V5N4O is Caswellsilverite-like structured and crystallizes in the tetragonal I4/m space group. There are three inequivalent V sites. In the first V site, V(1) is bonded to five equivalent N(1) and one O(1) atom to form VN5O octahedra that share  a cornercorner with one V(2)N4O2 octahedra; corners with five equivalent V(1)N5O octahedra; edges with three equivalent V(2)N4O2 octahedra; and edges with nine V(1,1)N5O octahedra. The corner-sharing octahedral tilt angles range from 0-4°. In the second V site, V(1) is bonded to five equivalent N(1) and one O(1) atom to form VN5O octahedra that share  a cornercorner with one V(2)N4O2 octahedra; corners with five V(1,1)N5O octahedra; edges with three equivalent V(2)N4O2 octahedra; and edges with nine V(1,1)N5O octahedra. The corner-sharing octahedral tilt angles range from 0-4°. In the third V site, V(2) is bonded to four equivalent N(1) and two equivalent O(1) atoms to form VN4O2 octahedra that share corners with two equivalent V(2)N4O2 octahedra; corners with four V(1,1)N5O octahedra; and edges with twelve V(1,1)N5O octahedra. The corner-sharing octahedral tilt angles range from 0-3°. N(1) is bonded to one V(2) and five V(1,1) atoms to form NV6 octahedra that share  a cornercorner with one O(1)V6 octahedra, corners with five equivalent N(1)V6 octahedra, edges with three equivalent O(1)V6 octahedra, and edges with nine equivalent N(1)V6 octahedra. The corner-sharing octahedral tilt angles range from 0-4°. O(1) is bonded to two equivalent V(2) and four equivalent V(1) atoms to form OV6 octahedra that share corners with two equivalent O(1)V6 octahedra, corners with four equivalent N(1)V6 octahedra, and edges with twelve equivalent N(1)V6 octahedra. The corner-sharing octahedral tilt angles range from 0-2°.
V5N4O is Caswellsilverite-like structured and crystallizes in the tetragonal I4/m space group. There are three inequivalent V sites. In the first V site, V(1) is bonded to five equivalent N(1) and one O(1) atom to form VN5O octahedra that share  a cornercorner with one V(2)N4O2 octahedra; corners with five equivalent V(1)N5O octahedra; edges with three equivalent V(2)N4O2 octahedra; and edges with nine V(1,1)N5O octahedra. The corner-sharing octahedral tilt angles range from 0-4°. There are a spread of V(1)-N(1) bond distances ranging from 2.10-2.22 Å. The V(1)-O(1) bond length is 2.23 Å. In the second V site, V(1) is bonded to five equivalent N(1) and one O(1) atom to form VN5O octahedra that share  a cornercorner with one V(2)N4O2 octahedra; corners with five V(1,1)N5O octahedra; edges with three equivalent V(2)N4O2 octahedra; and edges with nine V(1,1)N5O octahedra. The corner-sharing octahedral tilt angles range from 0-4°. There are a spread of V(1)-N(1) bond distances ranging from 2.10-2.22 Å. The V(1)-O(1) bond length is 2.23 Å. In the third V site, V(2) is bonded to four equivalent N(1) and two equivalent O(1) atoms to form VN4O2 octahedra that share corners with two equivalent V(2)N4O2 octahedra; corners with four V(1,1)N5O octahedra; and edges with twelve V(1,1)N5O octahedra. The corner-sharing octahedral tilt angles range from 0-3°. All V(2)-N(1) bond lengths are 2.16 Å. Both V(2)-O(1) bond lengths are 2.14 Å. N(1) is bonded to one V(2) and five V(1,1) atoms to form NV6 octahedra that share  a cornercorner with one O(1)V6 octahedra, corners with five equivalent N(1)V6 octahedra, edges with three equivalent O(1)V6 octahedra, and edges with nine equivalent N(1)V6 octahedra. The corner-sharing octahedral tilt angles range from 0-4°. O(1) is bonded to two equivalent V(2) and four equivalent V(1) atoms to form OV6 octahedra that share corners with two equivalent O(1)V6 octahedra, corners with four equivalent N(1)V6 octahedra, and edges with twelve equivalent N(1)V6 octahedra. The corner-sharing octahedral tilt angles range from 0-2°.