NaLiTi3O7 crystallizes in the orthorhombic Cmme space group. Na(1) is bonded in a 1-coordinate geometry to one O(5) and two equivalent O(4) atoms. Li(1) is bonded to one O(4), one O(6), and two equivalent O(1) atoms to form LiO4 tetrahedra that share corners with two equivalent Ti(1)O6 octahedra, corners with two equivalent Ti(2)O6 octahedra, and corners with six equivalent Ti(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-66°. There are three inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form TiO6 octahedra that share corners with four equivalent Li(1)O4 tetrahedra, edges with two equivalent Ti(2)O6 octahedra, and edges with four equivalent Ti(3)O6 octahedra. In the second Ti site, Ti(2) is bonded to two equivalent O(3) and four equivalent O(1) atoms to form TiO6 octahedra that share corners with four equivalent Li(1)O4 tetrahedra, edges with two equivalent Ti(1)O6 octahedra, and edges with four equivalent Ti(3)O6 octahedra. In the third Ti site, Ti(3) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form TiO6 octahedra that share corners with three equivalent Ti(3)O6 octahedra, corners with three equivalent Li(1)O4 tetrahedra,  an edgeedge with one Ti(1)O6 octahedra,  an edgeedge with one Ti(2)O6 octahedra, and  an edgeedge with one Ti(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 21-27°. There are six inequivalent O sites. In the first O site, O(6) is bonded in a 3-coordinate geometry to one Li(1) and two equivalent Ti(3) atoms. In the second O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Ti(1), one Ti(2), and one Ti(3) atom. In the third O site, O(2) is bonded in a distorted T-shaped geometry to one Ti(1) and two equivalent Ti(3) atoms. In the fourth O site, O(3) is bonded in a distorted T-shaped geometry to one Ti(2) and two equivalent Ti(3) atoms. In the fifth O site, O(4) is bonded in a 5-coordinate geometry to two equivalent Na(1), one Li(1), and two equivalent Ti(3) atoms. In the sixth O site, O(5) is bonded in a 3-coordinate geometry to one Na(1) and two equivalent Ti(3) atoms.
NaLiTi3O7 crystallizes in the orthorhombic Cmme space group. Na(1) is bonded in a 1-coordinate geometry to one O(5) and two equivalent O(4) atoms. The Na(1)-O(5) bond length is 2.31 Å. Both Na(1)-O(4) bond lengths are 2.78 Å. Li(1) is bonded to one O(4), one O(6), and two equivalent O(1) atoms to form LiO4 tetrahedra that share corners with two equivalent Ti(1)O6 octahedra, corners with two equivalent Ti(2)O6 octahedra, and corners with six equivalent Ti(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-66°. The Li(1)-O(4) bond length is 2.03 Å. The Li(1)-O(6) bond length is 2.07 Å. Both Li(1)-O(1) bond lengths are 2.02 Å. There are three inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form TiO6 octahedra that share corners with four equivalent Li(1)O4 tetrahedra, edges with two equivalent Ti(2)O6 octahedra, and edges with four equivalent Ti(3)O6 octahedra. Both Ti(1)-O(2) bond lengths are 1.97 Å. All Ti(1)-O(1) bond lengths are 1.96 Å. In the second Ti site, Ti(2) is bonded to two equivalent O(3) and four equivalent O(1) atoms to form TiO6 octahedra that share corners with four equivalent Li(1)O4 tetrahedra, edges with two equivalent Ti(1)O6 octahedra, and edges with four equivalent Ti(3)O6 octahedra. Both Ti(2)-O(3) bond lengths are 1.97 Å. All Ti(2)-O(1) bond lengths are 1.97 Å. In the third Ti site, Ti(3) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form TiO6 octahedra that share corners with three equivalent Ti(3)O6 octahedra, corners with three equivalent Li(1)O4 tetrahedra,  an edgeedge with one Ti(1)O6 octahedra,  an edgeedge with one Ti(2)O6 octahedra, and  an edgeedge with one Ti(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 21-27°. The Ti(3)-O(1) bond length is 2.12 Å. The Ti(3)-O(2) bond length is 2.05 Å. The Ti(3)-O(3) bond length is 2.03 Å. The Ti(3)-O(4) bond length is 1.94 Å. The Ti(3)-O(5) bond length is 1.86 Å. The Ti(3)-O(6) bond length is 1.93 Å. There are six inequivalent O sites. In the first O site, O(6) is bonded in a 3-coordinate geometry to one Li(1) and two equivalent Ti(3) atoms. In the second O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Ti(1), one Ti(2), and one Ti(3) atom. In the third O site, O(2) is bonded in a distorted T-shaped geometry to one Ti(1) and two equivalent Ti(3) atoms. In the fourth O site, O(3) is bonded in a distorted T-shaped geometry to one Ti(2) and two equivalent Ti(3) atoms. In the fifth O site, O(4) is bonded in a 5-coordinate geometry to two equivalent Na(1), one Li(1), and two equivalent Ti(3) atoms. In the sixth O site, O(5) is bonded in a 3-coordinate geometry to one Na(1) and two equivalent Ti(3) atoms.