CaV8(OF)8 crystallizes in the triclinic P1 space group. Ca(1) is bonded to one O(3), one O(4), one O(5), one O(7), one F(2), and one F(8) atom to form CaO4F2 octahedra that share  a cornercorner with one V(1)O3F3 octahedra,  a cornercorner with one V(3)O3F3 octahedra,  a cornercorner with one V(2)O4F2 octahedra, edges with two equivalent V(7)O2F4 octahedra, edges with two equivalent V(5)O3F3 octahedra, and  a faceface with one V(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 47-59°. There are eight inequivalent V sites. In the first V site, V(1) is bonded to one O(4), one O(5), one O(7), one F(2), one F(4), and one F(7) atom to form distorted VO3F3 octahedra that share  a cornercorner with one Ca(1)O4F2 octahedra, corners with two equivalent V(7)O2F4 octahedra, corners with two equivalent V(8)O2F4 octahedra, corners with four equivalent V(5)O3F3 octahedra,  an edgeedge with one V(2)O4F2 octahedra, and  a faceface with one Ca(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 46-59°. In the second V site, V(2) is bonded to one O(1), one O(2), one O(7), one O(8), one F(4), and one F(5) atom to form VO4F2 octahedra that share  a cornercorner with one Ca(1)O4F2 octahedra, corners with two equivalent V(5)O3F3 octahedra, corners with two equivalent V(6)O3F3 octahedra, corners with four equivalent V(8)O2F4 octahedra,  an edgeedge with one V(1)O3F3 octahedra, and  an edgeedge with one V(3)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 41-57°. In the third V site, V(3) is bonded to one O(2), one O(3), one O(6), one F(3), one F(5), and one F(6) atom to form VO3F3 octahedra that share  a cornercorner with one Ca(1)O4F2 octahedra, corners with two equivalent V(7)O2F4 octahedra, corners with two equivalent V(8)O2F4 octahedra, corners with four equivalent V(6)O3F3 octahedra, and  an edgeedge with one V(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 42-57°. In the fourth V site, V(4) is bonded in a 5-coordinate geometry to one O(3), one O(4), one O(5), one O(6), and one F(1) atom. In the fifth V site, V(5) is bonded to one O(1), one O(4), one O(7), one F(2), one F(7), and one F(8) atom to form VO3F3 octahedra that share corners with two equivalent V(2)O4F2 octahedra, corners with four equivalent V(1)O3F3 octahedra,  an edgeedge with one V(7)O2F4 octahedra,  an edgeedge with one V(8)O2F4 octahedra, and edges with two equivalent Ca(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 49-59°. In the sixth V site, V(6) is bonded to one O(2), one O(6), one O(8), one F(1), one F(3), and one F(6) atom to form VO3F3 octahedra that share corners with two equivalent V(2)O4F2 octahedra, corners with four equivalent V(3)O3F3 octahedra,  an edgeedge with one V(7)O2F4 octahedra, and  an edgeedge with one V(8)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 42-57°. In the seventh V site, V(7) is bonded to one O(3), one O(5), one F(1), one F(2), one F(6), and one F(8) atom to form VO2F4 octahedra that share corners with two equivalent V(1)O3F3 octahedra, corners with two equivalent V(3)O3F3 octahedra,  an edgeedge with one V(5)O3F3 octahedra,  an edgeedge with one V(6)O3F3 octahedra, and edges with two equivalent Ca(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 51-57°. In the eighth V site, V(8) is bonded to one O(1), one O(8), one F(3), one F(4), one F(5), and one F(7) atom to form VO2F4 octahedra that share corners with two equivalent V(1)O3F3 octahedra, corners with two equivalent V(3)O3F3 octahedra, corners with four equivalent V(2)O4F2 octahedra,  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 41-56°. