V4O7F5 crystallizes in the triclinic P1 space group. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(4), one O(7), one F(1), one F(2), and one F(5) atom to form distorted VO3F3 octahedra that share corners with three equivalent V(3)O3F3 octahedra and corners with three equivalent V(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 16-43°. In the second V site, V(2) is bonded to one O(2), one O(5), one O(6), one O(7), one F(2), and one F(4) atom to form distorted VO4F2 octahedra that share corners with three equivalent V(1)O3F3 octahedra and corners with three equivalent V(4)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 16-43°. In the third V site, V(3) is bonded to one O(1), one O(3), one O(4), one F(1), one F(3), and one F(5) atom to form distorted VO3F3 octahedra that share corners with three equivalent V(1)O3F3 octahedra and corners with three equivalent V(4)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 10-41°. In the fourth V site, V(4) is bonded to one O(1), one O(3), one O(5), one O(6), one F(3), and one F(4) atom to form VO4F2 octahedra that share corners with three equivalent V(3)O3F3 octahedra and corners with three equivalent V(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 10-28°. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a linear geometry to one V(3) and one V(4) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the third O site, O(3) is bonded in a distorted bent 150 degrees geometry to one V(3) and one V(4) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one V(1) and one V(3) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one V(2) and one V(4) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one V(2) and one V(4) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. There are five inequivalent F sites. In the first F site, F(1) is bonded in a distorted bent 150 degrees geometry to one V(1) and one V(3) atom. In the second F site, F(2) is bonded in a distorted linear geometry to one V(1) and one V(2) atom. In the third F site, F(3) is bonded in a linear geometry to one V(3) and one V(4) atom. In the fourth F site, F(4) is bonded in a linear geometry to one V(2) and one V(4) atom. In the fifth F site, F(5) is bonded in a bent 150 degrees geometry to one V(1) and one V(3) atom.
V4O7F5 crystallizes in the triclinic P1 space group. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(4), one O(7), one F(1), one F(2), and one F(5) atom to form distorted VO3F3 octahedra that share corners with three equivalent V(3)O3F3 octahedra and corners with three equivalent V(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 16-43°. The V(1)-O(2) bond length is 1.73 Å. The V(1)-O(4) bond length is 2.00 Å. The V(1)-O(7) bond length is 1.62 Å. The V(1)-F(1) bond length is 2.19 Å. The V(1)-F(2) bond length is 1.86 Å. The V(1)-F(5) bond length is 1.87 Å. In the second V site, V(2) is bonded to one O(2), one O(5), one O(6), one O(7), one F(2), and one F(4) atom to form distorted VO4F2 octahedra that share corners with three equivalent V(1)O3F3 octahedra and corners with three equivalent V(4)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 16-43°. The V(2)-O(2) bond length is 1.85 Å. The V(2)-O(5) bond length is 1.66 Å. The V(2)-O(6) bond length is 1.68 Å. The V(2)-O(7) bond length is 2.13 Å. The V(2)-F(2) bond length is 2.13 Å. The V(2)-F(4) bond length is 1.89 Å. In the third V site, V(3) is bonded to one O(1), one O(3), one O(4), one F(1), one F(3), and one F(5) atom to form distorted VO3F3 octahedra that share corners with three equivalent V(1)O3F3 octahedra and corners with three equivalent V(4)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 10-41°. The V(3)-O(1) bond length is 1.67 Å. The V(3)-O(3) bond length is 2.09 Å. The V(3)-O(4) bond length is 1.66 Å. The V(3)-F(1) bond length is 1.84 Å. The V(3)-F(3) bond length is 1.92 Å. The V(3)-F(5) bond length is 2.11 Å. In the fourth V site, V(4) is bonded to one O(1), one O(3), one O(5), one O(6), one F(3), and one F(4) atom to form VO4F2 octahedra that share corners with three equivalent V(3)O3F3 octahedra and corners with three equivalent V(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 10-28°. The V(4)-O(1) bond length is 1.89 Å. The V(4)-O(3) bond length is 1.63 Å. The V(4)-O(5) bond length is 1.94 Å. The V(4)-O(6) bond length is 1.89 Å. The V(4)-F(3) bond length is 1.96 Å. The V(4)-F(4) bond length is 2.09 Å. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a linear geometry to one V(3) and one V(4) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the third O site, O(3) is bonded in a distorted bent 150 degrees geometry to one V(3) and one V(4) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one V(1) and one V(3) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one V(2) and one V(4) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one V(2) and one V(4) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. There are five inequivalent F sites. In the first F site, F(1) is bonded in a distorted bent 150 degrees geometry to one V(1) and one V(3) atom. In the second F site, F(2) is bonded in a distorted linear geometry to one V(1) and one V(2) atom. In the third F site, F(3) is bonded in a linear geometry to one V(3) and one V(4) atom. In the fourth F site, F(4) is bonded in a linear geometry to one V(2) and one V(4) atom. In the fifth F site, F(5) is bonded in a bent 150 degrees geometry to one V(1) and one V(3) atom.