V4O7 crystallizes in the triclinic P-1 space group. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(3), one O(4), one O(5), and two equivalent O(1) atoms to form a mixture of distorted face, corner, and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 42-56°. In the second V site, V(2) is bonded to one O(1), one O(2), one O(4), one O(6), and two equivalent O(7) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 45-60°. In the third V site, V(3) is bonded to one O(2), one O(3), one O(4), one O(5), and two equivalent O(6) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 42-60°. In the fourth V site, V(4) is bonded to one O(1), one O(2), one O(5), one O(7), and two equivalent O(3) atoms to form a mixture of distorted face, corner, and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 45-55°. There are seven inequivalent O sites. In the first O site, O(1) is bonded to one V(2), one V(4), and two equivalent V(1) atoms to form a mixture of corner and edge-sharing OV4 trigonal pyramids. In the second O site, O(2) is bonded to one V(1), one V(2), one V(3), and one V(4) atom to form distorted edge-sharing OV4 trigonal pyramids. In the third O site, O(3) is bonded to one V(1), one V(3), and two equivalent V(4) atoms to form a mixture of corner and edge-sharing OV4 trigonal pyramids. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one V(1), one V(2), and one V(3) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar 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 T-shaped geometry to one V(2) and two equivalent V(3) atoms. In the seventh O site, O(7) is bonded in a distorted T-shaped geometry to one V(4) and two equivalent V(2) atoms.
V4O7 crystallizes in the triclinic P-1 space group. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(3), one O(4), one O(5), and two equivalent O(1) atoms to form a mixture of distorted face, corner, and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 42-56°. The V(1)-O(2) bond length is 2.10 Å. The V(1)-O(3) bond length is 1.97 Å. The V(1)-O(4) bond length is 1.91 Å. The V(1)-O(5) bond length is 1.78 Å. There is one shorter (1.97 Å) and one longer (2.14 Å) V(1)-O(1) bond length. In the second V site, V(2) is bonded to one O(1), one O(2), one O(4), one O(6), and two equivalent O(7) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 45-60°. The V(2)-O(1) bond length is 2.04 Å. The V(2)-O(2) bond length is 2.05 Å. The V(2)-O(4) bond length is 1.95 Å. The V(2)-O(6) bond length is 1.89 Å. There is one shorter (1.92 Å) and one longer (2.00 Å) V(2)-O(7) bond length. In the third V site, V(3) is bonded to one O(2), one O(3), one O(4), one O(5), and two equivalent O(6) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 42-60°. The V(3)-O(2) bond length is 2.01 Å. The V(3)-O(3) bond length is 2.05 Å. The V(3)-O(4) bond length is 1.91 Å. The V(3)-O(5) bond length is 2.07 Å. There is one shorter (1.90 Å) and one longer (1.93 Å) V(3)-O(6) bond length. In the fourth V site, V(4) is bonded to one O(1), one O(2), one O(5), one O(7), and two equivalent O(3) atoms to form a mixture of distorted face, corner, and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 45-55°. The V(4)-O(1) bond length is 1.97 Å. The V(4)-O(2) bond length is 2.06 Å. The V(4)-O(5) bond length is 1.93 Å. The V(4)-O(7) bond length is 1.81 Å. There is one shorter (1.98 Å) and one longer (2.11 Å) V(4)-O(3) bond length. There are seven inequivalent O sites. In the first O site, O(1) is bonded to one V(2), one V(4), and two equivalent V(1) atoms to form a mixture of corner and edge-sharing OV4 trigonal pyramids. In the second O site, O(2) is bonded to one V(1), one V(2), one V(3), and one V(4) atom to form distorted edge-sharing OV4 trigonal pyramids. In the third O site, O(3) is bonded to one V(1), one V(3), and two equivalent V(4) atoms to form a mixture of corner and edge-sharing OV4 trigonal pyramids. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one V(1), one V(2), and one V(3) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar 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 T-shaped geometry to one V(2) and two equivalent V(3) atoms. In the seventh O site, O(7) is bonded in a distorted T-shaped geometry to one V(4) and two equivalent V(2) atoms.