Na2LiTi3Al(PO4)6 crystallizes in the triclinic P1 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a distorted hexagonal planar geometry to one O(11), one O(14), one O(18), one O(21), one O(4), and one O(7) atom. In the second Na site, Na(2) is bonded in a distorted hexagonal planar geometry to one O(16), one O(17), one O(20), one O(5), one O(8), and one O(9) atom. Li(1) is bonded in a 6-coordinate geometry to one O(14), one O(19), one O(24), one O(4), one O(8), and one O(9) atom. There are three inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(22), one O(23), one O(24), one O(5), one O(8), and one O(9) atom to form TiO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. In the second Ti site, Ti(2) is bonded to one O(10), one O(12), one O(14), one O(19), one O(4), and one O(7) atom to form TiO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. In the third Ti site, Ti(3) is bonded to one O(1), one O(16), one O(17), one O(2), one O(20), and one O(3) atom to form TiO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. Al(1) is bonded to one O(11), one O(13), one O(15), one O(18), one O(21), and one O(6) atom to form AlO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. There are six inequivalent P sites. In the first P site, 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  a cornercorner with one Ti(1)O6 octahedra,  a cornercorner with one Ti(2)O6 octahedra,  a cornercorner with one Ti(3)O6 octahedra, and  a cornercorner with one Al(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 26-38°. In the second P site, P(2) is bonded to one O(1), one O(13), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Ti(1)O6 octahedra,  a cornercorner with one Ti(2)O6 octahedra,  a cornercorner with one Ti(3)O6 octahedra, and  a cornercorner with one Al(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 25-37°. In the third P site, P(3) is bonded to one O(14), one O(15), one O(2), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Ti(1)O6 octahedra,  a cornercorner with one Ti(2)O6 octahedra,  a cornercorner with one Ti(3)O6 octahedra, and  a cornercorner with one Al(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 25-36°. In the fourth P site, P(4) is bonded to one O(10), one O(11), one O(16), and one O(23) atom to form PO4 tetrahedra that share  a cornercorner with one Ti(1)O6 octahedra,  a cornercorner with one Ti(2)O6 octahedra,  a cornercorner with one Ti(3)O6 octahedra, and  a cornercorner with one Al(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 23-35°. In the fifth P site, P(5) is bonded to one O(12), one O(17), one O(18), and one O(24) atom to form PO4 tetrahedra that share  a cornercorner with one Ti(1)O6 octahedra,  a cornercorner with one Ti(2)O6 octahedra,  a cornercorner with one Ti(3)O6 octahedra, and  a cornercorner with one Al(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 23-36°. In the sixth P site, P(6) is bonded to one O(19), one O(20), one O(21), and one O(22) atom to form PO4 tetrahedra that share  a cornercorner with one Ti(1)O6 octahedra,  a cornercorner with one Ti(2)O6 octahedra,  a cornercorner with one Ti(3)O6 octahedra, and  a cornercorner with one Al(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 23-36°. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Ti(3) and one P(2) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Ti(3) and one P(3) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Ti(3) and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Li(1), one Ti(2), and one P(1) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Na(2), one Ti(1), and one P(1) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one Al(1) and one P(1) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Na(1), one Ti(2), and one P(2) atom. In the eighth O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to one Na(2), one Li(1), one Ti(1), and one P(2) atom. In the ninth O site, O(9) is bonded in a distorted rectangular see-saw-like geometry to one Na(2), one Li(1), one Ti(1), and one P(3) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one Ti(2) and one P(4) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Na(1), one Al(1), and one P(4) atom. In the twelfth O site, O(12) is bonded in a bent 150 degrees geometry to one Ti(2) and one P(5) atom. In the thirteenth O site, O(13) is bonded in a bent 150 degrees geometry to one Al(1) and one P(2) atom. In the fourteenth O site, O(14) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Li(1), one Ti(2), and one P(3) atom. In the fifteenth O site, O(15) is bonded in a bent 150 degrees geometry to