V4O7 crystallizes in the triclinic P-1 space group. There are four inequivalent V sites. In the first V site, V(1) is bonded in a 5-coordinate geometry to one O(1), one O(3), one O(5), one O(6), and one O(7) atom. In the second V site, V(2) is bonded to one O(1), one O(3), one O(4), and two equivalent O(6) atoms to form distorted edge-sharing VO5 trigonal bipyramids. In the third V site, V(3) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(4), one O(5), and one O(7) atom. In the fourth V site, V(4) is bonded in a 6-coordinate geometry to one O(1), one O(3), one O(5), one O(7), and two equivalent O(2) atoms. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a distorted see-saw-like geometry to one V(1), one V(2), one V(3), and one V(4) atom. In the second O site, O(2) is bonded in a trigonal non-coplanar geometry to one V(3) and two equivalent V(4) atoms. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one V(1), one V(2), and one V(4) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one V(2) and one V(3) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one V(1), one V(3), and one V(4) atom. In the sixth O site, O(6) is bonded in a distorted trigonal non-coplanar geometry to one V(1) and two equivalent V(2) atoms. In the seventh O site, O(7) is bonded in a T-shaped geometry to one V(1), one V(3), and one V(4) atom.
V4O7 crystallizes in the triclinic P-1 space group. There are four inequivalent V sites. In the first V site, V(1) is bonded in a 5-coordinate geometry to one O(1), one O(3), one O(5), one O(6), and one O(7) atom. The V(1)-O(1) bond length is 2.05 Å. The V(1)-O(3) bond length is 1.90 Å. The V(1)-O(5) bond length is 1.82 Å. The V(1)-O(6) bond length is 1.88 Å. The V(1)-O(7) bond length is 1.95 Å. In the second V site, V(2) is bonded to one O(1), one O(3), one O(4), and two equivalent O(6) atoms to form distorted edge-sharing VO5 trigonal bipyramids. The V(2)-O(1) bond length is 2.11 Å. The V(2)-O(3) bond length is 1.93 Å. The V(2)-O(4) bond length is 1.89 Å. There is one shorter (1.98 Å) and one longer (1.99 Å) V(2)-O(6) bond length. In the third V site, V(3) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(4), one O(5), and one O(7) atom. The V(3)-O(1) bond length is 1.99 Å. The V(3)-O(2) bond length is 1.90 Å. The V(3)-O(4) bond length is 1.74 Å. The V(3)-O(5) bond length is 2.11 Å. The V(3)-O(7) bond length is 1.93 Å. In the fourth V site, V(4) is bonded in a 6-coordinate geometry to one O(1), one O(3), one O(5), one O(7), and two equivalent O(2) atoms. The V(4)-O(1) bond length is 2.03 Å. The V(4)-O(3) bond length is 2.08 Å. The V(4)-O(5) bond length is 2.17 Å. The V(4)-O(7) bond length is 2.05 Å. There is one shorter (2.01 Å) and one longer (2.03 Å) V(4)-O(2) bond length. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a distorted see-saw-like geometry to one V(1), one V(2), one V(3), and one V(4) atom. In the second O site, O(2) is bonded in a trigonal non-coplanar geometry to one V(3) and two equivalent V(4) atoms. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one V(1), one V(2), and one V(4) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one V(2) and one V(3) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one V(1), one V(3), and one V(4) atom. In the sixth O site, O(6) is bonded in a distorted trigonal non-coplanar geometry to one V(1) and two equivalent V(2) atoms. In the seventh O site, O(7) is bonded in a T-shaped geometry to one V(1), one V(3), and one V(4) atom.