Na2TiO3 is Caswellsilverite-like structured and crystallizes in the monoclinic C2/c space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form distorted NaO6 octahedra that share corners with two equivalent Na(3)O6 octahedra, corners with two equivalent Ti(1)O6 octahedra, corners with two equivalent Ti(2)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent Ti(2)O6 octahedra, edges with three equivalent Na(1)O6 octahedra, and edges with three equivalent Na(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 13-16°. In the second Na site, Na(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form distorted NaO6 octahedra that share corners with two equivalent Na(3)O6 octahedra, corners with two equivalent Ti(1)O6 octahedra, corners with two equivalent Ti(2)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent Ti(2)O6 octahedra, and edges with six equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 13-16°. In the third Na site, Na(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form NaO6 octahedra that share corners with two equivalent Na(2)O6 octahedra, corners with four equivalent Na(1)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with three equivalent Ti(1)O6 octahedra, edges with three equivalent Ti(2)O6 octahedra, and edges with four equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles are 16°. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form TiO6 octahedra that share corners with two equivalent Na(2)O6 octahedra, corners with four equivalent Na(1)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with three equivalent Na(3)O6 octahedra, edges with three equivalent Ti(2)O6 octahedra, and edges with four equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles are 13°. In the second Ti site, Ti(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form TiO6 octahedra that share corners with two equivalent Na(2)O6 octahedra, corners with four equivalent Na(1)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with three equivalent Na(3)O6 octahedra, edges with three equivalent Ti(1)O6 octahedra, and edges with four equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 13-14°. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Na(2), one Na(3), two equivalent Na(1), one Ti(1), and one Ti(2) atom to form a mixture of corner and edge-sharing ONa4Ti2 octahedra. The corner-sharing octahedral tilt angles range from 0-11°. In the second O site, O(2) is bonded to one Na(2), one Na(3), two equivalent Na(1), one Ti(1), and one Ti(2) atom to form a mixture of distorted corner and edge-sharing ONa4Ti2 octahedra. The corner-sharing octahedral tilt angles range from 0-13°. In the third O site, O(3) is bonded to one Na(2), one Na(3), two equivalent Na(1), one Ti(1), and one Ti(2) atom to form a mixture of distorted corner and edge-sharing ONa4Ti2 octahedra. The corner-sharing octahedral tilt angles range from 0-13°.
Na2TiO3 is Caswellsilverite-like structured and crystallizes in the monoclinic C2/c space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form distorted NaO6 octahedra that share corners with two equivalent Na(3)O6 octahedra, corners with two equivalent Ti(1)O6 octahedra, corners with two equivalent Ti(2)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent Ti(2)O6 octahedra, edges with three equivalent Na(1)O6 octahedra, and edges with three equivalent Na(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 13-16°. There is one shorter (2.39 Å) and one longer (2.40 Å) Na(1)-O(1) bond length. There is one shorter (2.25 Å) and one longer (2.48 Å) Na(1)-O(2) bond length. There is one shorter (2.25 Å) and one longer (2.49 Å) Na(1)-O(3) bond length. In the second Na site, Na(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form distorted NaO6 octahedra that share corners with two equivalent Na(3)O6 octahedra, corners with two equivalent Ti(1)O6 octahedra, corners with two equivalent Ti(2)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent Ti(2)O6 octahedra, and edges with six equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 13-16°. Both Na(2)-O(1) bond lengths are 2.21 Å. Both Na(2)-O(2) bond lengths are 2.46 Å. Both Na(2)-O(3) bond lengths are 2.46 Å. In the third Na site, Na(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form NaO6 octahedra that share corners with two equivalent Na(2)O6 octahedra, corners with four equivalent Na(1)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with three equivalent Ti(1)O6 octahedra, edges with three equivalent Ti(2)O6 octahedra, and edges with four equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles are 16°. Both Na(3)-O(1) bond lengths are 2.27 Å. Both Na(3)-O(2) bond lengths are 2.28 Å. Both Na(3)-O(3) bond lengths are 2.28 Å. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form TiO6 octahedra that share corners with two equivalent Na(2)O6 octahedra, corners with four equivalent Na(1)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with three equivalent Na(3)O6 octahedra, edges with three equivalent Ti(2)O6 octahedra, and edges with four equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles are 13°. Both Ti(1)-O(1) bond lengths are 2.02 Å. Both Ti(1)-O(2) bond lengths are 1.98 Å. Both Ti(1)-O(3) bond lengths are 1.99 Å. In the second Ti site, Ti(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form TiO6 octahedra that share corners with two equivalent Na(2)O6 octahedra, corners with four equivalent Na(1)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with three equivalent Na(3)O6 octahedra, edges with three equivalent Ti(1)O6 octahedra, and edges with four equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 13-14°. Both Ti(2)-O(1) bond lengths are 2.00 Å. Both Ti(2)-O(2) bond lengths are 2.00 Å. Both Ti(2)-O(3) bond lengths are 1.99 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Na(2), one Na(3), two equivalent Na(1), one Ti(1), and one Ti(2) atom to form a mixture of corner and edge-sharing ONa4Ti2 octahedra. The corner-sharing octahedral tilt angles range from 0-11°. In the second O site, O(2) is bonded to one Na(2), one Na(3), two equivalent Na(1), one Ti(1), and one Ti(2) atom to form a mixture of distorted corner and edge-sharing ONa4Ti2 octahedra. The corner-sharing octahedral tilt angles range from 0-13°. In the third O site, O(3) is bonded to one Na(2), one Na(3), two equivalent Na(1), one Ti(1), and one Ti(2) atom to form a mixture of distorted corner and edge-sharing ONa4Ti2 octahedra. The corner-sharing octahedral tilt angles range from 0-13°.