Na4TiO4 crystallizes in the triclinic P-1 space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent O(1) and two equivalent O(4) atoms to form distorted NaO4 tetrahedra that share corners with two equivalent Na(2)O5 square pyramids, corners with two equivalent Na(3)O5 square pyramids, corners with four equivalent Ti(1)O4 tetrahedra, and edges with two equivalent Na(1)O4 tetrahedra. In the second Na site, Na(2) is bonded to one O(1), two equivalent O(2), and two equivalent O(3) atoms to form NaO5 square pyramids that share corners with three equivalent Na(3)O5 square pyramids,  a cornercorner with one Ti(1)O4 tetrahedra, corners with two equivalent Na(1)O4 tetrahedra, edges with two equivalent Na(2)O5 square pyramids, edges with three equivalent Na(3)O5 square pyramids, and edges with two equivalent Ti(1)O4 tetrahedra. In the third Na site, Na(3) is bonded to one O(1), two equivalent O(2), and two equivalent O(3) atoms to form NaO5 square pyramids that share corners with three equivalent Na(2)O5 square pyramids, corners with two equivalent Na(1)O4 tetrahedra, corners with three equivalent Ti(1)O4 tetrahedra, edges with two equivalent Na(3)O5 square pyramids, edges with three equivalent Na(2)O5 square pyramids, and  an edgeedge with one Ti(1)O4 tetrahedra. In the fourth Na site, Na(4) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one O(2), one O(3), and one O(4) atom. Ti(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form TiO4 tetrahedra that share  a cornercorner with one Na(2)O5 square pyramid, corners with three equivalent Na(3)O5 square pyramids, corners with four equivalent Na(1)O4 tetrahedra,  an edgeedge with one Na(3)O5 square pyramid, and edges with two equivalent Na(2)O5 square pyramids. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Na(2), one Na(3), one Na(4), two equivalent Na(1), and one Ti(1) atom to form distorted ONa5Ti octahedra that share corners with two equivalent O(3)Na5Ti octahedra, corners with six equivalent O(4)Na3Ti trigonal pyramids,  an edgeedge with one O(1)Na5Ti octahedra, edges with two equivalent O(3)Na5Ti octahedra, and edges with three equivalent O(2)Na5Ti octahedra. The corner-sharing octahedral tilt angles range from 12-15°. In the second O site, O(2) is bonded to one Na(4), two equivalent Na(2), two equivalent Na(3), and one Ti(1) atom to form distorted ONa5Ti octahedra that share corners with two equivalent O(3)Na5Ti octahedra, corners with two equivalent O(4)Na3Ti trigonal pyramids, edges with two equivalent O(2)Na5Ti octahedra, edges with three equivalent O(1)Na5Ti octahedra, and edges with four equivalent O(3)Na5Ti octahedra. The corner-sharing octahedral tilt angles range from 10-26°. In the third O site, O(3) is bonded to one Na(4), two equivalent Na(2), two equivalent Na(3), and one Ti(1) atom to form distorted ONa5Ti octahedra that share corners with two equivalent O(1)Na5Ti octahedra, corners with two equivalent O(2)Na5Ti octahedra, corners with two equivalent O(4)Na3Ti trigonal pyramids, edges with two equivalent O(1)Na5Ti octahedra, edges with two equivalent O(3)Na5Ti octahedra, and edges with four equivalent O(2)Na5Ti octahedra. The corner-sharing octahedral tilt angles range from 10-26°. In the fourth O site, O(4) is bonded to one Na(4), two equivalent Na(1), and one Ti(1) atom to form distorted ONa3Ti trigonal pyramids that share corners with two equivalent O(2)Na5Ti octahedra, corners with two equivalent O(3)Na5Ti octahedra, corners with six equivalent O(1)Na5Ti octahedra, and  an edgeedge with one O(4)Na3Ti trigonal pyramid. The corner-sharing octahedral tilt angles range from 56-71°.
