KNiAlF6 crystallizes in the orthorhombic Imma space group. K(1) is bonded to one F(2) and four equivalent F(3) atoms to form distorted KF5 square pyramids that share corners with four equivalent Al(1)F6 octahedra and corners with six equivalent Ni(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 63-71°. Ni(1) is bonded to two equivalent F(2) and four equivalent F(3) atoms to form NiF6 octahedra that share corners with two equivalent Ni(1)F6 octahedra, corners with four equivalent Al(1)F6 octahedra, and corners with six equivalent K(1)F5 square pyramids. The corner-sharing octahedral tilt angles range from 44-53°. Al(1) is bonded to two equivalent F(1) and four equivalent F(3) atoms to form AlF6 octahedra that share corners with two equivalent Al(1)F6 octahedra, corners with four equivalent Ni(1)F6 octahedra, and corners with four equivalent K(1)F5 square pyramids. The corner-sharing octahedral tilt angles range from 32-44°. There are three inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to two equivalent Al(1) atoms. In the second F site, F(2) is bonded in a trigonal planar geometry to one K(1) and two equivalent Ni(1) atoms. In the third F site, F(3) is bonded in a 2-coordinate geometry to one K(1), one Ni(1), and one Al(1) atom.
KNiAlF6 crystallizes in the orthorhombic Imma space group. K(1) is bonded to one F(2) and four equivalent F(3) atoms to form distorted KF5 square pyramids that share corners with four equivalent Al(1)F6 octahedra and corners with six equivalent Ni(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 63-71°. The K(1)-F(2) bond length is 2.82 Å. All K(1)-F(3) bond lengths are 3.06 Å. Ni(1) is bonded to two equivalent F(2) and four equivalent F(3) atoms to form NiF6 octahedra that share corners with two equivalent Ni(1)F6 octahedra, corners with four equivalent Al(1)F6 octahedra, and corners with six equivalent K(1)F5 square pyramids. The corner-sharing octahedral tilt angles range from 44-53°. Both Ni(1)-F(2) bond lengths are 1.99 Å. All Ni(1)-F(3) bond lengths are 2.03 Å. Al(1) is bonded to two equivalent F(1) and four equivalent F(3) atoms to form AlF6 octahedra that share corners with two equivalent Al(1)F6 octahedra, corners with four equivalent Ni(1)F6 octahedra, and corners with four equivalent K(1)F5 square pyramids. The corner-sharing octahedral tilt angles range from 32-44°. Both Al(1)-F(1) bond lengths are 1.85 Å. All Al(1)-F(3) bond lengths are 1.81 Å. There are three inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to two equivalent Al(1) atoms. In the second F site, F(2) is bonded in a trigonal planar geometry to one K(1) and two equivalent Ni(1) atoms. In the third F site, F(3) is bonded in a 2-coordinate geometry to one K(1), one Ni(1), and one Al(1) atom.