Ti3PO2 is Caswellsilverite-like structured and crystallizes in the trigonal P-3m1 space group. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to three equivalent P(1) and three equivalent O(1) atoms to form distorted TiP3O3 octahedra that share corners with three equivalent Ti(2)O6 octahedra, corners with three equivalent Ti(1)P3O3 octahedra, edges with three equivalent Ti(2)O6 octahedra, and edges with nine equivalent Ti(1)P3O3 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. 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)P3O3 octahedra, edges with six equivalent Ti(2)O6 octahedra, and edges with six equivalent Ti(1)P3O3 octahedra. The corner-sharing octahedral tilt angles are 2°. P(1) is bonded to six equivalent Ti(1) atoms to form PTi6 octahedra that share corners with six equivalent O(1)Ti6 octahedra, edges with six equivalent P(1)Ti6 octahedra, and edges with six equivalent O(1)Ti6 octahedra. The corner-sharing octahedral tilt angles are 9°. O(1) is bonded to three equivalent Ti(1) and three equivalent Ti(2) atoms to form OTi6 octahedra that share corners with three equivalent P(1)Ti6 octahedra, corners with three equivalent O(1)Ti6 octahedra, edges with three equivalent P(1)Ti6 octahedra, and edges with nine equivalent O(1)Ti6 octahedra. The corner-sharing octahedral tilt angles range from 0-9°.
Ti3PO2 is Caswellsilverite-like structured and crystallizes in the trigonal P-3m1 space group. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to three equivalent P(1) and three equivalent O(1) atoms to form distorted TiP3O3 octahedra that share corners with three equivalent Ti(2)O6 octahedra, corners with three equivalent Ti(1)P3O3 octahedra, edges with three equivalent Ti(2)O6 octahedra, and edges with nine equivalent Ti(1)P3O3 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. All Ti(1)-P(1) bond lengths are 2.47 Å. All Ti(1)-O(1) bond lengths are 2.20 Å. 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)P3O3 octahedra, edges with six equivalent Ti(2)O6 octahedra, and edges with six equivalent Ti(1)P3O3 octahedra. The corner-sharing octahedral tilt angles are 2°. All Ti(2)-O(1) bond lengths are 2.16 Å. P(1) is bonded to six equivalent Ti(1) atoms to form PTi6 octahedra that share corners with six equivalent O(1)Ti6 octahedra, edges with six equivalent P(1)Ti6 octahedra, and edges with six equivalent O(1)Ti6 octahedra. The corner-sharing octahedral tilt angles are 9°. O(1) is bonded to three equivalent Ti(1) and three equivalent Ti(2) atoms to form OTi6 octahedra that share corners with three equivalent P(1)Ti6 octahedra, corners with three equivalent O(1)Ti6 octahedra, edges with three equivalent P(1)Ti6 octahedra, and edges with nine equivalent O(1)Ti6 octahedra. The corner-sharing octahedral tilt angles range from 0-9°.