V4C3H is Caswellsilverite-like structured and crystallizes in the trigonal R-3m space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to three equivalent C(1) and three equivalent C(2) atoms to form VC6 octahedra that share corners with three equivalent V(1)C6 octahedra, corners with three equivalent V(2)H3C3 octahedra, edges with three equivalent V(2)H3C3 octahedra, and edges with nine equivalent V(1)C6 octahedra. The corner-sharing octahedral tilt angles range from 0-3°. In the second V site, V(2) is bonded to three equivalent C(1) and three equivalent H(1) atoms to form VH3C3 octahedra that share corners with three equivalent V(1)C6 octahedra, corners with three equivalent V(2)H3C3 octahedra, edges with three equivalent V(1)C6 octahedra, and edges with nine equivalent V(2)H3C3 octahedra. The corner-sharing octahedral tilt angles range from 0-3°. There are two inequivalent C sites. In the first C site, C(1) is bonded to three equivalent V(1) and three equivalent V(2) atoms to form CV6 octahedra that share corners with three equivalent C(2)V6 octahedra, corners with three equivalent H(1)V6 octahedra, edges with three equivalent C(2)V6 octahedra, edges with three equivalent H(1)V6 octahedra, and edges with six equivalent C(1)V6 octahedra. The corner-sharing octahedral tilt angles range from 1-4°. In the second C site, C(2) is bonded to six equivalent V(1) atoms to form a mixture of corner and edge-sharing CV6 octahedra. The corner-sharing octahedral tilt angles are 1°. H(1) is bonded to six equivalent V(2) atoms to form HV6 octahedra that share corners with six equivalent C(1)V6 octahedra, edges with six equivalent C(1)V6 octahedra, and edges with six equivalent H(1)V6 octahedra. The corner-sharing octahedral tilt angles are 4°.
V4C3H is Caswellsilverite-like structured and crystallizes in the trigonal R-3m space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to three equivalent C(1) and three equivalent C(2) atoms to form VC6 octahedra that share corners with three equivalent V(1)C6 octahedra, corners with three equivalent V(2)H3C3 octahedra, edges with three equivalent V(2)H3C3 octahedra, and edges with nine equivalent V(1)C6 octahedra. The corner-sharing octahedral tilt angles range from 0-3°. All V(1)-C(1) bond lengths are 2.08 Å. All V(1)-C(2) bond lengths are 2.10 Å. In the second V site, V(2) is bonded to three equivalent C(1) and three equivalent H(1) atoms to form VH3C3 octahedra that share corners with three equivalent V(1)C6 octahedra, corners with three equivalent V(2)H3C3 octahedra, edges with three equivalent V(1)C6 octahedra, and edges with nine equivalent V(2)H3C3 octahedra. The corner-sharing octahedral tilt angles range from 0-3°. All V(2)-C(1) bond lengths are 2.00 Å. All V(2)-H(1) bond lengths are 2.09 Å. There are two inequivalent C sites. In the first C site, C(1) is bonded to three equivalent V(1) and three equivalent V(2) atoms to form CV6 octahedra that share corners with three equivalent C(2)V6 octahedra, corners with three equivalent H(1)V6 octahedra, edges with three equivalent C(2)V6 octahedra, edges with three equivalent H(1)V6 octahedra, and edges with six equivalent C(1)V6 octahedra. The corner-sharing octahedral tilt angles range from 1-4°. In the second C site, C(2) is bonded to six equivalent V(1) atoms to form a mixture of corner and edge-sharing CV6 octahedra. The corner-sharing octahedral tilt angles are 1°. H(1) is bonded to six equivalent V(2) atoms to form HV6 octahedra that share corners with six equivalent C(1)V6 octahedra, edges with six equivalent C(1)V6 octahedra, and edges with six equivalent H(1)V6 octahedra. The corner-sharing octahedral tilt angles are 4°.