CaBiF5 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 Bi(1)F6 octahedra, edges with two equivalent Bi(1)F6 octahedra, and edges with two equivalent Ca(1)F7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 12-45°. Bi(1) is bonded to one F(1), one F(2), one F(3), one F(4), and two equivalent F(5) atoms to form BiF6 octahedra that share corners with two equivalent Bi(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 50°. There are five inequivalent F sites. In the first F site, F(1) is bonded in a 3-coordinate geometry to two equivalent Ca(1) and one Bi(1) atom. In the second F site, F(2) is bonded in a 3-coordinate geometry to two equivalent Ca(1) and one Bi(1) atom. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one Ca(1) and one Bi(1) atom. In the fourth F site, F(4) is bonded in a linear geometry to one Ca(1) and one Bi(1) atom. In the fifth F site, F(5) is bonded in a trigonal planar geometry to one Ca(1) and two equivalent Bi(1) atoms.
CaBiF5 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 Bi(1)F6 octahedra, edges with two equivalent Bi(1)F6 octahedra, and edges with two equivalent Ca(1)F7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 12-45°. The Ca(1)-F(3) bond length is 2.23 Å. The Ca(1)-F(4) bond length is 2.22 Å. The Ca(1)-F(5) bond length is 2.43 Å. There is one shorter (2.32 Å) and one longer (2.73 Å) Ca(1)-F(1) bond length. There is one shorter (2.29 Å) and one longer (2.67 Å) Ca(1)-F(2) bond length. Bi(1) is bonded to one F(1), one F(2), one F(3), one F(4), and two equivalent F(5) atoms to form BiF6 octahedra that share corners with two equivalent Bi(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 50°. The Bi(1)-F(1) bond length is 2.31 Å. The Bi(1)-F(2) bond length is 2.30 Å. The Bi(1)-F(3) bond length is 2.24 Å. The Bi(1)-F(4) bond length is 2.25 Å. There is one shorter (2.30 Å) and one longer (2.31 Å) Bi(1)-F(5) bond length. There are five inequivalent F sites. In the first F site, F(1) is bonded in a 3-coordinate geometry to two equivalent Ca(1) and one Bi(1) atom. In the second F site, F(2) is bonded in a 3-coordinate geometry to two equivalent Ca(1) and one Bi(1) atom. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one Ca(1) and one Bi(1) atom. In the fourth F site, F(4) is bonded in a linear geometry to one Ca(1) and one Bi(1) atom. In the fifth F site, F(5) is bonded in a trigonal planar geometry to one Ca(1) and two equivalent Bi(1) atoms.