one Al(1) and one P(3) atom. In the sixteenth O site, O(16) is bonded in a 3-coordinate geometry to one Na(2), one Ti(3), and one P(4) atom. In the seventeenth O site, O(17) is bonded in a 3-coordinate geometry to one Na(2), one Ti(3), and one P(5) atom. In the eighteenth O site, O(18) is bonded in a 3-coordinate geometry to one Na(1), one Al(1), and one P(5) atom. In the nineteenth O site, O(19) is bonded in a 3-coordinate geometry to one Li(1), one Ti(2), and one P(6) atom. In the twentieth O site, O(20) is bonded in a 3-coordinate geometry to one Na(2), one Ti(3), and one P(6) atom. In the twenty-first O site, O(21) is bonded in a 3-coordinate geometry to one Na(1), one Al(1), and one P(6) atom. In the twenty-second O site, O(22) is bonded in a bent 150 degrees geometry to one Ti(1) and one P(6) atom. In the twenty-third O site, O(23) is bonded in a bent 150 degrees geometry to one Ti(1) and one P(4) atom. In the twenty-fourth O site, O(24) is bonded in a 3-coordinate geometry to one Li(1), one Ti(1), and one P(5) atom.
Na2LiTi3Al(PO4)6 crystallizes in the triclinic P1 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a distorted hexagonal planar geometry to one O(11), one O(14), one O(18), one O(21), one O(4), and one O(7) atom. The Na(1)-O(11) bond length is 2.39 Å. The Na(1)-O(14) bond length is 2.57 Å. The Na(1)-O(18) bond length is 2.45 Å. The Na(1)-O(21) bond length is 2.39 Å. The Na(1)-O(4) bond length is 2.56 Å. The Na(1)-O(7) bond length is 2.50 Å. In the second Na site, Na(2) is bonded in a distorted hexagonal planar geometry to one O(16), one O(17), one O(20), one O(5), one O(8), and one O(9) atom. The Na(2)-O(16) bond length is 2.42 Å. The Na(2)-O(17) bond length is 2.43 Å. The Na(2)-O(20) bond length is 2.48 Å. The Na(2)-O(5) bond length is 2.44 Å. The Na(2)-O(8) bond length is 2.51 Å. The Na(2)-O(9) bond length is 2.51 Å. Li(1) is bonded in a 6-coordinate geometry to one O(14), one O(19), one O(24), one O(4), one O(8), and one O(9) atom. The Li(1)-O(14) bond length is 2.07 Å. The Li(1)-O(19) bond length is 2.52 Å. The Li(1)-O(24) bond length is 2.52 Å. The Li(1)-O(4) bond length is 2.28 Å. The Li(1)-O(8) bond length is 2.27 Å. The Li(1)-O(9) bond length is 2.08 Å. There are three inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(22), one O(23), one O(24), one O(5), one O(8), and one O(9) atom to form TiO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. The Ti(1)-O(22) bond length is 1.88 Å. The Ti(1)-O(23) bond length is 1.89 Å. The Ti(1)-O(24) bond length is 1.99 Å. The Ti(1)-O(5) bond length is 1.97 Å. The Ti(1)-O(8) bond length is 2.05 Å. The Ti(1)-O(9) bond length is 2.05 Å. In the second Ti site, Ti(2) is bonded to one O(10), one O(12), one O(14), one O(19), one O(4), and one O(7) atom to form TiO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. The Ti(2)-O(10) bond length is 1.88 Å. The Ti(2)-O(12) bond length is 1.87 Å. The Ti(2)-O(14) bond length is 2.03 Å. The Ti(2)-O(19) bond length is 1.98 Å. The Ti(2)-O(4) bond length is 2.04 Å. The Ti(2)-O(7) bond length is 1.96 Å. In the third Ti site, Ti(3) is bonded to one O(1), one O(16), one O(17), one O(2), one O(20), and one O(3) atom to form TiO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. The Ti(3)-O(1) bond length is 1.93 Å. The Ti(3)-O(16) bond length is 1.98 Å. The Ti(3)-O(17) bond length is 1.98 Å. The Ti(3)-O(2) bond length is 1.92 Å. The Ti(3)-O(20) bond length is 1.99 Å. The Ti(3)-O(3) bond length is 1.91 Å. Al(1) is bonded to one O(11), one O(13), one O(15), one O(18), one O(21), and one O(6) atom to form AlO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. The Al(1)-O(11) bond length is 1.92 Å. The Al(1)-O(13) bond length is 1.87 Å. The Al(1)-O(15) bond length is 1.87 Å. The Al(1)-O(18) bond length is 1.93 Å. The Al(1)-O(21) bond length is 1.93 Å. The Al(1)-O(6) bond length is 1.89 Å. There are six inequivalent P sites. In the first P site, 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  a cornercorner with one Ti(1)O6 octahedra,  a cornercorner with one Ti(2)O6 octahedra,  a cornercorner with one Ti(3)O6 octahedra, and  a cornercorner with one Al(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 26-38°. The P(1)-O(3) bond length is 1.55 Å. The P(1)-O(4) bond length is 1.56 Å. The P(1)-O(5) bond length is 1.55 Å. The P(1)-O(6) bond length is 1.51 Å. In the second P site, P(2) is bonded to one O(1), one O(13), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Ti(1)O6 octahedra,  a cornercorner with one Ti(2)O6 octahedra,  a cornercorner with one Ti(3)O6 octahedra, and  a cornercorner with