NaTi2(PO4)3 crystallizes in the triclinic P-1 space group. Na(1) is bonded in a 6-coordinate geometry to one O(1), one O(12), one O(2), one O(3), one O(6), and one O(9) atom. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(10), one O(11), one O(3), one O(4), one O(6), and one O(7) atom to form TiO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. In the second Ti site, Ti(2) is bonded to one O(1), one O(12), one O(2), one O(5), one O(8), and one O(9) atom to form TiO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(3), one O(4), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Ti(1)O6 octahedra and corners with two equivalent Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 27-35°. In the second P site, P(2) is bonded to one O(1), one O(10), one O(7), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Ti(1)O6 octahedra and corners with two equivalent Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 24-34°. In the third P site, P(3) is bonded to one O(11), one O(12), one O(5), and one O(6) atom to form PO4 tetrahedra that share corners with two equivalent Ti(1)O6 octahedra and corners with two equivalent Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 22-31°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one Na(1), one Ti(2), and one P(2) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Na(1), one Ti(2), and one P(1) atom. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one Na(1), one Ti(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one Ti(1) and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Ti(2) and one P(3) atom. In the sixth O site, O(6) is bonded in a distorted T-shaped geometry to one Na(1), one Ti(1), and one P(3) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one Ti(1) and one P(2) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one Ti(2) and one P(1) atom. In the ninth O site, O(9) is bonded in a distorted T-shaped geometry to one Na(1), one Ti(2), and one P(2) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one Ti(1) and one P(2) atom. In the eleventh O site, O(11) is bonded in a bent 150 degrees geometry to one Ti(1) and one P(3) atom. In the twelfth O site, O(12) is bonded in a distorted bent 150 degrees geometry to one Na(1), one Ti(2), and one P(3) atom.
NaTi2(PO4)3 crystallizes in the triclinic P-1 space group. Na(1) is bonded in a 6-coordinate geometry to one O(1), one O(12), one O(2), one O(3), one O(6), and one O(9) atom. The Na(1)-O(1) bond length is 2.33 Å. The Na(1)-O(12) bond length is 2.66 Å. The Na(1)-O(2) bond length is 2.33 Å. The Na(1)-O(3) bond length is 2.42 Å. The Na(1)-O(6) bond length is 2.25 Å. The Na(1)-O(9) bond length is 2.33 Å. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(10), one O(11), one O(3), one O(4), one O(6), and one O(7) atom to form TiO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. The Ti(1)-O(10) bond length is 1.91 Å. The Ti(1)-O(11) bond length is 1.93 Å. The Ti(1)-O(3) bond length is 1.98 Å. The Ti(1)-O(4) bond length is 1.99 Å. The Ti(1)-O(6) bond length is 2.00 Å. The Ti(1)-O(7) bond length is 1.94 Å. In the second Ti site, Ti(2) is bonded to one O(1), one O(12), one O(2), one O(5), one O(8), and one O(9) atom to form TiO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. The Ti(2)-O(1) bond length is 2.04 Å. The Ti(2)-O(12) bond length is 1.96 Å. The Ti(2)-O(2) bond length is 1.99 Å. The Ti(2)-O(5) bond length is 1.91 Å. The Ti(2)-O(8) bond length is 1.90 Å. The Ti(2)-O(9) bond length is 2.02 Å. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(3), one O(4), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Ti(1)O6 octahedra and corners with two equivalent Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 27-35°. The P(1)-O(2) bond length is 1.56 Å. The P(1)-O(3) bond length is 1.55 Å. The P(1)-O(4) bond length is 1.53 Å. The P(1)-O(8) bond length is 1.55 Å. In the second P site, P(2) is bonded to one O(1), one O(10), one O(7), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Ti(1)O6 octahedra and corners with two equivalent Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 24-34°. The P(2)-O(1) bond length is 1.54 Å. The P(2)-O(10) bond length is 1.54 Å. The P(2)-O(7) bond length is 1.54 Å. The P(2)-O(9) bond length is 1.55 Å. In the third P site, P(3) is bonded to one O(11), one O(12), one O(5), and one O(6) atom to form PO4 tetrahedra that share corners with two equivalent Ti(1)O6 octahedra and corners with two equivalent Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 22-31°. The P(3)-O(11) bond length is 1.53 Å. The P(3)-O(12) bond length is 1.55 Å. The P(3)-O(5) bond length is 1.55 Å. The P(3)-O(6) bond length is 1.54 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one Na(1), one Ti(2), and one P(2) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Na(1), one Ti(2), and one P(1) atom. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one Na(1), one Ti(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one Ti(1) and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Ti(2) and one P(3) atom. In the sixth O site, O(6) is bonded in a distorted T-shaped geometry to one Na(1), one Ti(1), and one P(3) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one Ti(1) and one P(2) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one Ti(2) and one P(1) atom. In the ninth O site, O(9) is bonded in a distorted T-shaped geometry to one Na(1), one Ti(2), and one P(2) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one Ti(1) and one P(2) atom. In the eleventh O site, O(11) is bonded in a bent 150 degrees geometry to one Ti(1) and one P(3) atom. In the twelfth O site, O(12) is bonded in a distorted bent 150 degrees geometry to one Na(1), one Ti(2), and one P(3) atom.