Na4TiO4 crystallizes in the triclinic P-1 space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent O(1) and two equivalent O(4) atoms to form distorted NaO4 tetrahedra that share corners with two equivalent Na(2)O5 square pyramids, corners with two equivalent Na(3)O5 square pyramids, corners with four equivalent Ti(1)O4 tetrahedra, and edges with two equivalent Na(1)O4 tetrahedra. There is one shorter (2.33 Å) and one longer (2.34 Å) Na(1)-O(1) bond length. There is one shorter (2.28 Å) and one longer (2.29 Å) Na(1)-O(4) bond length. In the second Na site, Na(2) is bonded to one O(1), two equivalent O(2), and two equivalent O(3) atoms to form NaO5 square pyramids that share corners with three equivalent Na(3)O5 square pyramids,  a cornercorner with one Ti(1)O4 tetrahedra, corners with two equivalent Na(1)O4 tetrahedra, edges with two equivalent Na(2)O5 square pyramids, edges with three equivalent Na(3)O5 square pyramids, and edges with two equivalent Ti(1)O4 tetrahedra. The Na(2)-O(1) bond length is 2.36 Å. There is one shorter (2.40 Å) and one longer (2.51 Å) Na(2)-O(2) bond length. There is one shorter (2.35 Å) and one longer (2.39 Å) Na(2)-O(3) bond length. In the third Na site, Na(3) is bonded to one O(1), two equivalent O(2), and two equivalent O(3) atoms to form NaO5 square pyramids that share corners with three equivalent Na(2)O5 square pyramids, corners with two equivalent Na(1)O4 tetrahedra, corners with three equivalent Ti(1)O4 tetrahedra, edges with two equivalent Na(3)O5 square pyramids, edges with three equivalent Na(2)O5 square pyramids, and  an edgeedge with one Ti(1)O4 tetrahedra. The Na(3)-O(1) bond length is 2.49 Å. There is one shorter (2.36 Å) and one longer (2.37 Å) Na(3)-O(2) bond length. There is one shorter (2.34 Å) and one longer (2.41 Å) Na(3)-O(3) bond length. In the fourth Na site, Na(4) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one O(2), one O(3), and one O(4) atom. The Na(4)-O(1) bond length is 2.33 Å. The Na(4)-O(2) bond length is 2.32 Å. The Na(4)-O(3) bond length is 2.35 Å. The Na(4)-O(4) bond length is 2.30 Å. Ti(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form TiO4 tetrahedra that share  a cornercorner with one Na(2)O5 square pyramid, corners with three equivalent Na(3)O5 square pyramids, corners with four equivalent Na(1)O4 tetrahedra,  an edgeedge with one Na(3)O5 square pyramid, and edges with two equivalent Na(2)O5 square pyramids. The Ti(1)-O(1) bond length is 1.83 Å. The Ti(1)-O(2) bond length is 1.84 Å. The Ti(1)-O(3) bond length is 1.84 Å. The Ti(1)-O(4) bond length is 1.82 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Na(2), one Na(3), one Na(4), two equivalent Na(1), and one Ti(1) atom to form distorted ONa5Ti octahedra that share corners with two equivalent O(3)Na5Ti octahedra, corners with six equivalent O(4)Na3Ti trigonal pyramids,  an edgeedge with one O(1)Na5Ti octahedra, edges with two equivalent O(3)Na5Ti octahedra, and edges with three equivalent O(2)Na5Ti octahedra. The corner-sharing octahedral tilt angles range from 12-15°. In the second O site, O(2) is bonded to one Na(4), two equivalent Na(2), two equivalent Na(3), and one Ti(1) atom to form distorted ONa5Ti octahedra that share corners with two equivalent O(3)Na5Ti octahedra, corners with two equivalent O(4)Na3Ti trigonal pyramids, edges with two equivalent O(2)Na5Ti octahedra, edges with three equivalent O(1)Na5Ti octahedra, and edges with four equivalent O(3)Na5Ti octahedra. The corner-sharing octahedral tilt angles range from 10-26°. In the third O site, O(3) is bonded to one Na(4), two equivalent Na(2), two equivalent Na(3), and one Ti(1) atom to form distorted ONa5Ti octahedra that share corners with two equivalent O(1)Na5Ti octahedra, corners with two equivalent O(2)Na5Ti octahedra, corners with two equivalent O(4)Na3Ti trigonal pyramids, edges with two equivalent O(1)Na5Ti octahedra, edges with two equivalent O(3)Na5Ti octahedra, and edges with four equivalent O(2)Na5Ti octahedra. The corner-sharing octahedral tilt angles range from 10-26°. In the fourth O site, O(4) is bonded to one Na(4), two equivalent Na(1), and one Ti(1) atom to form distorted ONa3Ti trigonal pyramids that share corners with two equivalent O(2)Na5Ti octahedra, corners with two equivalent O(3)Na5Ti octahedra, corners with six equivalent O(1)Na5Ti octahedra, and  an edgeedge with one O(4)Na3Ti trigonal pyramid. The corner-sharing octahedral tilt angles range from 56-71°.