Rb2NaMn3F12 crystallizes in the triclinic P-1 space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 8-coordinate geometry to one F(11), one F(2), one F(5), one F(6), two equivalent F(3), and two equivalent F(4) atoms. In the second Rb site, Rb(2) is bonded in a 10-coordinate geometry to one F(1), one F(10), one F(11), one F(12), one F(5), one F(6), two equivalent F(8), and two equivalent F(9) atoms. Na(1) is bonded in a 8-coordinate geometry to one F(1), one F(10), one F(2), one F(3), one F(4), one F(5), one F(6), and one F(7) atom. There are five inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one F(1), one F(10), one F(12), one F(2), one F(8), and one F(9) atom to form corner-sharing MnF6 octahedra. The corner-sharing octahedral tilt angles range from 38-45°. In the second Mn site, Mn(2) is bonded to two equivalent F(11), two equivalent F(12), and two equivalent F(3) atoms to form corner-sharing MnF6 octahedra. The corner-sharing octahedral tilt angles range from 40-43°. In the third Mn site, Mn(3) is bonded to two equivalent F(10), two equivalent F(11), and two equivalent F(4) atoms to form corner-sharing MnF6 octahedra. The corner-sharing octahedral tilt angles range from 38-43°. In the fourth Mn site, Mn(4) is bonded to two equivalent F(5), two equivalent F(7), and two equivalent F(9) atoms to form corner-sharing MnF6 octahedra. The corner-sharing octahedral tilt angles range from 36-45°. In the fifth Mn site, Mn(5) is bonded to two equivalent F(6), two equivalent F(7), and two equivalent F(8) atoms to form corner-sharing MnF6 octahedra. The corner-sharing octahedral tilt angles range from 36-43°. There are twelve inequivalent F sites. In the first F site, F(1) is bonded in a 3-coordinate geometry to one Rb(2), one Na(1), and one Mn(1) atom. In the second F site, F(2) is bonded in a 2-coordinate geometry to one Rb(1), one Na(1), and one Mn(1) atom. In the third F site, F(3) is bonded in a 4-coordinate geometry to two equivalent Rb(1), one Na(1), and one Mn(2) atom. In the fourth F site, F(4) is bonded in a 4-coordinate geometry to two equivalent Rb(1), one Na(1), and one Mn(3) atom. In the fifth F site, F(5) is bonded in a 4-coordinate geometry to one Rb(1), one Rb(2), one Na(1), and one Mn(4) atom. In the sixth F site, F(6) is bonded in a 4-coordinate geometry to one Rb(1), one Rb(2), one Na(1), and one Mn(5) atom. In the seventh F site, F(7) is bonded in a 3-coordinate geometry to one Na(1), one Mn(4), and one Mn(5) atom. In the eighth F site, F(8) is bonded in a 2-coordinate geometry to two equivalent Rb(2), one Mn(1), and one Mn(5) atom. In the ninth F site, F(9) is bonded in a 2-coordinate geometry to two equivalent Rb(2), one Mn(1), and one Mn(4) atom. In the tenth F site, F(10) is bonded in a 2-coordinate geometry to one Rb(2), one Na(1), one Mn(1), and one Mn(3) atom. In the eleventh F site, F(11) is bonded in a 2-coordinate geometry to one Rb(1), one Rb(2), one Mn(2), and one Mn(3) atom. In the twelfth F site, F(12) is bonded in a 2-coordinate geometry to one Rb(2), one Mn(1), and one Mn(2) atom.
