CaV8(OF)8 crystallizes in the triclinic P1 space group. Ca(1) is bonded to one O(3), one O(6), one O(7), one F(2), one F(3), and one F(5) atom to form distorted CaO3F3 octahedra that share  a cornercorner with one V(1)O3F3 octahedra,  a cornercorner with one V(2)O3F3 octahedra,  a cornercorner with one V(4)O3F3 octahedra,  a cornercorner with one V(3)O3F2 trigonal bipyramid, edges with two equivalent V(6)O3F3 octahedra,  an edgeedge with one V(3)O3F2 trigonal bipyramid, and  a faceface with one V(2)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 44-59°. There are eight inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(5), one O(8), one F(3), one F(4), and one F(6) atom to form VO3F3 octahedra that share  a cornercorner with one Ca(1)O3F3 octahedra, corners with two equivalent V(7)O3F3 octahedra, corners with four equivalent V(5)O3F3 octahedra,  an edgeedge with one V(2)O3F3 octahedra, and  an edgeedge with one V(4)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 43-60°. In the second V site, V(2) is bonded to one O(2), one O(3), one O(7), one F(3), one F(5), and one F(6) atom to form distorted VO3F3 octahedra that share  a cornercorner with one Ca(1)O3F3 octahedra, corners with two equivalent V(5)O3F3 octahedra, corners with two equivalent V(6)O3F3 octahedra,  a cornercorner with one V(3)O3F2 trigonal bipyramid,  an edgeedge with one V(1)O3F3 octahedra, and  a faceface with one Ca(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 49-59°. In the third V site, V(3) is bonded to one O(3), one O(4), one O(6), one F(2), and one F(7) atom to form distorted VO3F2 trigonal bipyramids that share  a cornercorner with one Ca(1)O3F3 octahedra,  a cornercorner with one V(2)O3F3 octahedra, corners with two equivalent V(7)O3F3 octahedra, corners with four equivalent V(6)O3F3 octahedra,  an edgeedge with one Ca(1)O3F3 octahedra, and  an edgeedge with one V(4)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 36-67°. In the fourth V site, V(4) is bonded to one O(4), one O(5), one O(6), one F(1), one F(4), and one F(8) atom to form VO3F3 octahedra that share  a cornercorner with one Ca(1)O3F3 octahedra, corners with two equivalent V(5)O3F3 octahedra, corners with two equivalent V(6)O3F3 octahedra, corners with four equivalent V(7)O3F3 octahedra,  an edgeedge with one V(1)O3F3 octahedra, and  an edgeedge with one V(3)O3F2 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 41-57°. In the fifth V site, V(5) is bonded to one O(1), one O(2), one O(8), one F(4), one F(6), and one F(8) atom to form a mixture of corner and edge-sharing VO3F3 octahedra. The corner-sharing octahedral tilt angles range from 43-54°. In the sixth V site, V(6) is bonded to one O(3), one O(6), one O(7), one F(1), one F(2), and one F(7) atom to form VO3F3 octahedra that share corners with two equivalent V(2)O3F3 octahedra, corners with two equivalent V(4)O3F3 octahedra, corners with four equivalent V(3)O3F2 trigonal bipyramids,  an edgeedge with one V(7)O3F3 octahedra, and edges with two equivalent Ca(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 49-58°. In the seventh V site, V(7) is bonded to one O(1), one O(4), one O(5), one F(1), one F(7), and one F(8) atom to form VO3F3 octahedra that share corners with two equivalent V(1)O3F3 octahedra, corners with four equivalent V(4)O3F3 octahedra, corners with two equivalent V(3)O3F2 trigonal bipyramids,  an edgeedge with one V(5)O3F3 octahedra, and  an edgeedge with one V(6)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 41-60°. In the eighth V site, V(8) is bonded in a 5-coordinate geometry to one O(2), one O(7), one O(8), one F(3), and one F(5) atom. