CaV6O11F crystallizes in the triclinic P1 space group. Ca(1) is bonded in a 7-coordinate geometry to one O(6), one O(7), one O(9), two equivalent O(3), and two equivalent F(1) atoms. There are six inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(10), one O(3), one O(4), and one O(7) atom to form a mixture of distorted corner and edge-sharing VO5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 46-60°. In the second V site, V(2) is bonded to one O(1), one O(10), one O(11), one O(2), one O(5), and one O(8) atom to form VO6 octahedra that share corners with four equivalent V(4)O6 octahedra, corners with four equivalent V(6)O5 trigonal bipyramids,  an edgeedge with one V(3)O4F trigonal bipyramid, and  an edgeedge with one V(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 44-49°. In the third V site, V(3) is bonded to one O(11), one O(2), one O(6), one O(9), and one F(1) atom to form distorted VO4F trigonal bipyramids that share corners with three equivalent V(6)O5 trigonal bipyramids and  an edgeedge with one V(2)O6 octahedra. In the fourth V site, V(4) is bonded to one O(1), one O(10), one O(4), one O(5), one O(7), and one O(8) atom to form VO6 octahedra that share corners with four equivalent V(2)O6 octahedra, corners with four equivalent V(1)O5 trigonal bipyramids, and  an edgeedge with one V(6)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 44-49°. In the fifth V site, V(5) is bonded in a 6-coordinate geometry to one O(4), one O(7), one O(9), two equivalent O(3), and one F(1) atom. In the sixth V site, V(6) is bonded to one O(11), one O(2), one O(5), one O(6), and one O(8) atom to form VO5 trigonal bipyramids that share corners with four equivalent V(2)O6 octahedra, corners with three equivalent V(3)O4F trigonal bipyramids, and  an edgeedge with one V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 50-57°. There are eleven inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one V(1), one V(2), and one V(4) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one V(2), one V(3), and one V(6) atom. In the third O site, O(3) is bonded to two equivalent Ca(1), one V(1), and two equivalent V(5) atoms to form distorted corner-sharing OCa2V3 trigonal bipyramids. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one V(1), one V(4), and one V(5) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one V(2), one V(4), and one V(6) atom. In the sixth O site, O(6) is bonded in a trigonal planar geometry to one Ca(1), one V(3), and one V(6) atom. In the seventh O site, O(7) is bonded in a distorted rectangular see-saw-like geometry to one Ca(1), one V(1), one V(4), and one V(5) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one V(2), one V(4), and one V(6) atom. In the ninth O site, O(9) is bonded in a distorted trigonal non-coplanar geometry to one Ca(1), one V(3), and one V(5) atom. In the tenth O site, O(10) is bonded in a distorted T-shaped geometry to one V(1), one V(2), and one V(4) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one V(2), one V(3), and one V(6) atom. F(1) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Ca(1), one V(3), and one V(5) atom.