one Al(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 25-37°. The P(2)-O(1) bond length is 1.55 Å. The P(2)-O(13) bond length is 1.52 Å. The P(2)-O(7) bond length is 1.55 Å. The P(2)-O(8) bond length is 1.56 Å. In the third P site, P(3) is bonded to one O(14), one O(15), one O(2), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Ti(1)O6 octahedra,  a cornercorner with one Ti(2)O6 octahedra,  a cornercorner with one Ti(3)O6 octahedra, and  a cornercorner with one Al(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 25-36°. The P(3)-O(14) bond length is 1.57 Å. The P(3)-O(15) bond length is 1.51 Å. The P(3)-O(2) bond length is 1.54 Å. The P(3)-O(9) bond length is 1.56 Å. In the fourth P site, P(4) is bonded to one O(10), one O(11), one O(16), and one O(23) atom to form PO4 tetrahedra that share  a cornercorner with one Ti(1)O6 octahedra,  a cornercorner with one Ti(2)O6 octahedra,  a cornercorner with one Ti(3)O6 octahedra, and  a cornercorner with one Al(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 23-35°. The P(4)-O(10) bond length is 1.55 Å. The P(4)-O(11) bond length is 1.52 Å. The P(4)-O(16) bond length is 1.54 Å. The P(4)-O(23) bond length is 1.56 Å. In the fifth P site, P(5) is bonded to one O(12), one O(17), one O(18), and one O(24) atom to form PO4 tetrahedra that share  a cornercorner with one Ti(1)O6 octahedra,  a cornercorner with one Ti(2)O6 octahedra,  a cornercorner with one Ti(3)O6 octahedra, and  a cornercorner with one Al(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 23-36°. The P(5)-O(12) bond length is 1.56 Å. The P(5)-O(17) bond length is 1.54 Å. The P(5)-O(18) bond length is 1.52 Å. The P(5)-O(24) bond length is 1.56 Å. In the sixth P site, P(6) is bonded to one O(19), one O(20), one O(21), and one O(22) atom to form PO4 tetrahedra that share  a cornercorner with one Ti(1)O6 octahedra,  a cornercorner with one Ti(2)O6 octahedra,  a cornercorner with one Ti(3)O6 octahedra, and  a cornercorner with one Al(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 23-36°. The P(6)-O(19) bond length is 1.55 Å. The P(6)-O(20) bond length is 1.54 Å. The P(6)-O(21) bond length is 1.52 Å. The P(6)-O(22) bond length is 1.57 Å. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Ti(3) and one P(2) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Ti(3) and one P(3) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Ti(3) and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Li(1), one Ti(2), and one P(1) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Na(2), one Ti(1), and one P(1) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one Al(1) and one P(1) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Na(1), one Ti(2), and one P(2) atom. In the eighth O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to one Na(2), one Li(1), one Ti(1), and one P(2) atom. In the ninth O site, O(9) is bonded in a distorted rectangular see-saw-like geometry to one Na(2), one Li(1), one Ti(1), and one P(3) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one Ti(2) and one P(4) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Na(1), one Al(1), and one P(4) atom. In the twelfth O site, O(12) is bonded in a bent 150 degrees geometry to one Ti(2) and one P(5) atom. In the thirteenth O site, O(13) is bonded in a bent 150 degrees geometry to one Al(1) and one P(2) atom. In the fourteenth O site, O(14) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Li(1), one Ti(2), and one P(3) atom. In the fifteenth O site, O(15) is bonded in a bent 150 degrees geometry to one Al(1) and one P(3) atom. In the sixteenth O site, O(16) is bonded in a 3-coordinate geometry to one Na(2), one Ti(3), and one P(4) atom. In the seventeenth O site, O(17) is bonded in a 3-coordinate geometry to one Na(2), one Ti(3), and one P(5) atom. In the eighteenth O site, O(18) is bonded in a 3-coordinate geometry to one Na(1), one Al(1), and one P(5) atom. In the nineteenth O site, O(19) is bonded in a 3-coordinate geometry to one Li(1), one Ti(2), and one P(6) atom. In the twentieth O site, O(20) is bonded in a 3-coordinate geometry to one Na(2), one Ti(3), and one P(6) atom. In the twenty-first O site, O(21) is bonded in a 3-coordinate geometry to one Na(1), one Al(1), and one P(6) atom. In the twenty-second O site, O(22) is bonded in a bent 150 degrees geometry to one Ti(1) and one P(6) atom. In the twenty-third O site, O(23) is bonded in a bent 150 degrees geometry to one Ti(1) and one P(4) atom. In the twenty-fourth O site, O(24) is bonded in a 3-coordinate geometry to one Li(1), one Ti(1), and one P(5) atom.