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one V(1), one V(5), and one V(7) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one V(2), one V(5), and one V(8) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Ca(1), one V(2), one V(3), and one V(6) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one V(3), one V(4), and one V(7) atom. In the fifth O site, O(5) is bonded in a trigonal planar geometry to one V(1), one V(4), and one V(7) atom. In the sixth O site, O(6) is bonded in a distorted see-saw-like geometry to one Ca(1), one V(3), one V(4), and one V(6) atom. In the seventh O site, O(7) is bonded in a distorted trigonal pyramidal geometry to one Ca(1), one V(2), one V(6), and one V(8) atom. In the eighth O site, O(8) is bonded in a distorted T-shaped geometry to one V(1), one V(5), and one V(8) atom. There are eight inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to one V(4), one V(6), and one V(7) atom. In the second F site, F(2) is bonded in a 3-coordinate geometry to one Ca(1), one V(3), and one V(6) atom. In the third F site, F(3) is bonded in a 4-coordinate geometry to one Ca(1), one V(1), one V(2), and one V(8) atom. In the fourth F site, F(4) is bonded in a distorted trigonal planar geometry to one V(1), one V(4), and one V(5) atom. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to one Ca(1), one V(2), and one V(8) atom. In the sixth F site, F(6) is bonded in a trigonal planar geometry to one V(1), one V(2), and one V(5) atom. In the seventh F site, F(7) is bonded in a trigonal planar geometry to one V(3), one V(6), and one V(7) atom. In the eighth F site, F(8) is bonded in a distorted T-shaped geometry to one V(4), one V(5), and one V(7) atom.
CaV8(OF)8 crystallizes in the triclinic P1 space group. Ca(1) is bonded to one O(3), one O(6), one O(7), one F(2), one F(3), and one F(5) atom to form distorted CaO3F3 octahedra that share  a cornercorner with one V(1)O3F3 octahedra,  a cornercorner with one V(2)O3F3 octahedra,  a cornercorner with one V(4)O3F3 octahedra,  a cornercorner with one V(3)O3F2 trigonal bipyramid, edges with two equivalent V(6)O3F3 octahedra,  an edgeedge with one V(3)O3F2 trigonal bipyramid, and  a faceface with one V(2)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 44-59°. The Ca(1)-O(3) bond length is 2.22 Å. The Ca(1)-O(6) bond length is 2.26 Å. The Ca(1)-O(7) bond length is 2.18 Å. The Ca(1)-F(2) bond length is 2.17 Å. The Ca(1)-F(3) bond length is 2.46 Å. The Ca(1)-F(5) bond length is 2.25 Å. There are eight inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(5), one O(8), one F(3), one F(4), and one F(6) atom to form VO3F3 octahedra that share  a cornercorner with one Ca(1)O3F3 octahedra, corners with two equivalent V(7)O3F3 octahedra, corners with four equivalent V(5)O3F3 octahedra,  an edgeedge with one V(2)O3F3 octahedra, and  an edgeedge with one V(4)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 43-60°. The V(1)-O(1) bond length is 2.00 Å. The V(1)-O(5) bond length is 1.97 Å. The V(1)-O(8) bond length is 1.97 Å. The V(1)-F(3) bond length is 2.25 Å. The V(1)-F(4) bond length is 2.10 Å. The V(1)-F(6) bond length is 2.10 Å. In the second V site, V(2) is bonded to one O(2), one O(3), one O(7), one F(3), one F(5), and one F(6) atom to form distorted VO3F3 octahedra that share  a cornercorner with one Ca(1)O3F3 octahedra, corners with two equivalent V(5)O3F3 octahedra, corners with two equivalent V(6)O3F3 octahedra,  a cornercorner with one V(3)O3F2 trigonal bipyramid,  an edgeedge with one V(1)O3F3 octahedra, and  a faceface with one Ca(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 49-59°. The V(2)-O(2) bond length is 2.03 Å. The V(2)-O(3) bond length is 2.23 Å. The V(2)-O(7) bond length is 2.39 Å. The V(2)-F(3) bond length is 2.15 Å. The V(2)-F(5) bond length is 2.03 Å. The V(2)-F(6) bond length is 2.17 Å. In the third V site, V(3) is bonded to one O(3), one O(4), one O(6), one F(2), and one F(7) atom to form distorted VO3F2 trigonal bipyramids that share  a cornercorner with one Ca(1)O3F3 octahedra,  a cornercorner with one V(2)O3F3 octahedra, corners with two equivalent V(7)O3F3 octahedra, corners with four equivalent V(6)O3F3 octahedra,  an edgeedge with one Ca(1)O3F3 octahedra, and  an edgeedge with one V(4)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 36-67°. The V(3)-O(3) bond length is 1.92 Å. The V(3)-O(4) bond length is 1.90 Å. The V(3)-O(6) bond length is 2.04 Å. The V(3)-F(2) bond length is 2.23 Å. The V(3)-F(7) bond length is 2.03 Å. In the fourth V site, V(4) is bonded to one O(4), one O(5), one O(6), one F(1), one F(4), and one F(8) atom to form VO3F3 octahedra that share  a cornercorner with one Ca(1)O3F3 octahedra, corners with two equivalent V(5)O3F3 octahedra, corners with two