V16O3 crystallizes in the tetragonal I4/mmm space group. There are eight inequivalent V sites. In the first V site, V(1) is bonded in a single-bond geometry to two equivalent V(3) and one O(1) atom. In the second V site, V(2) is bonded in an L-shaped geometry to two equivalent O(1) atoms. In the third V site, V(3) is bonded to one V(6), one V(7), two equivalent V(1), four equivalent V(4), and four equivalent V(5) atoms to form VV12 cuboctahedra that share corners with six equivalent V(3)V12 cuboctahedra, corners with six equivalent O(1)V6 octahedra,  a faceface with one V(7)V12 cuboctahedra, faces with two equivalent V(3)V12 cuboctahedra, and faces with two equivalent O(2)V6 octahedra. The corner-sharing octahedral tilt angles range from 45-46°. In the fourth V site, V(4) is bonded in a single-bond geometry to two equivalent V(3) and one O(2) atom. In the fifth V site, V(5) is bonded in a single-bond geometry to one V(7), two equivalent V(3), and one O(1) atom. In the sixth V site, V(6) is bonded in a linear geometry to two equivalent V(3) and two equivalent O(2) atoms. In the seventh V site, V(7) is bonded to four equivalent V(3) and eight equivalent V(5) atoms to form VV12 cuboctahedra that share corners with eight equivalent O(1)V6 octahedra and faces with four equivalent V(3)V12 cuboctahedra. The corner-sharing octahedral tilt angles are 46°. In the eighth V site, V(8) is bonded in a square co-planar geometry to four equivalent O(1) atoms. There are two inequivalent O sites. In the first O site, O(1) is bonded to one V(1), one V(8), two equivalent V(2), and two equivalent V(5) atoms to form OV6 octahedra that share corners with two equivalent V(7)V12 cuboctahedra, corners with six equivalent V(3)V12 cuboctahedra,  a cornercorner with one O(1)V6 octahedra, and edges with two equivalent O(1)V6 octahedra. The corner-sharing octahedra are not tilted. In the second O site, O(2) is bonded to two equivalent V(6) and four equivalent V(4) atoms to form OV6 octahedra that share corners with two equivalent O(2)V6 octahedra and faces with four equivalent V(3)V12 cuboctahedra. The corner-sharing octahedra are not tilted.
V16O3 crystallizes in the tetragonal I4/mmm space group. There are eight inequivalent V sites. In the first V site, V(1) is bonded in a single-bond geometry to two equivalent V(3) and one O(1) atom. Both V(1)-V(3) bond lengths are 3.07 Å. The V(1)-O(1) bond length is 2.19 Å. In the second V site, V(2) is bonded in an L-shaped geometry to two equivalent O(1) atoms. Both V(2)-O(1) bond lengths are 2.20 Å. In the third V site, V(3) is bonded to one V(6), one V(7), two equivalent V(1), four equivalent V(4), and four equivalent V(5) atoms to form VV12 cuboctahedra that share corners with six equivalent V(3)V12 cuboctahedra, corners with six equivalent O(1)V6 octahedra,  a faceface with one V(7)V12 cuboctahedra, faces with two equivalent V(3)V12 cuboctahedra, and faces with two equivalent O(2)V6 octahedra. The corner-sharing octahedral tilt angles range from 45-46°. The V(3)-V(6) bond length is 3.09 Å. The V(3)-V(7) bond length is 3.06 Å. All V(3)-V(4) bond lengths are 3.04 Å. All V(3)-V(5) bond lengths are 2.98 Å. In the fourth V site, V(4) is bonded in a single-bond geometry to two equivalent V(3) and one O(2) atom. The V(4)-O(2) bond length is 2.17 Å. In the fifth V site, V(5) is bonded in a single-bond geometry to one V(7), two equivalent V(3), and one O(1) atom. The V(5)-V(7) bond length is 2.98 Å. The V(5)-O(1) bond length is 2.19 Å. In the sixth V site, V(6) is bonded in a linear geometry to two equivalent V(3) and two equivalent O(2) atoms. Both V(6)-O(2) bond lengths are 2.12 Å. In the seventh V site, V(7) is bonded to four equivalent V(3) and eight equivalent V(5) atoms to form VV12 cuboctahedra that share corners with eight equivalent O(1)V6 octahedra and faces with four equivalent V(3)V12 cuboctahedra. The corner-sharing octahedral tilt angles are 46°. In the eighth V site, V(8) is bonded in a square co-planar geometry to four equivalent O(1) atoms. All V(8)-O(1) bond lengths are 2.17 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to one V(1), one V(8), two equivalent V(2), and two equivalent V(5) atoms to form OV6 octahedra that share corners with two equivalent V(7)V12 cuboctahedra, corners with six equivalent V(3)V12 cuboctahedra,  a cornercorner with one O(1)V6 octahedra, and edges with two equivalent O(1)V6 octahedra. The corner-sharing octahedra are not tilted. In the second O site, O(2) is bonded to two equivalent V(6) and four equivalent V(4) atoms to form OV6 octahedra that share corners with two equivalent O(2)V6 octahedra and faces with four equivalent V(3)V12 cuboctahedra. The corner-sharing octahedra are not tilted.