CaNiF5 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 Ni(1)F6 octahedra, edges with two equivalent Ni(1)F6 octahedra, and edges with two equivalent Ca(1)F7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 18-45°. Ni(1) is bonded to one F(1), one F(2), one F(3), one F(4), and two equivalent F(5) atoms to form NiF6 octahedra that share corners with two equivalent Ni(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 35°. 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 Ni(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 Ni(1) atom. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one Ca(1) and one Ni(1) atom. In the fourth F site, F(4) is bonded in a distorted bent 150 degrees geometry to one Ca(1) and one Ni(1) atom. In the fifth F site, F(5) is bonded in a distorted trigonal non-coplanar geometry to one Ca(1) and two equivalent Ni(1) atoms.
CaNiF5 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 Ni(1)F6 octahedra, edges with two equivalent Ni(1)F6 octahedra, and edges with two equivalent Ca(1)F7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 18-45°. The Ca(1)-F(3) bond length is 2.24 Å. The Ca(1)-F(4) bond length is 2.24 Å. The Ca(1)-F(5) bond length is 2.36 Å. There is one shorter (2.31 Å) and one longer (2.38 Å) Ca(1)-F(1) bond length. There is one shorter (2.30 Å) and one longer (2.38 Å) Ca(1)-F(2) bond length. Ni(1) is bonded to one F(1), one F(2), one F(3), one F(4), and two equivalent F(5) atoms to form NiF6 octahedra that share corners with two equivalent Ni(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 35°. The Ni(1)-F(1) bond length is 1.93 Å. The Ni(1)-F(2) bond length is 1.89 Å. The Ni(1)-F(3) bond length is 1.83 Å. The Ni(1)-F(4) bond length is 1.82 Å. Both Ni(1)-F(5) bond lengths are 1.97 Å. 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 Ni(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 Ni(1) atom. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one Ca(1) and one Ni(1) atom. In the fourth F site, F(4) is bonded in a distorted bent 150 degrees geometry to one Ca(1) and one Ni(1) atom. In the fifth F site, F(5) is bonded in a distorted trigonal non-coplanar geometry to one Ca(1) and two equivalent Ni(1) atoms.