V7O3 crystallizes in the monoclinic C2/m space group. There are four inequivalent V sites. In the first V site, V(1) is bonded to two equivalent V(1), four equivalent V(4), and six equivalent V(3) atoms to form distorted VV12 cuboctahedra that share corners with two equivalent V(1)V12 cuboctahedra, corners with four equivalent O(1)V6 octahedra, corners with eight equivalent O(2)V6 octahedra, edges with four equivalent V(1)V12 cuboctahedra, faces with two equivalent V(1)V12 cuboctahedra, and faces with two equivalent O(2)V6 octahedra. The corner-sharing octahedral tilt angles range from 37-50°. In the second V site, V(2) is bonded to two equivalent O(1) and three equivalent O(2) atoms to form a mixture of corner and edge-sharing VO5 square pyramids. In the third V site, V(3) is bonded in a single-bond geometry to three equivalent V(1) and one O(2) atom. In the fourth V site, V(4) is bonded in a distorted T-shaped geometry to two equivalent V(1), one O(1), and two equivalent O(2) atoms. There are two inequivalent O sites. In the first O site, O(1) is bonded to two equivalent V(4) and four equivalent V(2) atoms to form OV6 octahedra that share corners with four equivalent V(1)V12 cuboctahedra, corners with four equivalent O(2)V6 octahedra, edges with two equivalent O(1)V6 octahedra, and edges with six equivalent O(2)V6 octahedra. The corner-sharing octahedral tilt angles are 4°. In the second O site, O(2) is bonded to one V(3), two equivalent V(4), and three equivalent V(2) atoms to form OV6 octahedra that share corners with four equivalent V(1)V12 cuboctahedra, corners with two equivalent O(1)V6 octahedra, edges with three equivalent O(1)V6 octahedra, edges with four equivalent O(2)V6 octahedra, and  a faceface with one V(1)V12 cuboctahedra. The corner-sharing octahedral tilt angles are 4°.
V7O3 crystallizes in the monoclinic C2/m space group. There are four inequivalent V sites. In the first V site, V(1) is bonded to two equivalent V(1), four equivalent V(4), and six equivalent V(3) atoms to form distorted VV12 cuboctahedra that share corners with two equivalent V(1)V12 cuboctahedra, corners with four equivalent O(1)V6 octahedra, corners with eight equivalent O(2)V6 octahedra, edges with four equivalent V(1)V12 cuboctahedra, faces with two equivalent V(1)V12 cuboctahedra, and faces with two equivalent O(2)V6 octahedra. The corner-sharing octahedral tilt angles range from 37-50°. Both V(1)-V(1) bond lengths are 3.14 Å. All V(1)-V(4) bond lengths are 2.95 Å. There are four shorter (2.86 Å) and two longer (3.24 Å) V(1)-V(3) bond lengths. In the second V site, V(2) is bonded to two equivalent O(1) and three equivalent O(2) atoms to form a mixture of corner and edge-sharing VO5 square pyramids. Both V(2)-O(1) bond lengths are 2.22 Å. There is one shorter (2.21 Å) and two longer (2.22 Å) V(2)-O(2) bond lengths. In the third V site, V(3) is bonded in a single-bond geometry to three equivalent V(1) and one O(2) atom. The V(3)-O(2) bond length is 2.19 Å. In the fourth V site, V(4) is bonded in a distorted T-shaped geometry to two equivalent V(1), one O(1), and two equivalent O(2) atoms. The V(4)-O(1) bond length is 2.22 Å. Both V(4)-O(2) bond lengths are 2.23 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to two equivalent V(4) and four equivalent V(2) atoms to form OV6 octahedra that share corners with four equivalent V(1)V12 cuboctahedra, corners with four equivalent O(2)V6 octahedra, edges with two equivalent O(1)V6 octahedra, and edges with six equivalent O(2)V6 octahedra. The corner-sharing octahedral tilt angles are 4°. In the second O site, O(2) is bonded to one V(3), two equivalent V(4), and three equivalent V(2) atoms to form OV6 octahedra that share corners with four equivalent V(1)V12 cuboctahedra, corners with two equivalent O(1)V6 octahedra, edges with three equivalent O(1)V6 octahedra, edges with four equivalent O(2)V6 octahedra, and  a faceface with one V(1)V12 cuboctahedra. The corner-sharing octahedral tilt angles are 4°.