V6F13 crystallizes in the triclinic P-1 space group. There are six inequivalent V sites. In the first V site, V(1) is bonded to one F(1), one F(12), one F(13), one F(2), one F(6), and one F(8) atom to form a mixture of edge and corner-sharing VF6 octahedra. The corner-sharing octahedral tilt angles range from 38-51°. In the second V site, V(2) is bonded to one F(1), one F(13), one F(3), one F(4), and two equivalent F(7) atoms to form a mixture of edge and corner-sharing VF6 octahedra. The corner-sharing octahedral tilt angles range from 47-54°. In the third V site, V(3) is bonded to one F(11), one F(2), one F(5), one F(8), and two equivalent F(9) atoms to form a mixture of edge, face, and corner-sharing VF6 octahedra. The corner-sharing octahedral tilt angles range from 38-46°. In the fourth V site, V(4) is bonded to one F(1), one F(10), one F(4), one F(6), and two equivalent F(3) atoms to form a mixture of edge and corner-sharing VF6 octahedra. The corner-sharing octahedral tilt angles range from 47-57°. In the fifth V site, V(5) is bonded to one F(10), one F(11), one F(12), one F(5), one F(6), and one F(7) atom to form a mixture of edge and corner-sharing VF6 octahedra. The corner-sharing octahedral tilt angles range from 42-50°. In the sixth V site, V(6) is bonded to one F(10), one F(11), one F(13), one F(4), one F(8), and one F(9) atom to form a mixture of edge, face, and corner-sharing VF6 octahedra. The corner-sharing octahedral tilt angles range from 45-57°. There are thirteen inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one V(1), one V(2), and one V(4) atom. In the second F site, F(2) is bonded in a distorted bent 120 degrees geometry to one V(1) and one V(3) atom. In the third F site, F(3) is bonded in a trigonal non-coplanar geometry to one V(2) and two equivalent V(4) atoms. In the fourth F site, F(4) is bonded in a trigonal planar geometry to one V(2), one V(4), and one V(6) atom. In the fifth F site, F(5) is bonded in a bent 150 degrees geometry to one V(3) and one V(5) atom. In the sixth F site, F(6) is bonded in a distorted trigonal planar geometry to one V(1), one V(4), and one V(5) atom. In the seventh F site, F(7) is bonded in a distorted trigonal planar geometry to one V(5) and two equivalent V(2) atoms. In the eighth F site, F(8) is bonded in a T-shaped geometry to one V(1), one V(3), and one V(6) atom. In the ninth F site, F(9) is bonded in a T-shaped geometry to one V(6) and two equivalent V(3) atoms. In the tenth F site, F(10) is bonded in a trigonal planar geometry to one V(4), one V(5), and one V(6) atom. In the eleventh F site, F(11) is bonded in a T-shaped geometry to one V(3), one V(5), and one V(6) atom. In the twelfth F site, F(12) is bonded in a water-like geometry to one V(1) and one V(5) atom. In the thirteenth F site, F(13) is bonded in a distorted trigonal planar geometry to one V(1), one V(2), and one V(6) atom.