CaV6O11F crystallizes in the triclinic P1 space group. Ca(1) is bonded in a 7-coordinate geometry to one O(6), one O(7), one O(9), two equivalent O(3), and two equivalent F(1) atoms. The Ca(1)-O(6) bond length is 2.25 Å. The Ca(1)-O(7) bond length is 2.84 Å. The Ca(1)-O(9) bond length is 2.42 Å. There is one shorter (2.43 Å) and one longer (2.63 Å) Ca(1)-O(3) bond length. There is one shorter (2.43 Å) and one longer (2.48 Å) Ca(1)-F(1) bond length. There are six inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(10), one O(3), one O(4), and one O(7) atom to form a mixture of distorted corner and edge-sharing VO5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 46-60°. The V(1)-O(1) bond length is 1.84 Å. The V(1)-O(10) bond length is 1.77 Å. The V(1)-O(3) bond length is 1.87 Å. The V(1)-O(4) bond length is 2.00 Å. The V(1)-O(7) bond length is 2.07 Å. In the second V site, V(2) is bonded to one O(1), one O(10), one O(11), one O(2), one O(5), and one O(8) atom to form VO6 octahedra that share corners with four equivalent V(4)O6 octahedra, corners with four equivalent V(6)O5 trigonal bipyramids,  an edgeedge with one V(3)O4F trigonal bipyramid, and  an edgeedge with one V(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 44-49°. The V(2)-O(1) bond length is 2.03 Å. The V(2)-O(10) bond length is 2.07 Å. The V(2)-O(11) bond length is 2.03 Å. The V(2)-O(2) bond length is 2.04 Å. The V(2)-O(5) bond length is 2.08 Å. The V(2)-O(8) bond length is 2.06 Å. In the third V site, V(3) is bonded to one O(11), one O(2), one O(6), one O(9), and one F(1) atom to form distorted VO4F trigonal bipyramids that share corners with three equivalent V(6)O5 trigonal bipyramids and  an edgeedge with one V(2)O6 octahedra. The V(3)-O(11) bond length is 1.93 Å. The V(3)-O(2) bond length is 2.01 Å. The V(3)-O(6) bond length is 1.89 Å. The V(3)-O(9) bond length is 1.88 Å. The V(3)-F(1) bond length is 2.48 Å. In the fourth V site, V(4) is bonded to one O(1), one O(10), one O(4), one O(5), one O(7), and one O(8) atom to form VO6 octahedra that share corners with four equivalent V(2)O6 octahedra, corners with four equivalent V(1)O5 trigonal bipyramids, and  an edgeedge with one V(6)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 44-49°. The V(4)-O(1) bond length is 1.90 Å. The V(4)-O(10) bond length is 1.98 Å. The V(4)-O(4) bond length is 1.94 Å. The V(4)-O(5) bond length is 2.05 Å. The V(4)-O(7) bond length is 2.09 Å. The V(4)-O(8) bond length is 1.91 Å. In the fifth V site, V(5) is bonded in a 6-coordinate geometry to one O(4), one O(7), one O(9), two equivalent O(3), and one F(1) atom. The V(5)-O(4) bond length is 2.08 Å. The V(5)-O(7) bond length is 1.98 Å. The V(5)-O(9) bond length is 1.90 Å. There is one shorter (2.12 Å) and one longer (2.50 Å) V(5)-O(3) bond length. The V(5)-F(1) bond length is 2.01 Å. In the sixth V site, V(6) is bonded to one O(11), one O(2), one O(5), one O(6), and one O(8) atom to form VO5 trigonal bipyramids that share corners with four equivalent V(2)O6 octahedra, corners with three equivalent V(3)O4F trigonal bipyramids, and  an edgeedge with one V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 50-57°. The V(6)-O(11) bond length is 1.94 Å. The V(6)-O(2) bond length is 1.90 Å. The V(6)-O(5) bond length is 1.84 Å. The V(6)-O(6) bond length is 1.93 Å. The V(6)-O(8) bond length is 2.04 Å. There are eleven inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one V(1), one V(2), and one V(4) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one V(2), one V(3), and one V(6) atom. In the third O site, O(3) is bonded to two equivalent Ca(1), one V(1), and two equivalent V(5) atoms to form distorted corner-sharing OCa2V3 trigonal bipyramids. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one V(1), one V(4), and one V(5) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one V(2), one V(4), and one V(6) atom. In the sixth O site, O(6) is bonded in a trigonal planar geometry to one Ca(1), one V(3), and one V(6) atom. In the seventh O site, O(7) is bonded in a distorted rectangular see-saw-like geometry to one Ca(1), one V(1), one V(4), and one V(5) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one V(2), one V(4), and one V(6) atom. In the ninth O site, O(9) is bonded in a distorted trigonal non-coplanar geometry to one Ca(1), one V(3), and one V(5) atom. In the tenth O site, O(10) is bonded in a distorted T-shaped geometry to one V(1), one V(2), and one V(4) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one V(2), one V(3), and one V(6) atom. F(1) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Ca(1), one V(3), and one V(5) atom.