CaCr6(OF)4 crystallizes in the triclinic P1 space group. Ca(1) is bonded to one O(1), one O(3), one O(4), one F(1), one F(3), and one F(4) atom to form distorted CaO3F3 octahedra that share corners with two equivalent Cr(5)O3F3 octahedra, corners with four equivalent Cr(6)O3F3 octahedra, edges with two equivalent Cr(3)O3F3 octahedra, edges with two equivalent Cr(4)O3F3 octahedra, and edges with two equivalent Cr(5)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 6-20°. There are six inequivalent Cr sites. In the first Cr site, Cr(1) is bonded in a 4-coordinate geometry to one O(1), one O(4), one F(2), and one F(4) atom. In the second Cr site, Cr(2) is bonded in a distorted linear geometry to one O(2) and one O(3) atom. In the third Cr site, Cr(3) is bonded to one O(1), one O(2), one O(3), one F(2), one F(3), and one F(4) atom to form distorted CrO3F3 octahedra that share edges with two equivalent Ca(1)O3F3 octahedra, edges with two equivalent Cr(4)O3F3 octahedra, edges with two equivalent Cr(5)O3F3 octahedra, and edges with two equivalent Cr(6)O3F3 octahedra. In the fourth Cr site, Cr(4) is bonded to one O(1), one O(2), one O(4), one F(1), one F(2), and one F(4) atom to form CrO3F3 octahedra that share edges with two equivalent Ca(1)O3F3 octahedra, edges with two equivalent Cr(3)O3F3 octahedra, edges with two equivalent Cr(5)O3F3 octahedra, and edges with two equivalent Cr(6)O3F3 octahedra. In the fifth Cr site, Cr(5) is bonded to one O(1), one O(3), one O(4), one F(1), one F(3), and one F(4) atom to form CrO3F3 octahedra that share corners with two equivalent Ca(1)O3F3 octahedra, edges with two equivalent Ca(1)O3F3 octahedra, edges with two equivalent Cr(3)O3F3 octahedra, edges with two equivalent Cr(4)O3F3 octahedra, and edges with two equivalent Cr(6)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 6-20°. In the sixth Cr site, Cr(6) is bonded to one O(2), one O(3), one O(4), one F(1), one F(2), and one F(3) atom to form distorted CrO3F3 octahedra that share corners with four equivalent Ca(1)O3F3 octahedra, edges with two equivalent Cr(3)O3F3 octahedra, edges with two equivalent Cr(4)O3F3 octahedra, and edges with two equivalent Cr(5)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 6-20°. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Ca(1), one Cr(1), one Cr(3), one Cr(4), and one Cr(5) atom to form distorted OCaCr4 square pyramids that share corners with three equivalent F(4)CaCr4 square pyramids,  a cornercorner with one O(3)CaCr4 trigonal bipyramid, corners with two equivalent O(2)Cr4 trigonal pyramids,  an edgeedge with one F(4)CaCr4 square pyramid, edges with two equivalent O(4)CaCr4 square pyramids, and  an edgeedge with one O(3)CaCr4 trigonal bipyramid. In the second O site, O(2) is bonded to one Cr(2), one Cr(3), one Cr(4), and one Cr(6) atom to form OCr4 trigonal pyramids that share corners with two equivalent O(1)CaCr4 square pyramids, corners with two equivalent O(4)CaCr4 square pyramids, corners with two equivalent F(4)CaCr4 square pyramids,  a cornercorner with one O(3)CaCr4 trigonal bipyramid, and  an edgeedge with one O(3)CaCr4 trigonal bipyramid. In the third O site, O(3) is bonded to one Ca(1), one Cr(2), one Cr(3), one Cr(5), and one Cr(6) atom to form OCaCr4 trigonal bipyramids that share  a cornercorner with one O(1)CaCr4 square pyramid,  a cornercorner with one F(4)CaCr4 square pyramid, corners with three equivalent O(4)CaCr4 square pyramids,  a cornercorner with one O(2)Cr4 trigonal pyramid,  an edgeedge with one O(1)CaCr4 square pyramid,  an edgeedge with one F(4)CaCr4 square pyramid, and  an edgeedge with one O(2)Cr4 trigonal pyramid. In the fourth O site, O(4) is bonded to one Ca(1), one Cr(1), one Cr(4), one Cr(5), and one