V6F13 crystallizes in the triclinic P-1 space group. There are six inequivalent V sites. In the first V site, V(1) is bonded to one F(1), one F(12), one F(13), one F(2), one F(6), and one F(8) atom to form a mixture of edge and corner-sharing VF6 octahedra. The corner-sharing octahedral tilt angles range from 38-51°. The V(1)-F(1) bond length is 2.16 Å. The V(1)-F(12) bond length is 2.05 Å. The V(1)-F(13) bond length is 2.17 Å. The V(1)-F(2) bond length is 2.03 Å. The V(1)-F(6) bond length is 2.17 Å. The V(1)-F(8) bond length is 2.11 Å. In the second V site, V(2) is bonded to one F(1), one F(13), one F(3), one F(4), and two equivalent F(7) atoms to form a mixture of edge and corner-sharing VF6 octahedra. The corner-sharing octahedral tilt angles range from 47-54°. The V(2)-F(1) bond length is 2.13 Å. The V(2)-F(13) bond length is 2.14 Å. The V(2)-F(3) bond length is 2.11 Å. The V(2)-F(4) bond length is 2.15 Å. There is one shorter (2.13 Å) and one longer (2.16 Å) V(2)-F(7) bond length. In the third V site, V(3) is bonded to one F(11), one F(2), one F(5), one F(8), and two equivalent F(9) atoms to form a mixture of edge, face, and corner-sharing VF6 octahedra. The corner-sharing octahedral tilt angles range from 38-46°. The V(3)-F(11) bond length is 2.22 Å. The V(3)-F(2) bond length is 2.01 Å. The V(3)-F(5) bond length is 2.04 Å. The V(3)-F(8) bond length is 2.25 Å. There is one shorter (2.12 Å) and one longer (2.23 Å) V(3)-F(9) bond length. In the fourth V site, V(4) is bonded to one F(1), one F(10), one F(4), one F(6), and two equivalent F(3) atoms to form a mixture of edge and corner-sharing VF6 octahedra. The corner-sharing octahedral tilt angles range from 47-57°. The V(4)-F(1) bond length is 2.18 Å. The V(4)-F(10) bond length is 2.13 Å. The V(4)-F(4) bond length is 2.14 Å. The V(4)-F(6) bond length is 2.19 Å. There is one shorter (2.13 Å) and one longer (2.18 Å) V(4)-F(3) bond length. In the fifth V site, V(5) is bonded to one F(10), one F(11), one F(12), one F(5), one F(6), and one F(7) atom to form a mixture of edge and corner-sharing VF6 octahedra. The corner-sharing octahedral tilt angles range from 42-50°. The V(5)-F(10) bond length is 2.15 Å. The V(5)-F(11) bond length is 2.10 Å. The V(5)-F(12) bond length is 2.01 Å. The V(5)-F(5) bond length is 1.99 Å. The V(5)-F(6) bond length is 2.16 Å. The V(5)-F(7) bond length is 2.14 Å. In the sixth V site, V(6) is bonded to one F(10), one F(11), one F(13), one F(4), one F(8), and one F(9) atom to form a mixture of edge, face, and corner-sharing VF6 octahedra. The corner-sharing octahedral tilt angles range from 45-57°. The V(6)-F(10) bond length is 2.13 Å. The V(6)-F(11) bond length is 2.12 Å. The V(6)-F(13) bond length is 2.10 Å. The V(6)-F(4) bond length is 2.13 Å. The V(6)-F(8) bond length is 2.15 Å. The V(6)-F(9) bond length is 2.12 Å. There are thirteen inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one V(1), one V(2), and one V(4) atom. In the second F site, F(2) is bonded in a distorted bent 120 degrees geometry to one V(1) and one V(3) atom. In the third F site, F(3) is bonded in a trigonal non-coplanar geometry to one V(2) and two equivalent V(4) atoms. In the fourth F site, F(4) is bonded in a trigonal planar geometry to one V(2), one V(4), and one V(6) atom. In the fifth F site, F(5) is bonded in a bent 150 degrees geometry to one V(3) and one V(5) atom. In the sixth F site, F(6) is bonded in a distorted trigonal planar geometry to one V(1), one V(4), and one V(5) atom. In the seventh F site, F(7) is bonded in a distorted trigonal planar geometry to one V(5) and two equivalent V(2) atoms. In the eighth F site, F(8) is bonded in a T-shaped geometry to one V(1), one V(3), and one V(6) atom. In the ninth F site, F(9) is bonded in a T-shaped geometry to one V(6) and two equivalent V(3) atoms. In the tenth F site, F(10) is bonded in a trigonal planar geometry to one V(4), one V(5), and one V(6) atom. In the eleventh F site, F(11) is bonded in a T-shaped geometry to one V(3), one V(5), and one V(6) atom. In the twelfth F site, F(12) is bonded in a water-like geometry to one V(1) and one V(5) atom. In the thirteenth F site, F(13) is bonded in a distorted trigonal planar geometry to one V(1), one V(2), and one V(6) atom.