Rb2NaMn3F12 crystallizes in the triclinic P-1 space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 8-coordinate geometry to one F(11), one F(2), one F(5), one F(6), two equivalent F(3), and two equivalent F(4) atoms. The Rb(1)-F(11) bond length is 3.06 Å. The Rb(1)-F(2) bond length is 2.98 Å. The Rb(1)-F(5) bond length is 2.97 Å. The Rb(1)-F(6) bond length is 2.94 Å. There is one shorter (2.97 Å) and one longer (3.06 Å) Rb(1)-F(3) bond length. There is one shorter (2.88 Å) and one longer (2.91 Å) Rb(1)-F(4) bond length. In the second Rb site, Rb(2) is bonded in a 10-coordinate geometry to one F(1), one F(10), one F(11), one F(12), one F(5), one F(6), two equivalent F(8), and two equivalent F(9) atoms. The Rb(2)-F(1) bond length is 2.77 Å. The Rb(2)-F(10) bond length is 3.06 Å. The Rb(2)-F(11) bond length is 3.00 Å. The Rb(2)-F(12) bond length is 2.97 Å. The Rb(2)-F(5) bond length is 2.91 Å. The Rb(2)-F(6) bond length is 2.97 Å. There is one shorter (3.06 Å) and one longer (3.13 Å) Rb(2)-F(8) bond length. There is one shorter (3.15 Å) and one longer (3.21 Å) Rb(2)-F(9) bond length. Na(1) is bonded in a 8-coordinate geometry to one F(1), one F(10), one F(2), one F(3), one F(4), one F(5), one F(6), and one F(7) atom. The Na(1)-F(1) bond length is 2.27 Å. The Na(1)-F(10) bond length is 2.86 Å. The Na(1)-F(2) bond length is 2.23 Å. The Na(1)-F(3) bond length is 2.32 Å. The Na(1)-F(4) bond length is 2.44 Å. The Na(1)-F(5) bond length is 2.38 Å. The Na(1)-F(6) bond length is 2.46 Å. The Na(1)-F(7) bond length is 2.52 Å. There are five inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one F(1), one F(10), one F(12), one F(2), one F(8), and one F(9) atom to form corner-sharing MnF6 octahedra. The corner-sharing octahedral tilt angles range from 38-45°. The Mn(1)-F(1) bond length is 1.83 Å. The Mn(1)-F(10) bond length is 2.11 Å. The Mn(1)-F(12) bond length is 1.89 Å. The Mn(1)-F(2) bond length is 1.82 Å. The Mn(1)-F(8) bond length is 2.12 Å. The Mn(1)-F(9) bond length is 1.89 Å. In the second Mn site, Mn(2) is bonded to two equivalent F(11), two equivalent F(12), and two equivalent F(3) atoms to form corner-sharing MnF6 octahedra. The corner-sharing octahedral tilt angles range from 40-43°. Both Mn(2)-F(11) bond lengths are 1.89 Å. Both Mn(2)-F(12) bond lengths are 2.09 Å. Both Mn(2)-F(3) bond lengths are 1.83 Å. In the third Mn site, Mn(3) is bonded to two equivalent F(10), two equivalent F(11), and two equivalent F(4) atoms to form corner-sharing MnF6 octahedra. The corner-sharing octahedral tilt angles range from 38-43°. Both Mn(3)-F(10) bond lengths are 1.88 Å. Both Mn(3)-F(11) bond lengths are 2.13 Å. Both Mn(3)-F(4) bond lengths are 1.84 Å. In the fourth Mn site, Mn(4) is bonded to two equivalent F(5), two equivalent F(7), and two equivalent F(9) atoms to form corner-sharing MnF6 octahedra. The corner-sharing octahedral tilt angles range from 36-45°. Both Mn(4)-F(5) bond lengths are 1.85 Å. Both Mn(4)-F(7) bond lengths are 1.86 Å. Both Mn(4)-F(9) bond lengths are 2.14 Å. In the fifth Mn site, Mn(5) is bonded to two equivalent F(6), two equivalent F(7), and two equivalent F(8) atoms to form corner-sharing MnF6 octahedra. The corner-sharing octahedral tilt angles range from 36-43°. Both Mn(5)-F(6) bond lengths are 1.83 Å. Both Mn(5)-F(7) bond lengths are 2.07 Å. Both Mn(5)-F(8) bond lengths are 1.89 Å. There are twelve inequivalent F sites. In the first F site, F(1) is bonded in a 3-coordinate geometry to one Rb(2), one Na(1), and one Mn(1) atom. In the second F site, F(2) is bonded in a 2-coordinate geometry to one Rb(1), one Na(1), and one Mn(1) atom. In the third F site, F(3) is bonded in a 4-coordinate geometry to two equivalent Rb(1), one Na(1), and one Mn(2) atom. In the fourth F site, F(4) is bonded in a 4-coordinate geometry to two equivalent Rb(1), one Na(1), and one Mn(3) atom. In the fifth F site, F(5) is bonded in a 4-coordinate geometry to one Rb(1), one Rb(2), one Na(1), and one Mn(4) atom. In the sixth F site, F(6) is bonded in a 4-coordinate geometry to one Rb(1), one Rb(2), one Na(1), and one Mn(5) atom. In the seventh F site, F(7) is bonded in a 3-coordinate geometry to one Na(1), one Mn(4), and one Mn(5) atom. In the eighth F site, F(8) is bonded in a 2-coordinate geometry to two equivalent Rb(2), one Mn(1), and one Mn(5) atom. In the ninth F site, F(9) is bonded in a 2-coordinate geometry to two equivalent Rb(2), one Mn(1), and one Mn(4) atom. In the tenth F site, F(10) is bonded in a 2-coordinate geometry to one Rb(2), one Na(1), one Mn(1), and one Mn(3) atom. In the eleventh F site, F(11) is bonded in a 2-coordinate geometry to one Rb(1), one Rb(2), one Mn(2), and one Mn(3) atom. In the twelfth F site, F(12) is bonded in a 2-coordinate geometry to one Rb(2), one Mn(1), and one Mn(2) atom.