KNa(WO3)4 crystallizes in the tetragonal P4/mmm space group. K(1) is bonded to four equivalent O(2) and eight equivalent O(1) atoms to form KO12 cuboctahedra that share corners with four equivalent K(1)O12 cuboctahedra, corners with eight equivalent Na(1)O12 cuboctahedra, and faces with eight equivalent W(1)O6 octahedra. Na(1) is bonded to four equivalent O(3) and eight equivalent O(1) atoms to form NaO12 cuboctahedra that share corners with four equivalent Na(1)O12 cuboctahedra, corners with eight equivalent K(1)O12 cuboctahedra, and faces with eight equivalent W(1)O6 octahedra. W(1) is bonded to one O(2), one O(3), and four equivalent O(1) atoms to form WO6 octahedra that share corners with six equivalent W(1)O6 octahedra, faces with two equivalent K(1)O12 cuboctahedra, and faces with two equivalent Na(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-1°. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted square co-planar geometry to one K(1), one Na(1), and two equivalent W(1) atoms. In the second O site, O(2) is bonded in a square co-planar geometry to two equivalent K(1) and two equivalent W(1) atoms. In the third O site, O(3) is bonded in a distorted square co-planar geometry to two equivalent Na(1) and two equivalent W(1) atoms.
KNa(WO3)4 crystallizes in the tetragonal P4/mmm space group. K(1) is bonded to four equivalent O(2) and eight equivalent O(1) atoms to form KO12 cuboctahedra that share corners with four equivalent K(1)O12 cuboctahedra, corners with eight equivalent Na(1)O12 cuboctahedra, and faces with eight equivalent W(1)O6 octahedra. All K(1)-O(2) bond lengths are 2.77 Å. All K(1)-O(1) bond lengths are 2.80 Å. Na(1) is bonded to four equivalent O(3) and eight equivalent O(1) atoms to form NaO12 cuboctahedra that share corners with four equivalent Na(1)O12 cuboctahedra, corners with eight equivalent K(1)O12 cuboctahedra, and faces with eight equivalent W(1)O6 octahedra. All Na(1)-O(3) bond lengths are 2.77 Å. All Na(1)-O(1) bond lengths are 2.75 Å. W(1) is bonded to one O(2), one O(3), and four equivalent O(1) atoms to form WO6 octahedra that share corners with six equivalent W(1)O6 octahedra, faces with two equivalent K(1)O12 cuboctahedra, and faces with two equivalent Na(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-1°. The W(1)-O(2) bond length is 1.97 Å. The W(1)-O(3) bond length is 1.95 Å. All W(1)-O(1) bond lengths are 1.96 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted square co-planar geometry to one K(1), one Na(1), and two equivalent W(1) atoms. In the second O site, O(2) is bonded in a square co-planar geometry to two equivalent K(1) and two equivalent W(1) atoms. In the third O site, O(3) is bonded in a distorted square co-planar geometry to two equivalent Na(1) and two equivalent W(1) atoms.