CaTi4O8 is beta indium sulfide-derived structured and crystallizes in the trigonal R-3m space group. Ca(1) is bonded in a 6-coordinate geometry to six equivalent O(1) atoms. 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 edge-sharing TiO6 octahedra. In the second Ti site, Ti(2) is bonded to six equivalent O(1) atoms to form edge-sharing TiO6 octahedra. There are two inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Ca(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 three equivalent Ti(1) atoms.
CaTi4O8 is beta indium sulfide-derived structured and crystallizes in the trigonal R-3m space group. Ca(1) is bonded in a 6-coordinate geometry to six equivalent O(1) atoms. All Ca(1)-O(1) bond lengths are 2.42 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 edge-sharing TiO6 octahedra. Both Ti(1)-O(2) bond lengths are 1.98 Å. All Ti(1)-O(1) bond lengths are 2.02 Å. In the second Ti site, Ti(2) is bonded to six equivalent O(1) atoms to form edge-sharing TiO6 octahedra. All Ti(2)-O(1) bond lengths are 2.07 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Ca(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 three equivalent Ti(1) atoms.