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one V(2), one V(5), and one V(8) atom. In the second O site, O(2) is bonded in a 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 one Ca(1), one V(3), one V(4), and one V(7) atom to form distorted OCaV3 trigonal pyramids that share  an edgeedge with one F(2)CaV3 trigonal pyramid. In the fourth O site, O(4) is bonded in a distorted see-saw-like geometry to one Ca(1), one V(1), one V(4), and one V(5) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Ca(1), one V(1), one V(4), and one V(7) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one V(3), one V(4), and one V(6) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Ca(1), one V(1), one V(2), 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(6), 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 to one Ca(1), one V(1), one V(5), and one V(7) atom to form distorted FCaV3 trigonal pyramids that share  an edgeedge with one O(3)CaV3 trigonal pyramid. In the third F site, F(3) is bonded in a distorted T-shaped geometry to one V(3), one V(6), and one V(8) atom. In the fourth F site, F(4) is bonded in a trigonal planar geometry to one V(1), one V(2), and one V(8) atom. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to one V(2), one V(3), and one V(8) atom. In the sixth F site, F(6) is bonded in a distorted trigonal planar geometry to one V(3), one V(6), and one V(7) atom. In the seventh F site, F(7) is bonded in a distorted trigonal planar geometry to one V(1), one V(5), and one V(8) atom. In the eighth F site, F(8) is bonded in a 3-coordinate geometry to one Ca(1), 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(4), one O(5), one O(7), one F(2), and one F(8) atom to form CaO4F2 octahedra that share  a cornercorner with one V(1)O3F3 octahedra,  a cornercorner with one V(3)O3F3 octahedra,  a cornercorner with one V(2)O4F2 octahedra, edges with two equivalent V(7)O2F4 octahedra, edges with two equivalent V(5)O3F3 octahedra, and  a faceface with one V(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 47-59°. The Ca(1)-O(3) bond length is 2.30 Å. The Ca(1)-O(4) bond length is 2.18 Å. The Ca(1)-O(5) bond length is 2.28 Å. The Ca(1)-O(7) bond length is 2.32 Å. The Ca(1)-F(2) bond length is 2.18 Å. The Ca(1)-F(8) bond length is 2.12 Å. There are eight inequivalent V sites. In the first V site, V(1) is bonded to one O(4), one O(5), one O(7), one F(2), one F(4), and one F(7) atom to form distorted VO3F3 octahedra that share  a cornercorner with one Ca(1)O4F2 octahedra, corners with two equivalent V(7)O2F4 octahedra, corners with two equivalent V(8)O2F4 octahedra, corners with four equivalent V(5)O3F3 octahedra,  an edgeedge with one V(2)O4F2 octahedra, and  a faceface with one Ca(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 46-59°. The V(1)-O(4) bond length is 2.03 Å. The V(1)-O(5) bond length is 2.17 Å. The V(1)-O(7) bond length is 2.28 Å. The V(1)-F(2) bond length is 2.44 Å. The V(1)-F(4) bond length is 2.13 Å. The V(1)-F(7) bond length is 2.10 Å. In the second V site, V(2) is bonded to one O(1), one O(2), one O(7), one O(8), one F(4), and one F(5) atom to form VO4F2 octahedra that share  a cornercorner with one Ca(1)O4F2 octahedra, corners with two equivalent V(5)O3F3 octahedra, corners with two equivalent V(6)O3F3 octahedra, corners with four equivalent V(8)O2F4 octahedra,  an edgeedge with one V(1)O3F3 octahedra, and  an edgeedge with one V(3)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 41-57°. The V(2)-O(1) bond length is 2.19 Å. The V(2)-O(2) bond length is 2.00 Å. The V(2)-O(7) bond length is 2.02 Å. The V(2)-O(8) bond length is 2.19 Å. The V(2)-F(4) bond length is 2.08 Å. The V(2)-F(5) bond length is 2.09 Å. In the third V site, V(3) is bonded to one O(2), one O(3), one O(6), one F(3), one F(5), and one F(6) atom to form VO3F3 octahedra that share  a cornercorner with one Ca(1)O4F2 octahedra, corners with two equivalent V(7)O2F4 octahedra, corners with two equivalent V(8)O2F4 octahedra, corners with four equivalent V(6)O3F3 octahedra, and  an edgeedge with one V(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 42-57°. The V(3)-O(2) bond length is 2.05 Å. The V(3)-O(3) bond length is 1.94 Å. The V(3)-O(6) bond length is 2.02 Å. The V(3)-F(3) bond length is 2.19 Å. The V(3)-F(5) bond length is 2.13 Å. The V(3)-F(6) bond length is 2.10 Å. In the fourth V site, V(4) is bonded in a 5-coordinate geometry to one O(3), one O(4), one O(5), one O(6), and one F(1) atom. The V(4)-O(3) bond length is 2.07 Å. The V(4)-O(4) bond length is 2.36 Å. The V(4)-O(5) bond length is 1.91 Å. The V(4)-O(6) bond length is 1.97 Å. The