Rb2KGaF6 crystallizes in the tetragonal I4/m space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded to four equivalent F(4), four equivalent F(5), and four equivalent F(7) atoms to form RbF12 cuboctahedra that share faces with two equivalent Rb(1)F12 cuboctahedra, faces with four equivalent Ga(2)F6 octahedra, and faces with four equivalent K(2)F7 pentagonal bipyramids. In the second Rb site, Rb(2) is bonded in a 11-coordinate geometry to one F(1), one F(2), one F(4), one F(5), two equivalent F(3), two equivalent F(6), and three equivalent F(7) atoms. There are two inequivalent K sites. In the first K site, K(1) is bonded to two equivalent F(2) and four equivalent F(3) atoms to form KF6 octahedra that share corners with two equivalent Ga(1)F6 octahedra and corners with four equivalent Ga(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. In the second K site, K(2) is bonded to one F(4), one F(5), one F(6), two equivalent F(1), and two equivalent F(7) atoms to form distorted KF7 pentagonal bipyramids that share corners with five equivalent Ga(2)F6 octahedra, corners with two equivalent K(2)F7 pentagonal bipyramids,  an edgeedge with one Ga(1)F6 octahedra, and faces with two equivalent Rb(1)F12 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-15°. There are two inequivalent Ga sites. In the first Ga site, Ga(1) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form GaF6 octahedra that share corners with two equivalent K(1)F6 octahedra and edges with four equivalent K(2)F7 pentagonal bipyramids. The corner-sharing octahedra are not tilted. In the second Ga site, Ga(2) is bonded to one F(3), one F(4), one F(5), one F(6), and two equivalent F(7) atoms to form GaF6 octahedra that share  a cornercorner with one K(1)F6 octahedra, corners with five equivalent K(2)F7 pentagonal bipyramids, and faces with two equivalent Rb(1)F12 cuboctahedra. The corner-sharing octahedral tilt angles are 2°. There are seven inequivalent F sites. In the first F site, F(1) is bonded in a 5-coordinate geometry to two equivalent Rb(2), two equivalent K(2), and one Ga(1) atom. In the second F site, F(2) is bonded in a distorted linear geometry to four equivalent Rb(2), one K(1), and one Ga(1) atom. In the third F site, F(3) is bonded in a 2-coordinate geometry to four equivalent Rb(2), one K(1), and one Ga(2) atom. In the fourth F site, F(4) is bonded in a distorted single-bond geometry to two equivalent Rb(1), two equivalent Rb(2), one K(2), and one Ga(2) atom. In the fifth F site, F(5) is bonded in a 2-coordinate geometry to two equivalent Rb(1), two equivalent Rb(2), one K(2), and one Ga(2) atom. In the sixth F site, F(7) is bonded in a 6-coordinate geometry to one Rb(1), three equivalent Rb(2), one K(2), and one Ga(2) atom. In the seventh F site, F(6) is bonded in a 6-coordinate geometry to four equivalent Rb(2), one K(2), and one Ga(2) atom.
Rb2KGaF6 crystallizes in the tetragonal I4/m space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded to four equivalent F(4), four equivalent F(5), and four equivalent F(7) atoms to form RbF12 cuboctahedra that share faces with two equivalent Rb(1)F12 cuboctahedra, faces with four equivalent Ga(2)F6 octahedra, and faces with four equivalent K(2)F7 pentagonal bipyramids. All Rb(1)-F(4) bond lengths are 3.08 Å. All Rb(1)-F(5) bond lengths are 3.03 Å. All Rb(1)-F(7) bond lengths are 3.03 Å. In the second Rb site, Rb(2) is bonded in a 11-coordinate geometry to one F(1), one F(2), one F(4), one F(5), two equivalent F(3), two equivalent F(6), and three equivalent F(7) atoms. The Rb(2)-F(1) bond length is 2.76 Å. The Rb(2)-F(2) bond length is 3.28 Å. The Rb(2)-F(4) bond length is 2.87 Å. The Rb(2)-F(5) bond length is 3.23 Å. There is one shorter (2.98 Å) and one longer (3.10 Å) Rb(2)-F(3) bond length. There is one shorter (2.88 Å) and one longer (3.15 Å) Rb(2)-F(6) bond length. There are a spread of Rb(2)-F(7) bond distances ranging from 2.95-3.09 Å. There are two inequivalent K sites. In the first K site, K(1) is bonded to two equivalent F(2) and four equivalent F(3) atoms to form KF6 octahedra that share corners with two equivalent Ga(1)F6 octahedra and corners with four equivalent Ga(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. Both K(1)-F(2) bond lengths are 2.52 Å. All K(1)-F(3) bond lengths are 2.46 Å. In the second K site, K(2) is bonded to one F(4), one F(5), one F(6), two equivalent F(1), and two equivalent F(7) atoms to form distorted KF7 pentagonal bipyramids that share corners with five equivalent Ga(2)F6 octahedra, corners with two equivalent K(2)F7 pentagonal bipyramids,  an edgeedge with one Ga(1)F6 octahedra, and faces with two equivalent Rb(1)F12 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-15°. The K(2)-F(4) bond length is 2.84 Å. The K(2)-F(5) bond length is 2.48 Å. The K(2)-F(6) bond length is 2.54 Å. Both K(2)-F(1) bond lengths are 2.78 Å. Both K(2)-F(7) bond lengths are 2.55 Å. There are two inequivalent Ga sites. In the first Ga site, Ga(1) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form GaF6 octahedra that share corners with two equivalent K(1)F6 octahedra and edges with four equivalent K(2)F7 pentagonal bipyramids. The corner-sharing octahedra are not tilted. Both Ga(1)-F(2) bond lengths are 1.90 Å. All Ga(1)-F(1) bond lengths are 1.91 Å. In the second Ga site, Ga(2) is bonded to one F(3), one F(4), one F(5), one F(6), and two equivalent F(7) atoms to form GaF6 octahedra that share  a cornercorner with one K(1)F6 octahedra, corners with five equivalent K(2)F7 pentagonal bipyramids, and faces with two equivalent Rb(1)F12 cuboctahedra. The corner-sharing octahedral tilt angles are 2°. The Ga(2)-F(3) bond length is 1.89 Å. The Ga(2)-F(4) bond length is 1.91 Å. The Ga(2)-F(5) bond length is 1.87 Å. The Ga(2)-F(6) bond length is 1.91 Å. Both Ga(2)-F(7) bond lengths are 1.92 Å. There are seven inequivalent F sites. In the first F site, F(1) is bonded in a 5-coordinate geometry to two equivalent Rb(2), two equivalent K(2), and one Ga(1) atom. In the second F site, F(2) is bonded in a distorted linear geometry to four equivalent Rb(2), one K(1), and one Ga(1) atom. In the third F site, F(3) is bonded in a 2-coordinate geometry to four equivalent Rb(2), one K(1), and one Ga(2) atom. In the fourth F site, F(4) is bonded in a distorted single-bond geometry to two equivalent Rb(1), two equivalent Rb(2), one K(2), and one Ga(2) atom. In the fifth F site, F(5) is bonded in a 2-coordinate geometry to two equivalent Rb(1), two equivalent Rb(2), one K(2), and one Ga(2) atom. In the sixth F site, F(7) is bonded in a 6-coordinate geometry to one Rb(1), three equivalent Rb(2), one K(2), and one Ga(2) atom. In the seventh F site, F(6) is bonded in a 6-coordinate geometry to four equivalent Rb(2), one K(2), and one Ga(2) atom.