In the third P site, P(3) is bonded to one O(10), one O(11), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Ni(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles are 45°. In the fourth P site, P(4) is bonded to one O(11), one O(12), one O(3), and one O(6) 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(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 50-58°. There are twelve 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 P(1) and one P(2) atom. In the third O site, O(3) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Ni(1), and one P(4) atom. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one Li(2), one Ni(1), and one P(2) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Li(1), one Li(2), and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted bent 120 degrees geometry to one P(1) and one P(4) atom. In the seventh O site, O(7) is bonded in a bent 120 degrees geometry to one Li(1) and one P(3) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Li(1), one Ni(1), and one P(3) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Li(2), one Ni(1), and one P(1) atom. In the tenth O site, O(10) is bonded in a distorted bent 120 degrees geometry to one Li(2), one P(2), and one P(3) atom. In the eleventh O site, O(11) is bonded in a bent 150 degrees geometry to one P(3) and one P(4) atom. In the twelfth O site, O(12) is bonded in a distorted bent 120 degrees geometry to one Ni(1) and one P(4) atom.
Li2Ni(PO3)4 crystallizes in the monoclinic Cc space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one O(3), one O(5), one O(7), and one O(8) atom. The Li(1)-O(3) bond length is 2.53 Å. The Li(1)-O(5) bond length is 1.97 Å. The Li(1)-O(7) bond length is 2.01 Å. The Li(1)-O(8) bond length is 2.50 Å. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(10), one O(4), one O(5), and one O(9) atom. The Li(2)-O(10) bond length is 2.64 Å. The Li(2)-O(4) bond length is 2.41 Å. The Li(2)-O(5) bond length is 2.26 Å. The Li(2)-O(9) bond length is 2.26 Å. Ni(1) is bonded to one O(1), one O(12), one O(3), one O(4), one O(8), and one O(9) atom to form NiO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(4)O4 tetrahedra. The Ni(1)-O(1) bond length is 2.03 Å. The Ni(1)-O(12) bond length is 2.03 Å. The Ni(1)-O(3) bond length is 2.25 Å. The Ni(1)-O(4) bond length is 2.01 Å. The Ni(1)-O(8) bond length is 2.02 Å. The Ni(1)-O(9) bond length is 2.26 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), one O(6), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Ni(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 50-59°. The P(1)-O(1) bond length is 1.49 Å. The P(1)-O(2) bond length is 1.61 Å. The P(1)-O(6) bond length is 1.61 Å. The P(1)-O(9) bond length is 1.52 Å. In the second P site, P(2) is bonded to one O(10), one O(2), one O(4), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one Ni(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 44°. The P(2)-O(10) bond length is 1.63 Å. The P(2)-O(2) bond length is 1.60 Å. The P(2)-O(4) bond length is 1.51 Å. The P(2)-O(5) bond length is 1.49 Å. In the third P site, P(3) is bonded to one O(10), one O(11), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Ni(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles are 45°. The P(3)-O(10) bond length is 1.65 Å. The P(3)-O(11) bond length is 1.61 Å. The P(3)-O(7) bond length is 1.48 Å. The P(3)-O(8) bond length is 1.51 Å. In the fourth P site, P(4) is bonded to one O(11), one O(12), one O(3), and one O(6) 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(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 50-58°. The P(4)-O(11) bond length is 1.62 Å. The P(4)-O(12) bond length is 1.50 Å. The P(4)-O(3) bond length is 1.51 Å. The P(4)-O(6) bond length is 1.62 Å. There are twelve 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 P(1) and one P(2) atom. In the third O site, O(3) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Ni(1), and one P(4) atom. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one Li(2), one Ni(1), and one P(2) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Li(1), one Li(2), and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted bent 120 degrees geometry to one P(1) and one P(4) atom. In the seventh O site, O(7) is bonded in a bent 120 degrees geometry to one Li(1) and one P(3) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Li(1), one Ni(1), and one P(3) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Li(2), one Ni(1), and one P(1) atom. In the tenth O site, O(10) is bonded in a distorted bent 120 degrees geometry to one Li(2), one P(2), and one P(3) atom. In the eleventh O site, O(11) is bonded in a bent 150 degrees geometry to one P(3) and one P(4) atom. In the twelfth O site, O(12) is bonded in a distorted bent 120 degrees geometry to one Ni(1) and one P(4) atom.