Cr(6) atom to form distorted OCaCr4 square pyramids that share corners with three equivalent O(3)CaCr4 trigonal bipyramids, corners with two equivalent O(2)Cr4 trigonal pyramids, edges with two equivalent O(1)CaCr4 square pyramids, and edges with two equivalent F(4)CaCr4 square pyramids. There are four inequivalent F sites. In the first F site, F(1) is bonded in a distorted see-saw-like geometry to one Ca(1), one Cr(4), one Cr(5), and one Cr(6) atom. In the second F site, F(2) is bonded in a 4-coordinate geometry to one Cr(1), one Cr(3), one Cr(4), and one Cr(6) atom. In the third F site, F(3) is bonded in a distorted rectangular see-saw-like geometry to one Ca(1), one Cr(3), one Cr(5), and one Cr(6) atom. In the fourth F site, F(4) is bonded to one Ca(1), one Cr(1), one Cr(3), one Cr(4), and one Cr(5) atom to form distorted FCaCr4 square pyramids that share corners with three equivalent O(1)CaCr4 square pyramids,  a cornercorner with one O(3)CaCr4 trigonal bipyramid, corners with two equivalent O(2)Cr4 trigonal pyramids,  an edgeedge with one O(1)CaCr4 square pyramid, edges with two equivalent O(4)CaCr4 square pyramids, and  an edgeedge with one O(3)CaCr4 trigonal bipyramid.
CaCr6(OF)4 crystallizes in the triclinic P1 space group. Ca(1) is bonded to one O(1), one O(3), one O(4), one F(1), one F(3), and one F(4) atom to form distorted CaO3F3 octahedra that share corners with two equivalent Cr(5)O3F3 octahedra, corners with four equivalent Cr(6)O3F3 octahedra, edges with two equivalent Cr(3)O3F3 octahedra, edges with two equivalent Cr(4)O3F3 octahedra, and edges with two equivalent Cr(5)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 6-20°. The Ca(1)-O(1) bond length is 2.33 Å. The Ca(1)-O(3) bond length is 2.59 Å. The Ca(1)-O(4) bond length is 2.63 Å. The Ca(1)-F(1) bond length is 2.29 Å. The Ca(1)-F(3) bond length is 2.32 Å. The Ca(1)-F(4) bond length is 2.42 Å. There are six inequivalent Cr sites. In the first Cr site, Cr(1) is bonded in a 4-coordinate geometry to one O(1), one O(4), one F(2), and one F(4) atom. The Cr(1)-O(1) bond length is 2.51 Å. The Cr(1)-O(4) bond length is 2.17 Å. The Cr(1)-F(2) bond length is 2.35 Å. The Cr(1)-F(4) bond length is 2.50 Å. In the second Cr site, Cr(2) is bonded in a distorted linear geometry to one O(2) and one O(3) atom. The Cr(2)-O(2) bond length is 2.03 Å. The Cr(2)-O(3) bond length is 2.08 Å. In the third Cr site, Cr(3) is bonded to one O(1), one O(2), one O(3), one F(2), one F(3), and one F(4) atom to form distorted CrO3F3 octahedra that share edges with two equivalent Ca(1)O3F3 octahedra, edges with two equivalent Cr(4)O3F3 octahedra, edges with two equivalent Cr(5)O3F3 octahedra, and edges with two equivalent Cr(6)O3F3 octahedra. The Cr(3)-O(1) bond length is 2.13 Å. The Cr(3)-O(2) bond length is 2.10 Å. The Cr(3)-O(3) bond length is 2.06 Å. The Cr(3)-F(2) bond length is 2.40 Å. The Cr(3)-F(3) bond length is 2.12 Å. The Cr(3)-F(4) bond length is 2.59 Å. In the fourth Cr site, Cr(4) is bonded to one O(1), one O(2), one O(4), one F(1), one F(2), and one F(4) atom to form CrO3F3 octahedra that share edges with two equivalent Ca(1)O3F3 octahedra, edges with two equivalent Cr(3)O3F3 octahedra, edges with two equivalent Cr(5)O3F3 octahedra, and edges with two equivalent Cr(6)O3F3 octahedra. The Cr(4)-O(1) bond length is 2.09 Å. The Cr(4)-O(2) bond length is 2.07 Å. The Cr(4)-O(4) bond length is 2.09 Å. The Cr(4)-F(1) bond length is 2.15 Å. The Cr(4)-F(2) bond length is 2.44 Å. The Cr(4)-F(4) bond length is 2.49 Å. In the fifth Cr site, Cr(5) is bonded to one O(1), one O(3), one O(4), one F(1), one F(3), and one F(4) atom to form CrO3F3 octahedra that share corners with two equivalent Ca(1)O3F3 octahedra, edges with two equivalent