K2NaMoO3F3 crystallizes in the tetragonal P4_2nm space group. K(1) is bonded to two equivalent O(1), four equivalent O(2), two equivalent F(2), and four equivalent F(1) atoms to form KO6F6 cuboctahedra that share corners with twelve equivalent K(1)O6F6 cuboctahedra, faces with six equivalent K(1)O6F6 cuboctahedra, faces with four equivalent Na(1)O3F3 octahedra, and faces with four equivalent Mo(1)O3F3 octahedra. Na(1) is bonded to one O(1), two equivalent O(2), one F(2), and two equivalent F(1) atoms to form NaO3F3 octahedra that share corners with six equivalent Mo(1)O3F3 octahedra and faces with eight equivalent K(1)O6F6 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-16°. Mo(1) is bonded to one O(1), two equivalent O(2), one F(2), and two equivalent F(1) atoms to form MoO3F3 octahedra that share corners with six equivalent Na(1)O3F3 octahedra and faces with eight equivalent K(1)O6F6 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-16°. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 6-coordinate geometry to four equivalent K(1), one Na(1), and one Mo(1) atom. In the second O site, O(2) is bonded in a 2-coordinate geometry to four equivalent K(1), one Na(1), and one Mo(1) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a distorted linear geometry to four equivalent K(1), one Na(1), and one Mo(1) atom. In the second F site, F(2) is bonded to four equivalent K(1), one Na(1), and one Mo(1) atom to form distorted corner-sharing FK4NaMo octahedra. The corner-sharing octahedral tilt angles are 2°.
K2NaMoO3F3 crystallizes in the tetragonal P4_2nm space group. K(1) is bonded to two equivalent O(1), four equivalent O(2), two equivalent F(2), and four equivalent F(1) atoms to form KO6F6 cuboctahedra that share corners with twelve equivalent K(1)O6F6 cuboctahedra, faces with six equivalent K(1)O6F6 cuboctahedra, faces with four equivalent Na(1)O3F3 octahedra, and faces with four equivalent Mo(1)O3F3 octahedra. Both K(1)-O(1) bond lengths are 3.02 Å. There are two shorter (2.89 Å) and two longer (3.23 Å) K(1)-O(2) bond lengths. Both K(1)-F(2) bond lengths are 3.01 Å. There are two shorter (3.01 Å) and two longer (3.07 Å) K(1)-F(1) bond lengths. Na(1) is bonded to one O(1), two equivalent O(2), one F(2), and two equivalent F(1) atoms to form NaO3F3 octahedra that share corners with six equivalent Mo(1)O3F3 octahedra and faces with eight equivalent K(1)O6F6 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-16°. The Na(1)-O(1) bond length is 2.41 Å. Both Na(1)-O(2) bond lengths are 2.46 Å. The Na(1)-F(2) bond length is 2.26 Å. Both Na(1)-F(1) bond lengths are 2.25 Å. Mo(1) is bonded to one O(1), two equivalent O(2), one F(2), and two equivalent F(1) atoms to form MoO3F3 octahedra that share corners with six equivalent Na(1)O3F3 octahedra and faces with eight equivalent K(1)O6F6 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-16°. The Mo(1)-O(1) bond length is 1.78 Å. Both Mo(1)-O(2) bond lengths are 1.85 Å. The Mo(1)-F(2) bond length is 2.23 Å. Both Mo(1)-F(1) bond lengths are 2.02 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 6-coordinate geometry to four equivalent K(1), one Na(1), and one Mo(1) atom. In the second O site, O(2) is bonded in a 2-coordinate geometry to four equivalent K(1), one Na(1), and one Mo(1) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a distorted linear geometry to four equivalent K(1), one Na(1), and one Mo(1) atom. In the second F site, F(2) is bonded to four equivalent K(1), one Na(1), and one Mo(1) atom to form distorted corner-sharing FK4NaMo octahedra. The corner-sharing octahedral tilt angles are 2°.