NaLiTi3O7 crystallizes in the orthorhombic Fmmm space group. Na(1) is bonded in a 1-coordinate geometry to one O(4) and four equivalent O(3) atoms. Li(1) is bonded to two equivalent O(1) and two equivalent O(3) atoms to form LiO4 tetrahedra that share corners with four equivalent Ti(1)O6 octahedra and corners with six equivalent Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-65°. There are two 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(1)O6 octahedra, and edges with four equivalent Ti(2)O6 octahedra. In the second Ti site, Ti(2) is bonded to one O(1), one O(4), two equivalent O(2), and two equivalent O(3) atoms to form TiO6 octahedra that share corners with three equivalent Ti(2)O6 octahedra, corners with three equivalent Li(1)O4 tetrahedra,  an edgeedge with one Ti(2)O6 octahedra, and edges with two equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 21-27°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Ti(2), and two equivalent Ti(1) atoms. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one Ti(1) and two equivalent Ti(2) atoms. In the third O site, O(3) is bonded in a 5-coordinate geometry to two equivalent Na(1), one Li(1), and two equivalent Ti(2) atoms. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Na(1) and two equivalent Ti(2) atoms.
NaLiTi3O7 crystallizes in the orthorhombic Fmmm space group. Na(1) is bonded in a 1-coordinate geometry to one O(4) and four equivalent O(3) atoms. The Na(1)-O(4) bond length is 2.31 Å. All Na(1)-O(3) bond lengths are 2.80 Å. Li(1) is bonded to two equivalent O(1) and two equivalent O(3) atoms to form LiO4 tetrahedra that share corners with four equivalent Ti(1)O6 octahedra and corners with six equivalent Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-65°. Both Li(1)-O(1) bond lengths are 2.02 Å. Both Li(1)-O(3) bond lengths are 2.05 Å. There are two 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(1)O6 octahedra, and edges with four equivalent Ti(2)O6 octahedra. Both Ti(1)-O(2) bond lengths are 1.97 Å. All Ti(1)-O(1) bond lengths are 1.97 Å. In the second Ti site, Ti(2) is bonded to one O(1), one O(4), two equivalent O(2), and two equivalent O(3) atoms to form TiO6 octahedra that share corners with three equivalent Ti(2)O6 octahedra, corners with three equivalent Li(1)O4 tetrahedra,  an edgeedge with one Ti(2)O6 octahedra, and edges with two equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 21-27°. The Ti(2)-O(1) bond length is 2.12 Å. The Ti(2)-O(4) bond length is 1.86 Å. Both Ti(2)-O(2) bond lengths are 2.04 Å. Both Ti(2)-O(3) bond lengths are 1.94 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Ti(2), and two equivalent Ti(1) atoms. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one Ti(1) and two equivalent Ti(2) atoms. In the third O site, O(3) is bonded in a 5-coordinate geometry to two equivalent Na(1), one Li(1), and two equivalent Ti(2) atoms. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Na(1) and two equivalent Ti(2) atoms.