V(4)-F(1) bond length is 2.01 Å. In the fifth V site, V(5) is bonded to one O(1), one O(4), one O(7), one F(2), one F(7), and one F(8) atom to form VO3F3 octahedra that share corners with two equivalent V(2)O4F2 octahedra, corners with four equivalent V(1)O3F3 octahedra,  an edgeedge with one V(7)O2F4 octahedra,  an edgeedge with one V(8)O2F4 octahedra, and edges with two equivalent Ca(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 49-59°. The V(5)-O(1) bond length is 1.93 Å. The V(5)-O(4) bond length is 2.02 Å. The V(5)-O(7) bond length is 2.04 Å. The V(5)-F(2) bond length is 2.15 Å. The V(5)-F(7) bond length is 2.07 Å. The V(5)-F(8) bond length is 2.26 Å. In the sixth V site, V(6) is bonded to one O(2), one O(6), one O(8), one F(1), one F(3), and one F(6) atom to form VO3F3 octahedra that share corners with two equivalent V(2)O4F2 octahedra, corners with four equivalent V(3)O3F3 octahedra,  an edgeedge with one V(7)O2F4 octahedra, and  an edgeedge with one V(8)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 42-57°. The V(6)-O(2) bond length is 2.06 Å. The V(6)-O(6) bond length is 2.03 Å. The V(6)-O(8) bond length is 1.92 Å. The V(6)-F(1) bond length is 2.13 Å. The V(6)-F(3) bond length is 2.13 Å. The V(6)-F(6) bond length is 2.11 Å. In the seventh V site, V(7) is bonded to one O(3), one O(5), one F(1), one F(2), one F(6), and one F(8) atom to form VO2F4 octahedra that share corners with two equivalent V(1)O3F3 octahedra, corners with two equivalent V(3)O3F3 octahedra,  an edgeedge with one V(5)O3F3 octahedra,  an edgeedge with one V(6)O3F3 octahedra, and edges with two equivalent Ca(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 51-57°. The V(7)-O(3) bond length is 2.15 Å. The V(7)-O(5) bond length is 2.13 Å. The V(7)-F(1) bond length is 2.08 Å. The V(7)-F(2) bond length is 2.25 Å. The V(7)-F(6) bond length is 2.15 Å. The V(7)-F(8) bond length is 2.10 Å. In the eighth V site, V(8) is bonded to one O(1), one O(8), one F(3), one F(4), one F(5), and one F(7) atom to form VO2F4 octahedra that share corners with two equivalent V(1)O3F3 octahedra, corners with two equivalent V(3)O3F3 octahedra, corners with four equivalent V(2)O4F2 octahedra,  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 41-56°. The V(8)-O(1) bond length is 2.01 Å. The V(8)-O(8) bond length is 2.01 Å. The V(8)-F(3) bond length is 2.06 Å. The V(8)-F(4) bond length is 1.99 Å. The V(8)-F(5) bond length is 2.00 Å. The V(8)-F(7) bond length is 2.04 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one V(2), one V(5), and one V(8) atom. In the second O site, O(2) is bonded in a 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 one Ca(1), one V(3), one V(4), and one V(7) atom to form distorted OCaV3 trigonal pyramids that share  an edgeedge with one F(2)CaV3 trigonal pyramid. In the fourth O site, O(4) is bonded in a distorted see-saw-like geometry to one Ca(1), one V(1), one V(4), and one V(5) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Ca(1), one V(1), one V(4), and one V(7) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one V(3), one V(4), and one V(6) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Ca(1), one V(1), one V(2), 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(6), 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 to one Ca(1), one V(1), one V(5), and one V(7) atom to form distorted FCaV3 trigonal pyramids that share  an edgeedge with one O(3)CaV3 trigonal pyramid. In the third F site, F(3) is bonded in a distorted T-shaped geometry to one V(3), one V(6), and one V(8) atom. In the fourth F site, F(4) is bonded in a trigonal planar geometry to one V(1), one V(2), and one V(8) atom. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to one V(2), one V(3), and one V(8) atom. In the sixth F site, F(6) is bonded in a distorted trigonal planar geometry to one V(3), one V(6), and one V(7) atom. In the seventh F site, F(7) is bonded in a distorted trigonal planar geometry to one V(1), one V(5), and one V(8) atom. In the eighth F site, F(8) is bonded in a 3-coordinate geometry to one Ca(1), one V(5), and one V(7) atom.