NaTi2(P2O7)2 crystallizes in the triclinic P1 space group. Na(1) is bonded to one O(14), one O(5), one O(6), one O(7), and one O(8) atom to form distorted NaO5 trigonal bipyramids that share  a cornercorner with one Ti(1)O6 octahedra, corners with two equivalent Ti(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra, and  an edgeedge with one Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 58-71°. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(1), one O(13), one O(14), one O(2), one O(7), and one O(8) atom to form TiO6 octahedra that share  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  a cornercorner with one Na(1)O5 trigonal bipyramid, and  an edgeedge with one Na(1)O5 trigonal bipyramid. In the second Ti site, Ti(2) is bonded to one O(10), one O(11), one O(12), one O(5), one O(6), 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, corners with two equivalent P(3)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra, and corners with two equivalent Na(1)O5 trigonal bipyramids. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(11), one O(3), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Ti(2)O6 octahedra, corners with two equivalent Ti(1)O6 octahedra,  a cornercorner with one P(3)O4 tetrahedra, and  a cornercorner with one Na(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 27-51°. In the second P site, P(2) is bonded to one O(12), one O(2), one O(4), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Ti(2)O6 octahedra, corners with two equivalent Ti(1)O6 octahedra,  a cornercorner with one P(4)O4 tetrahedra, and  a cornercorner with one Na(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 27-51°. In the third P site, P(3) is bonded to one O(13), one O(3), one O(5), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Ti(1)O6 octahedra, corners with two equivalent Ti(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one Na(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 31-51°. In the fourth P site, P(4) is bonded to one O(10), one O(14), one O(4), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Ti(1)O6 octahedra, corners with two equivalent Ti(2)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, and corners with two equivalent Na(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 31-52°. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Ti(1) 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 120 degrees geometry to one P(1) and one P(3) atom. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to one P(2) and one P(4) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Na(1), one Ti(2), and one P(3) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Na(1), one Ti(2), and one P(4) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Na(1), one Ti(1), and one P(1) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Na(1), one Ti(1), and one P(2) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one Ti(2) 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 bent 150 degrees geometry to one Ti(2) and one P(1) atom. In the twelfth O site, O(12) is bonded in a bent 150 degrees geometry to one Ti(2) and one P(2) atom. In the thirteenth O site, O(13) is bonded in a bent 120 degrees geometry to one Ti(1) and one P(3) atom. In the fourteenth O site, O(14) is bonded in a 3-coordinate geometry to one Na(1), one Ti(1), and one P(4) atom.
NaTi2(P2O7)2 crystallizes in the triclinic P1 space group. Na(1) is bonded to one O(14), one O(5), one O(6), one O(7), and one O(8) atom to form distorted NaO5 trigonal bipyramids that share  a cornercorner with one Ti(1)O6 octahedra, corners with two equivalent Ti(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra, and  an edgeedge with one Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 58-71°. The Na(1)-O(14) bond length is 2.73 Å. The Na(1)-O(5) bond length is 2.77 Å. The Na(1)-O(6) bond length is 2.81 Å. The Na(1)-O(7) bond length is 2.36 Å. The Na(1)-O(8) bond length is 2.41 Å. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(1), one O(13), one O(14), one O(2), one O(7), and one O(8) atom to form TiO6 octahedra that share  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  a cornercorner with one Na(1)O5 trigonal bipyramid, and  an edgeedge with one Na(1)O5 trigonal bipyramid. The Ti(1)-O(1) bond length is 1.96 Å. The Ti(1)-O(13) bond length is 2.04 Å. The Ti(1)-O(14) bond length is 2.06 Å. The Ti(1)-O(2) bond length is 1.96 Å. The Ti(1)-O(7) bond length is 2.04 Å. The Ti(1)-O(8) bond length is 2.03 Å. In the second Ti site, Ti(2) is bonded to one O(10), one O(11), one O(12), one O(5), one O(6), 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, corners with two equivalent P(3)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra, and corners with two equivalent Na(1)O5 trigonal bipyramids. The Ti(2)-O(10) bond length is 1.95 Å. The Ti(2)-O(11) bond length is 1.97 Å. The Ti(2)-O(12) bond length is 1.99 Å. The Ti(2)-O(5) bond length is 2.05 Å. The Ti(2)-O(6) bond length is 2.06 Å. The Ti(2)-O(9) bond length is 1.95 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(11), one O(3), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Ti(2)O6 octahedra, corners with two equivalent Ti(1)O6 octahedra,  a cornercorner with one P(3)O4 tetrahedra, and  a cornercorner with one Na(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 27-51°. The P(1)-O(1) bond length is 1.53 Å. The P(1)-O(11) bond length is 1.52 Å. The P(1)-O(3) bond length is 1.61 Å. The P(1)-O(7) bond length is 1.54 Å. In the second P site, P(2) is bonded to one O(12), one O(2), one O(4), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Ti(2)O6 octahedra, corners with two equivalent Ti(1)O6 octahedra,  a cornercorner with one P(4)O4 tetrahedra, and  a cornercorner with one Na(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 27-51°. The P(2)-O(12) bond length is 1.52 Å. The P(2)-O(2) bond length is 1.53 Å. The P(2)-O(4) bond length is 1.61 Å. The P(2)-O(8) bond length is 1.54 Å. In the third P site, P(3) is bonded to one O(13), one O(3), one O(5), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Ti(1)O6 octahedra, corners with two equivalent Ti(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one Na(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 31-51°. The P(3)-O(13) bond length is 1.54 Å. The P(3)-O(3) bond length is 1.62 Å. The P(3)-O(5) bond length is 1.54 Å. The P(3)-O(9) bond length is 1.52 Å. In the fourth P site, P(4) is bonded to one O(10), one O(14), one O(4), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Ti(1)O6 octahedra, corners with two equivalent Ti(2)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, and corners with two equivalent Na(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 31-52°. The P(4)-O(10) bond length is 1.52 Å. The P(4)-O(14) bond length is 1.54 Å. The P(4)-O(4) bond length is 1.62 Å. The P(4)-O(6) bond length is 1.53 Å. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Ti(1) 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 120 degrees geometry to one P(1) and one P(3) atom. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to one P(2) and one P(4) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Na(1), one Ti(2), and one P(3) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Na(1), one Ti(2), and one P(4) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Na(1), one Ti(1), and one P(1) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Na(1), one Ti(1), and one P(2) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one Ti(2) 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 bent 150 degrees geometry to one Ti(2) and one P(1) atom. In the twelfth O site, O(12) is bonded in a bent 150 degrees geometry to one Ti(2) and one P(2) atom. In the thirteenth O site, O(13) is bonded in a bent 120 degrees geometry to one Ti(1) and one P(3) atom. In the fourteenth O site, O(14) is bonded in a 3-coordinate geometry to one Na(1), one Ti(1), and one P(4) atom.