KNaW(OF2)2 crystallizes in the tetragonal P4/nmm space group. K(1) is bonded to four equivalent O(2) and eight equivalent F(1) atoms to form KO4F8 cuboctahedra that share corners with four equivalent K(1)O4F8 cuboctahedra, faces with four equivalent K(1)O4F8 cuboctahedra, faces with four equivalent Na(1)O2F4 octahedra, and faces with four equivalent W(1)O2F4 octahedra. Na(1) is bonded to one O(1), one O(2), and four equivalent F(1) atoms to form NaO2F4 octahedra that share corners with six equivalent W(1)O2F4 octahedra and faces with four equivalent K(1)O4F8 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-10°. W(1) is bonded to one O(1), one O(2), and four equivalent F(1) atoms to form WO2F4 octahedra that share corners with six equivalent Na(1)O2F4 octahedra and faces with four equivalent K(1)O4F8 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-10°. There are two inequivalent O sites. In the first O site, O(1) is bonded in a linear geometry to one Na(1) and one W(1) atom. In the second O site, O(2) is bonded in a distorted linear geometry to four equivalent K(1), one Na(1), and one W(1) atom. F(1) is bonded in a distorted rectangular see-saw-like geometry to two equivalent K(1), one Na(1), and one W(1) atom.
KNaW(OF2)2 crystallizes in the tetragonal P4/nmm space group. K(1) is bonded to four equivalent O(2) and eight equivalent F(1) atoms to form KO4F8 cuboctahedra that share corners with four equivalent K(1)O4F8 cuboctahedra, faces with four equivalent K(1)O4F8 cuboctahedra, faces with four equivalent Na(1)O2F4 octahedra, and faces with four equivalent W(1)O2F4 octahedra. All K(1)-O(2) bond lengths are 3.09 Å. All K(1)-F(1) bond lengths are 2.93 Å. Na(1) is bonded to one O(1), one O(2), and four equivalent F(1) atoms to form NaO2F4 octahedra that share corners with six equivalent W(1)O2F4 octahedra and faces with four equivalent K(1)O4F8 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-10°. The Na(1)-O(1) bond length is 2.27 Å. The Na(1)-O(2) bond length is 2.45 Å. All Na(1)-F(1) bond lengths are 2.41 Å. W(1) is bonded to one O(1), one O(2), and four equivalent F(1) atoms to form WO2F4 octahedra that share corners with six equivalent Na(1)O2F4 octahedra and faces with four equivalent K(1)O4F8 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-10°. The W(1)-O(1) bond length is 1.80 Å. The W(1)-O(2) bond length is 1.87 Å. All W(1)-F(1) bond lengths are 1.97 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a linear geometry to one Na(1) and one W(1) atom. In the second O site, O(2) is bonded in a distorted linear geometry to four equivalent K(1), one Na(1), and one W(1) atom. F(1) is bonded in a distorted rectangular see-saw-like geometry to two equivalent K(1), one Na(1), and one W(1) atom.