Rb2KWO3F3 crystallizes in the orthorhombic Fmm2 space group. Rb(1) is bonded to two equivalent O(2), four equivalent O(1), two equivalent F(2), and four equivalent F(1) atoms to form distorted RbO6F6 cuboctahedra that share corners with twelve equivalent Rb(1)O6F6 cuboctahedra, faces with six equivalent Rb(1)O6F6 cuboctahedra, faces with four equivalent K(1)O3F3 octahedra, and faces with four equivalent W(1)O3F3 octahedra. K(1) is bonded to one O(2), two equivalent O(1), one F(2), and two equivalent F(1) atoms to form KO3F3 octahedra that share corners with six equivalent W(1)O3F3 octahedra and faces with eight equivalent Rb(1)O6F6 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-13°. W(1) is bonded to one O(2), two equivalent O(1), one F(2), and two equivalent F(1) atoms to form WO3F3 octahedra that share corners with six equivalent K(1)O3F3 octahedra and faces with eight equivalent Rb(1)O6F6 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-13°. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 2-coordinate geometry to four equivalent Rb(1), one K(1), and one W(1) atom. In the second O site, O(2) is bonded in a 6-coordinate geometry to four equivalent Rb(1), one K(1), and one W(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 Rb(1), one K(1), and one W(1) atom. In the second F site, F(2) is bonded to four equivalent Rb(1), one K(1), and one W(1) atom to form distorted corner-sharing FKRb4W octahedra. The corner-sharing octahedral tilt angles are 8°.
Rb2KWO3F3 crystallizes in the orthorhombic Fmm2 space group. Rb(1) is bonded to two equivalent O(2), four equivalent O(1), two equivalent F(2), and four equivalent F(1) atoms to form distorted RbO6F6 cuboctahedra that share corners with twelve equivalent Rb(1)O6F6 cuboctahedra, faces with six equivalent Rb(1)O6F6 cuboctahedra, faces with four equivalent K(1)O3F3 octahedra, and faces with four equivalent W(1)O3F3 octahedra. Both Rb(1)-O(2) bond lengths are 3.24 Å. There are two shorter (3.12 Å) and two longer (3.44 Å) Rb(1)-O(1) bond lengths. Both Rb(1)-F(2) bond lengths are 3.22 Å. There are two shorter (3.20 Å) and two longer (3.29 Å) Rb(1)-F(1) bond lengths. K(1) is bonded to one O(2), two equivalent O(1), one F(2), and two equivalent F(1) atoms to form KO3F3 octahedra that share corners with six equivalent W(1)O3F3 octahedra and faces with eight equivalent Rb(1)O6F6 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-13°. The K(1)-O(2) bond length is 2.67 Å. Both K(1)-O(1) bond lengths are 2.69 Å. The K(1)-F(2) bond length is 2.58 Å. Both K(1)-F(1) bond lengths are 2.56 Å. W(1) is bonded to one O(2), two equivalent O(1), one F(2), and two equivalent F(1) atoms to form WO3F3 octahedra that share corners with six equivalent K(1)O3F3 octahedra and faces with eight equivalent Rb(1)O6F6 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-13°. The W(1)-O(2) bond length is 1.81 Å. Both W(1)-O(1) bond lengths are 1.86 Å. The W(1)-F(2) bond length is 2.17 Å. Both W(1)-F(1) bond lengths are 2.01 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 2-coordinate geometry to four equivalent Rb(1), one K(1), and one W(1) atom. In the second O site, O(2) is bonded in a 6-coordinate geometry to four equivalent Rb(1), one K(1), and one W(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 Rb(1), one K(1), and one W(1) atom. In the second F site, F(2) is bonded to four equivalent Rb(1), one K(1), and one W(1) atom to form distorted corner-sharing FKRb4W octahedra. The corner-sharing octahedral tilt angles are 8°.