CaV6O11F crystallizes in the triclinic P1 space group. Ca(1) is bonded in a 3-coordinate geometry to one O(2), one O(3), one O(9), and two equivalent O(6) 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 distorted VO5 trigonal bipyramids that share corners with three equivalent V(5)O4F trigonal bipyramids, corners with three equivalent V(4)O5 trigonal bipyramids, and  an edgeedge with one V(2)O6 octahedra. 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 distorted VO6 octahedra that share corners with two equivalent V(6)O5 trigonal bipyramids, corners with three equivalent V(4)O5 trigonal bipyramids,  an edgeedge with one V(3)O4F trigonal bipyramid,  an edgeedge with one V(1)O5 trigonal bipyramid, and  an edgeedge with one V(6)O5 trigonal bipyramid. 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  a cornercorner with one V(6)O5 trigonal bipyramid, corners with two equivalent V(5)O4F trigonal bipyramids,  an edgeedge with one V(2)O6 octahedra, and  an edgeedge with one V(6)O5 trigonal bipyramid. In the fourth V site, V(4) is bonded to one O(10), one O(4), one O(5), one O(7), and one O(8) atom to form distorted VO5 trigonal bipyramids that share corners with three equivalent V(2)O6 octahedra, corners with three equivalent V(1)O5 trigonal bipyramids,  an edgeedge with one V(5)O4F trigonal bipyramid, and  an edgeedge with one V(6)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 40-52°. In the fifth V site, V(5) is bonded to one O(3), one O(4), one O(6), one O(7), and one F(1) atom to form distorted VO4F trigonal bipyramids that share corners with two equivalent V(3)O4F trigonal bipyramids, corners with three equivalent V(1)O5 trigonal bipyramids, and  an edgeedge with one V(4)O5 trigonal bipyramid. In the sixth V site, V(6) is bonded to one O(11), one O(2), one O(5), one O(8), and one O(9) atom to form distorted VO5 trigonal bipyramids that share corners with two equivalent V(2)O6 octahedra,  a cornercorner with one V(3)O4F trigonal bipyramid,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(3)O4F trigonal bipyramid, and  an edgeedge with one V(4)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 34-53°. There are eleven inequivalent O sites. In the first O site, O(1) is bonded in a distorted water-like geometry to one V(1) and one V(2) atom. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Ca(1), one V(2), one V(3), and one V(6) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Ca(1), one V(1), and one V(5) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one V(1), one V(4), and one V(5) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one V(2), one V(4), and one V(6) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to two equivalent Ca(1), one V(3), and one V(5) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one V(1), one V(4), and one V(5) atom. In the eighth O site, O(8) is bonded in a distorted trigonal non-coplanar 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(6) 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 bent 150 degrees geometry to one V(3) and one V(5) atom.
CaV6O11F crystallizes in the triclinic P1 space group. Ca(1) is bonded in a 3-coordinate geometry to one O(2), one O(3), one O(9), and two equivalent O(6) atoms. The Ca(1)-O(2) bond length is 2.29 Å. The Ca(1)-O(3) bond length is 2.31 Å. The Ca(1)-O(9) bond length is 2.20 Å. There is one shorter (2.51 Å) and one longer (2.70 Å) Ca(1)-O(6) 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 distorted VO5 trigonal bipyramids that share corners with three equivalent V(5)O4F trigonal bipyramids, corners with three equivalent V(4)O5 trigonal bipyramids, and  an edgeedge with one V(2)O6 octahedra. The V(1)-O(1) bond length is 1.67 Å. The V(1)-O(10) bond length is 2.08 Å. The V(1)-O(3) bond length is 1.82 Å. The V(1)-O(4) bond length is 1.92 Å. The V(1)-O(7) bond length is 1.85 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 distorted VO6 octahedra that share corners with two equivalent V(6)O5 trigonal bipyramids, corners with three equivalent V(4)O5 trigonal bipyramids,  an edgeedge with one V(3)O4F trigonal bipyramid,  an edgeedge with one V(1)O5 trigonal bipyramid, and  an edgeedge with one V(6)O5 trigonal bipyramid. The V(2)-O(1) bond length is 2.15 Å. The V(2)-O(10) bond length is 2.05 Å. The V(2)-O(11) bond length is 1.99 Å. The V(2)-O(2) bond length is 1.99 Å. The V(2)-O(5) bond length is 1.82 Å. The V(2)-O(8) bond length is 2.01 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  a cornercorner with one V(6)O5 trigonal bipyramid, corners with two equivalent V(5)O4F trigonal bipyramids,  an edgeedge with one V(2)O6 octahedra, and  an edgeedge with one V(6)O5 trigonal bipyramid. The V(3)-O(11) bond length is 1.93 Å. The V(3)-O(2) bond length is 2.06 Å. The V(3)-O(6) bond length is 1.87 Å. The V(3)-O(9) bond length is 1.95 Å. The V(3)-F(1) bond length is 2.06 Å. In the fourth V site, V(4) is bonded to one O(10), one O(4), one O(5), one O(7), and one O(8) atom to form distorted VO5 trigonal bipyramids that share corners with three equivalent V(2)O6 octahedra, corners with three equivalent V(1)O5 trigonal bipyramids,  an edgeedge with one V(5)O4F trigonal bipyramid, and  an edgeedge with one V(6)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 40-52°. The V(4)-O(10) bond length is 1.96 Å. The V(4)-O(4) bond length is 1.95 Å. The V(4)-O(5) bond length is 2.23 Å. The V(4)-O(7) bond length is 2.12 Å. The V(4)-O(8) bond length is 1.93 Å. In the fifth V site, V(5) is bonded to one O(3), one O(4), one O(6), one O(7), and one F(1) atom to form distorted VO4F trigonal bipyramids that share corners with two equivalent V(3)O4F trigonal bipyramids, corners with three equivalent V(1)O5 trigonal bipyramids, and  an edgeedge with one V(4)O5 trigonal bipyramid. The V(5)-O(3) bond length is 1.98 Å. The V(5)-O(4) bond length is 1.99 Å. The V(5)-O(6) bond length is 1.93 Å. The V(5)-O(7) bond length is 2.00 Å. The V(5)-F(1) bond length is 2.03 Å. In the sixth V site, V(6) is bonded to one O(11), one O(2), one O(5), one O(8), and one O(9) atom to form distorted VO5 trigonal bipyramids that share corners with two equivalent V(2)O6 octahedra,  a cornercorner with one V(3)O4F trigonal bipyramid,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(3)O4F trigonal bipyramid, and  an edgeedge with one V(4)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 34-53°. The V(6)-O(11) bond length is 1.92 Å. The V(6)-O(2) bond length is 2.12 Å. The V(6)-O(5) bond length is 2.03 Å. The V(6)-O(8) bond length is 1.90 Å. The V(6)-O(9) bond length is 1.94 Å. There are eleven inequivalent O sites. In the first O site, O(1) is bonded in a distorted water-like geometry to one V(1) and one V(2) atom. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Ca(1), one V(2), one V(3), and one V(6) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Ca(1), one V(1), and one V(5) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one V(1), one V(4), and one V(5) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one V(2), one V(4), and one V(6) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to two equivalent Ca(1), one V(3), and one V(5) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one V(1), one V(4), and one V(5) atom. In the eighth O site, O(8) is bonded in a distorted trigonal non-coplanar 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(6) 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 bent 150 degrees geometry to one V(3) and one V(5) atom.