Ca(1)O3F3 octahedra, edges with two equivalent Cr(3)O3F3 octahedra, edges with two equivalent Cr(4)O3F3 octahedra, and edges with two equivalent Cr(6)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 6-20°. The Cr(5)-O(1) bond length is 2.12 Å. The Cr(5)-O(3) bond length is 2.12 Å. The Cr(5)-O(4) bond length is 2.07 Å. The Cr(5)-F(1) bond length is 2.47 Å. The Cr(5)-F(3) bond length is 2.41 Å. The Cr(5)-F(4) bond length is 2.26 Å. In the sixth Cr site, Cr(6) is bonded to one O(2), one O(3), one O(4), one F(1), one F(2), and one F(3) atom to form distorted CrO3F3 octahedra that share corners with four equivalent Ca(1)O3F3 octahedra, edges with two equivalent Cr(3)O3F3 octahedra, edges with two equivalent Cr(4)O3F3 octahedra, and edges with two equivalent Cr(5)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 6-20°. The Cr(6)-O(2) bond length is 2.03 Å. The Cr(6)-O(3) bond length is 2.23 Å. The Cr(6)-O(4) bond length is 2.21 Å. The Cr(6)-F(1) bond length is 2.56 Å. The Cr(6)-F(2) bond length is 2.05 Å. The Cr(6)-F(3) bond length is 2.56 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Ca(1), one Cr(1), one Cr(3), one Cr(4), and one Cr(5) atom to form distorted OCaCr4 square pyramids that share corners with three equivalent F(4)CaCr4 square pyramids,  a cornercorner with one O(3)CaCr4 trigonal bipyramid, corners with two equivalent O(2)Cr4 trigonal pyramids,  an edgeedge with one F(4)CaCr4 square pyramid, edges with two equivalent O(4)CaCr4 square pyramids, and  an edgeedge with one O(3)CaCr4 trigonal bipyramid. In the second O site, O(2) is bonded to one Cr(2), one Cr(3), one Cr(4), and one Cr(6) atom to form OCr4 trigonal pyramids that share corners with two equivalent O(1)CaCr4 square pyramids, corners with two equivalent O(4)CaCr4 square pyramids, corners with two equivalent F(4)CaCr4 square pyramids,  a cornercorner with one O(3)CaCr4 trigonal bipyramid, and  an edgeedge with one O(3)CaCr4 trigonal bipyramid. In the third O site, O(3) is bonded to one Ca(1), one Cr(2), one Cr(3), one Cr(5), and one Cr(6) atom to form OCaCr4 trigonal bipyramids that share  a cornercorner with one O(1)CaCr4 square pyramid,  a cornercorner with one F(4)CaCr4 square pyramid, corners with three equivalent O(4)CaCr4 square pyramids,  a cornercorner with one O(2)Cr4 trigonal pyramid,  an edgeedge with one O(1)CaCr4 square pyramid,  an edgeedge with one F(4)CaCr4 square pyramid, and  an edgeedge with one O(2)Cr4 trigonal pyramid. In the fourth O site, O(4) is bonded to one Ca(1), one Cr(1), one Cr(4), one Cr(5), and one Cr(6) atom to form distorted OCaCr4 square pyramids that share corners with three equivalent O(3)CaCr4 trigonal bipyramids, corners with two equivalent O(2)Cr4 trigonal pyramids, edges with two equivalent O(1)CaCr4 square pyramids, and edges with two equivalent F(4)CaCr4 square pyramids. There are four inequivalent F sites. In the first F site, F(1) is bonded in a distorted see-saw-like geometry to one Ca(1), one Cr(4), one Cr(5), and one Cr(6) atom. In the second F site, F(2) is bonded in a 4-coordinate geometry to one Cr(1), one Cr(3), one Cr(4), and one Cr(6) atom. In the third F site, F(3) is bonded in a distorted rectangular see-saw-like geometry to one Ca(1), one Cr(3), one Cr(5), and one Cr(6) atom. In the fourth F site, F(4) is bonded to one Ca(1), one Cr(1), one Cr(3), one Cr(4), and one Cr(5) atom to form distorted FCaCr4 square pyramids that share corners with three equivalent O(1)CaCr4 square pyramids,  a cornercorner with one O(3)CaCr4 trigonal bipyramid, corners with two equivalent O(2)Cr4 trigonal pyramids,  an edgeedge with one O(1)CaCr4 square pyramid, edges with two equivalent O(4)CaCr4 square pyramids, and  an edgeedge with one O(3)CaCr4 trigonal bipyramid.