CaCrF5 crystallizes in the monoclinic P2_1/c space group. Ca(1) is bonded to one F(3), one F(4), one F(5), two equivalent F(1), and two equivalent F(2) atoms to form distorted CaF7 pentagonal bipyramids that share corners with four equivalent Cr(1)F6 octahedra, edges with two equivalent Cr(1)F6 octahedra, and edges with two equivalent Ca(1)F7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 15-45°. Cr(1) is bonded to one F(1), one F(2), one F(3), one F(4), and two equivalent F(5) atoms to form CrF6 octahedra that share corners with two equivalent Cr(1)F6 octahedra, corners with four equivalent Ca(1)F7 pentagonal bipyramids, and edges with two equivalent Ca(1)F7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 31°. There are five inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Ca(1) and one Cr(1) atom. In the second F site, F(2) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Ca(1) and one Cr(1) atom. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one Ca(1) and one Cr(1) atom. In the fourth F site, F(4) is bonded in a linear geometry to one Ca(1) and one Cr(1) atom. In the fifth F site, F(5) is bonded in a 3-coordinate geometry to one Ca(1) and two equivalent Cr(1) atoms.
CaCrF5 crystallizes in the monoclinic P2_1/c space group. Ca(1) is bonded to one F(3), one F(4), one F(5), two equivalent F(1), and two equivalent F(2) atoms to form distorted CaF7 pentagonal bipyramids that share corners with four equivalent Cr(1)F6 octahedra, edges with two equivalent Cr(1)F6 octahedra, and edges with two equivalent Ca(1)F7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 15-45°. The Ca(1)-F(3) bond length is 2.22 Å. The Ca(1)-F(4) bond length is 2.21 Å. The Ca(1)-F(5) bond length is 2.48 Å. There is one shorter (2.31 Å) and one longer (2.38 Å) Ca(1)-F(1) bond length. There is one shorter (2.29 Å) and one longer (2.37 Å) Ca(1)-F(2) bond length. Cr(1) is bonded to one F(1), one F(2), one F(3), one F(4), and two equivalent F(5) atoms to form CrF6 octahedra that share corners with two equivalent Cr(1)F6 octahedra, corners with four equivalent Ca(1)F7 pentagonal bipyramids, and edges with two equivalent Ca(1)F7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 31°. The Cr(1)-F(1) bond length is 1.94 Å. The Cr(1)-F(2) bond length is 1.92 Å. The Cr(1)-F(3) bond length is 1.87 Å. The Cr(1)-F(4) bond length is 1.86 Å. There is one shorter (1.94 Å) and one longer (1.95 Å) Cr(1)-F(5) bond length. There are five inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Ca(1) and one Cr(1) atom. In the second F site, F(2) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Ca(1) and one Cr(1) atom. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one Ca(1) and one Cr(1) atom. In the fourth F site, F(4) is bonded in a linear geometry to one Ca(1) and one Cr(1) atom. In the fifth F site, F(5) is bonded in a 3-coordinate geometry to one Ca(1) and two equivalent Cr(1) atoms.