equivalent V(6)O3F3 octahedra, corners with four equivalent V(7)O3F3 octahedra,  an edgeedge with one V(1)O3F3 octahedra, and  an edgeedge with one V(3)O3F2 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 41-57°. The V(4)-O(4) bond length is 2.02 Å. The V(4)-O(5) bond length is 2.04 Å. The V(4)-O(6) bond length is 2.02 Å. The V(4)-F(1) bond length is 2.05 Å. The V(4)-F(4) bond length is 2.13 Å. The V(4)-F(8) bond length is 2.08 Å. In the fifth V site, V(5) is bonded to one O(1), one O(2), one O(8), one F(4), one F(6), and one F(8) atom to form a mixture of corner and edge-sharing VO3F3 octahedra. The corner-sharing octahedral tilt angles range from 43-54°. The V(5)-O(1) bond length is 2.09 Å. The V(5)-O(2) bond length is 1.92 Å. The V(5)-O(8) bond length is 2.10 Å. The V(5)-F(4) bond length is 2.09 Å. The V(5)-F(6) bond length is 2.07 Å. The V(5)-F(8) bond length is 2.16 Å. In the sixth V site, V(6) is bonded to one O(3), one O(6), one O(7), one F(1), one F(2), and one F(7) atom to form VO3F3 octahedra that share corners with two equivalent V(2)O3F3 octahedra, corners with two equivalent V(4)O3F3 octahedra, corners with four equivalent V(3)O3F2 trigonal bipyramids,  an edgeedge with one V(7)O3F3 octahedra, and edges with two equivalent Ca(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 49-58°. The V(6)-O(3) bond length is 2.30 Å. The V(6)-O(6) bond length is 2.25 Å. The V(6)-O(7) bond length is 2.16 Å. The V(6)-F(1) bond length is 2.17 Å. The V(6)-F(2) bond length is 2.15 Å. The V(6)-F(7) bond length is 2.12 Å. In the seventh V site, V(7) is bonded to one O(1), one O(4), one O(5), one F(1), one F(7), and one F(8) atom to form VO3F3 octahedra that share corners with two equivalent V(1)O3F3 octahedra, corners with four equivalent V(4)O3F3 octahedra, corners with two equivalent V(3)O3F2 trigonal bipyramids,  an edgeedge with one V(5)O3F3 octahedra, and  an edgeedge with one V(6)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 41-60°. The V(7)-O(1) bond length is 1.91 Å. The V(7)-O(4) bond length is 2.05 Å. The V(7)-O(5) bond length is 2.03 Å. The V(7)-F(1) bond length is 2.10 Å. The V(7)-F(7) bond length is 2.14 Å. The V(7)-F(8) bond length is 2.11 Å. In the eighth V site, V(8) is bonded in a 5-coordinate geometry to one O(2), one O(7), one O(8), one F(3), and one F(5) atom. The V(8)-O(2) bond length is 1.98 Å. The V(8)-O(7) bond length is 1.94 Å. The V(8)-O(8) bond length is 1.88 Å. The V(8)-F(3) bond length is 2.17 Å. The V(8)-F(5) bond length is 2.04 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one V(1), one V(5), and one V(7) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one V(2), one V(5), and one V(8) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Ca(1), one V(2), one V(3), and one V(6) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one V(3), one V(4), and one V(7) atom. In the fifth O site, O(5) is bonded in a trigonal planar geometry to one V(1), one V(4), and one V(7) atom. In the sixth O site, O(6) is bonded in a distorted see-saw-like geometry to one Ca(1), one V(3), one V(4), and one V(6) atom. In the seventh O site, O(7) is bonded in a distorted trigonal pyramidal geometry to one Ca(1), one V(2), one V(6), and one V(8) atom. In the eighth O site, O(8) is bonded in a distorted T-shaped geometry to one V(1), one V(5), and one V(8) atom. There are eight inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to one V(4), one V(6), and one V(7) atom. In the second F site, F(2) is bonded in a 3-coordinate geometry to one Ca(1), one V(3), and one V(6) atom. In the third F site, F(3) is bonded in a 4-coordinate geometry to one Ca(1), one V(1), one V(2), and one V(8) atom. In the fourth F site, F(4) is bonded in a distorted trigonal planar geometry to one V(1), one V(4), and one V(5) atom. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to one Ca(1), one V(2), and one V(8) atom. In the sixth F site, F(6) is bonded in a trigonal planar geometry to one V(1), one V(2), and one V(5) atom. In the seventh F site, F(7) is bonded in a trigonal planar geometry to one V(3), one V(6), and one V(7) atom. In the eighth F site, F(8) is bonded in a distorted T-shaped geometry to one V(4), one V(5), and one V(7) atom.