NaTi2O3 is Caswellsilverite-like structured and crystallizes in the hexagonal P6_3/mcm space group. Na(1) is bonded to six equivalent O(1) atoms to form NaO6 octahedra that share corners with six equivalent Ti(1)O6 pentagonal pyramids, edges with three equivalent Na(1)O6 octahedra, edges with three equivalent Ti(2)O6 octahedra, and edges with six equivalent Ti(1)O6 pentagonal pyramids. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to six equivalent O(1) atoms to form distorted TiO6 pentagonal pyramids that share corners with two equivalent Ti(2)O6 octahedra, corners with four equivalent Na(1)O6 octahedra, edges with two equivalent Ti(2)O6 octahedra, edges with four equivalent Na(1)O6 octahedra, and edges with six equivalent Ti(1)O6 pentagonal pyramids. The corner-sharing octahedral tilt angles are 4°. In the second Ti site, Ti(2) is bonded to six equivalent O(1) atoms to form TiO6 octahedra that share corners with six equivalent Ti(1)O6 pentagonal pyramids, edges with six equivalent Na(1)O6 octahedra, and edges with six equivalent Ti(1)O6 pentagonal pyramids. O(1) is bonded to two equivalent Na(1), one Ti(2), and three equivalent Ti(1) atoms to form a mixture of corner, edge, and face-sharing ONa2Ti4 octahedra. The corner-sharing octahedral tilt angles range from 0-51°.
NaTi2O3 is Caswellsilverite-like structured and crystallizes in the hexagonal P6_3/mcm space group. Na(1) is bonded to six equivalent O(1) atoms to form NaO6 octahedra that share corners with six equivalent Ti(1)O6 pentagonal pyramids, edges with three equivalent Na(1)O6 octahedra, edges with three equivalent Ti(2)O6 octahedra, and edges with six equivalent Ti(1)O6 pentagonal pyramids. All Na(1)-O(1) bond lengths are 2.21 Å. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to six equivalent O(1) atoms to form distorted TiO6 pentagonal pyramids that share corners with two equivalent Ti(2)O6 octahedra, corners with four equivalent Na(1)O6 octahedra, edges with two equivalent Ti(2)O6 octahedra, edges with four equivalent Na(1)O6 octahedra, and edges with six equivalent Ti(1)O6 pentagonal pyramids. The corner-sharing octahedral tilt angles are 4°. There are four shorter (2.11 Å) and two longer (2.22 Å) Ti(1)-O(1) bond lengths. In the second Ti site, Ti(2) is bonded to six equivalent O(1) atoms to form TiO6 octahedra that share corners with six equivalent Ti(1)O6 pentagonal pyramids, edges with six equivalent Na(1)O6 octahedra, and edges with six equivalent Ti(1)O6 pentagonal pyramids. All Ti(2)-O(1) bond lengths are 2.10 Å. O(1) is bonded to two equivalent Na(1), one Ti(2), and three equivalent Ti(1) atoms to form a mixture of corner, edge, and face-sharing ONa2Ti4 octahedra. The corner-sharing octahedral tilt angles range from 0-51°.