Li2Ti4Ni(PO5)4 crystallizes in the triclinic P-1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1), two equivalent O(5), and two equivalent O(8) atoms to form distorted LiO6 octahedra that share corners with two equivalent Ti(1)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, edges with two equivalent Li(2)O6 octahedra, and faces with two equivalent Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles are 60°. In the second Li site, Li(2) is bonded to two equivalent O(5), two equivalent O(8), and two equivalent O(9) atoms to form distorted LiO6 octahedra that share corners with two equivalent Ti(1)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, edges with two equivalent Li(1)O6 octahedra, and faces with two equivalent Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles are 58°. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(10), one O(2), one O(3), one O(5), one O(6), and one O(7) atom to form distorted TiO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Li(2)O6 octahedra, corners with two equivalent Ti(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and  a faceface with one Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 38-60°. In the second Ti site, Ti(2) is bonded to one O(1), one O(4), one O(5), one O(6), one O(8), and one O(9) atom to form distorted TiO6 octahedra that share  a cornercorner with one Ni(1)O6 octahedra, corners with two equivalent Ti(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra,  a faceface with one Li(1)O6 octahedra, and  a faceface with one Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 38-51°. Ni(1) is bonded to two equivalent O(10), two equivalent O(6), and two equivalent O(7) atoms to form NiO6 octahedra that share corners with two equivalent Ti(2)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and faces with two equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles are 51°. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(4), one O(7), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Li(2)O6 octahedra,  a cornercorner with one Ti(1)O6 octahedra,  a cornercorner with one Ni(1)O6 octahedra, and corners with three equivalent Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 30-53°. In the second P site, P(2) is bonded to one O(10), one O(2), one O(3), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Li(2)O6 octahedra,  a cornercorner with one Ti(2)O6 octahedra,  a cornercorner with one Ni(1)O6 octahedra, and corners with three equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 31-57°. There are ten inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one Li(1), one Ti(2), and one P(1) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Ti(1) and one P(2) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Ti(1) and one P(2) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one Ti(2) and one P(1) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Ti(1), and one Ti(2) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Ti(1), one Ti(2), and one Ni(1) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Ti(1), one Ni(1), and one P(1) atom. In the eighth O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one Ti(2), and one P(2) atom. In the ninth O site, O(9) is bonded in a distorted T-shaped geometry to one Li(2), one Ti(2), and one P(1) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Ti(1), one Ni(1), and one P(2) atom.
Li2Ti4Ni(PO5)4 crystallizes in the triclinic P-1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1), two equivalent O(5), and two equivalent O(8) atoms to form distorted LiO6 octahedra that share corners with two equivalent Ti(1)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, edges with two equivalent Li(2)O6 octahedra, and faces with two equivalent Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles are 60°. Both Li(1)-O(1) bond lengths are 2.12 Å. Both Li(1)-O(5) bond lengths are 2.17 Å. Both Li(1)-O(8) bond lengths are 2.21 Å. In the second Li site, Li(2) is bonded to two equivalent O(5), two equivalent O(8), and two equivalent O(9) atoms to form distorted LiO6 octahedra that share corners with two equivalent Ti(1)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, edges with two equivalent Li(1)O6 octahedra, and faces with two equivalent Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles are 58°. Both Li(2)-O(5) bond lengths are 2.19 Å. Both Li(2)-O(8) bond lengths are 2.21 Å. Both Li(2)-O(9) bond lengths are 2.02 Å. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(10), one O(2), one O(3), one O(5), one O(6), and one O(7) atom to form distorted TiO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Li(2)O6 octahedra, corners with two equivalent Ti(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and  a faceface with one Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 38-60°. The Ti(1)-O(10) bond length is 2.11 Å. The Ti(1)-O(2) bond length is 1.92 Å. The Ti(1)-O(3) bond length is 1.93 Å. The Ti(1)-O(5) bond length is 1.74 Å. The Ti(1)-O(6) bond length is 2.23 Å. The Ti(1)-O(7) bond length is 2.08 Å. In the second Ti site, Ti(2) is bonded to one O(1), one O(4), one O(5), one O(6), one O(8), and one O(9) atom to form distorted TiO6 octahedra that share  a cornercorner with one Ni(1)O6 octahedra, corners with two equivalent Ti(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra,  a faceface with one Li(1)O6 octahedra, and  a faceface with one Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 38-51°. The Ti(2)-O(1) bond length is 2.01 Å. The Ti(2)-O(4) bond length is 1.91 Å. The Ti(2)-O(5) bond length is 2.21 Å. The Ti(2)-O(6) bond length is 1.74 Å. The Ti(2)-O(8) bond length is 2.08 Å. The Ti(2)-O(9) bond length is 2.03 Å. Ni(1) is bonded to two equivalent O(10), two equivalent O(6), and two equivalent O(7) atoms to form NiO6 octahedra that share corners with two equivalent Ti(2)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and faces with two equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles are 51°. Both Ni(1)-O(10) bond lengths are 2.07 Å. Both Ni(1)-O(6) bond lengths are 2.03 Å. Both Ni(1)-O(7) bond lengths are 2.12 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(4), one O(7), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Li(2)O6 octahedra,  a cornercorner with one Ti(1)O6 octahedra,  a cornercorner with one Ni(1)O6 octahedra, and corners with three equivalent Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 30-53°. The P(1)-O(1) bond length is 1.54 Å. The P(1)-O(4) bond length is 1.55 Å. The P(1)-O(7) bond length is 1.56 Å. The P(1)-O(9) bond length is 1.54 Å. In the second P site, P(2) is bonded to one O(10), one O(2), one O(3), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Li(2)O6 octahedra,  a cornercorner with one Ti(2)O6 octahedra,  a cornercorner with one Ni(1)O6 octahedra, and corners with three equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 31-57°. The P(2)-O(10) bond length is 1.55 Å. The P(2)-O(2) bond length is 1.54 Å. The P(2)-O(3) bond length is 1.54 Å. The P(2)-O(8) bond length is 1.56 Å. There are ten inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one Li(1), one Ti(2), and one P(1) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Ti(1) and one P(2) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Ti(1) and one P(2) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one Ti(2) and one P(1) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Ti(1), and one Ti(2) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Ti(1), one Ti(2), and one Ni(1) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Ti(1), one Ni(1), and one P(1) atom. In the eighth O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one Ti(2), and one P(2) atom. In the ninth O site, O(9) is bonded in a distorted T-shaped geometry to one Li(2), one Ti(2), and one P(1) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Ti(1), one Ni(1), and one P(2) atom.