Ti5CN4 is Caswellsilverite-like structured and crystallizes in the trigonal R-3m space group. There are three inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to three equivalent N(1) and three equivalent N(2) atoms to form TiN6 octahedra that share corners with three equivalent Ti(3)C3N3 octahedra, corners with three equivalent Ti(2)N6 octahedra, edges with three equivalent Ti(3)C3N3 octahedra, edges with three equivalent Ti(2)N6 octahedra, and edges with six equivalent Ti(1)N6 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the second Ti site, Ti(2) is bonded to six equivalent N(2) atoms to form a mixture of corner and edge-sharing TiN6 octahedra. The corner-sharing octahedra are not tilted. In the third Ti site, Ti(3) is bonded to three equivalent C(1) and three equivalent N(1) atoms to form TiC3N3 octahedra that share corners with three equivalent Ti(3)C3N3 octahedra, corners with three equivalent Ti(1)N6 octahedra, edges with three equivalent Ti(1)N6 octahedra, and edges with nine equivalent Ti(3)C3N3 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. C(1) is bonded to six equivalent Ti(3) atoms to form CTi6 octahedra that share corners with six equivalent N(1)Ti6 octahedra, edges with six equivalent C(1)Ti6 octahedra, and edges with six equivalent N(1)Ti6 octahedra. The corner-sharing octahedral tilt angles are 1°. There are two inequivalent N sites. In the first N site, N(1) is bonded to three equivalent Ti(1) and three equivalent Ti(3) atoms to form NTi6 octahedra that share corners with three equivalent C(1)Ti6 octahedra, corners with three equivalent N(2)Ti6 octahedra, edges with three equivalent C(1)Ti6 octahedra, edges with three equivalent N(2)Ti6 octahedra, and edges with six equivalent N(1)Ti6 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the second N site, N(2) is bonded to three equivalent Ti(1) and three equivalent Ti(2) atoms to form a mixture of corner and edge-sharing NTi6 octahedra. The corner-sharing octahedra are not tilted.
Ti5CN4 is Caswellsilverite-like structured and crystallizes in the trigonal R-3m space group. There are three inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to three equivalent N(1) and three equivalent N(2) atoms to form TiN6 octahedra that share corners with three equivalent Ti(3)C3N3 octahedra, corners with three equivalent Ti(2)N6 octahedra, edges with three equivalent Ti(3)C3N3 octahedra, edges with three equivalent Ti(2)N6 octahedra, and edges with six equivalent Ti(1)N6 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. All Ti(1)-N(1) bond lengths are 2.12 Å. All Ti(1)-N(2) bond lengths are 2.12 Å. In the second Ti site, Ti(2) is bonded to six equivalent N(2) atoms to form a mixture of corner and edge-sharing TiN6 octahedra. The corner-sharing octahedra are not tilted. All Ti(2)-N(2) bond lengths are 2.13 Å. In the third Ti site, Ti(3) is bonded to three equivalent C(1) and three equivalent N(1) atoms to form TiC3N3 octahedra that share corners with three equivalent Ti(3)C3N3 octahedra, corners with three equivalent Ti(1)N6 octahedra, edges with three equivalent Ti(1)N6 octahedra, and edges with nine equivalent Ti(3)C3N3 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. All Ti(3)-C(1) bond lengths are 2.13 Å. All Ti(3)-N(1) bond lengths are 2.16 Å. C(1) is bonded to six equivalent Ti(3) atoms to form CTi6 octahedra that share corners with six equivalent N(1)Ti6 octahedra, edges with six equivalent C(1)Ti6 octahedra, and edges with six equivalent N(1)Ti6 octahedra. The corner-sharing octahedral tilt angles are 1°. There are two inequivalent N sites. In the first N site, N(1) is bonded to three equivalent Ti(1) and three equivalent Ti(3) atoms to form NTi6 octahedra that share corners with three equivalent C(1)Ti6 octahedra, corners with three equivalent N(2)Ti6 octahedra, edges with three equivalent C(1)Ti6 octahedra, edges with three equivalent N(2)Ti6 octahedra, and edges with six equivalent N(1)Ti6 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the second N site, N(2) is bonded to three equivalent Ti(1) and three equivalent Ti(2) atoms to form a mixture of corner and edge-sharing NTi6 octahedra. The corner-sharing octahedra are not tilted.