KNa3Mg4F12 is Orthorhombic Perovskite-derived structured and crystallizes in the monoclinic Pm space group. K(1) is bonded in a 10-coordinate geometry to two equivalent F(1), two equivalent F(2), two equivalent F(4), two equivalent F(5), and two equivalent F(6) atoms. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 8-coordinate geometry to one F(5), one F(6), two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms. In the second Na site, Na(2) is bonded in a 8-coordinate geometry to one F(7), one F(8), two equivalent F(2), two equivalent F(3), and two equivalent F(4) atoms. In the third Na site, Na(3) is bonded in a 8-coordinate geometry to one F(7), one F(8), two equivalent F(1), two equivalent F(3), and two equivalent F(4) atoms. There are two inequivalent Mg sites. In the first Mg site, Mg(1) is bonded to one F(1), one F(2), one F(3), one F(4), one F(6), and one F(8) atom to form corner-sharing MgF6 octahedra. The corner-sharing octahedral tilt angles range from 16-28°. In the second Mg site, Mg(2) is bonded to one F(1), one F(2), one F(3), one F(4), one F(5), and one F(7) atom to form corner-sharing MgF6 octahedra. The corner-sharing octahedral tilt angles range from 18-28°. There are eight inequivalent F sites. In the first F site, F(1) is bonded in a 5-coordinate geometry to one K(1), one Na(1), one Na(3), one Mg(1), and one Mg(2) atom. In the second F site, F(2) is bonded in a 5-coordinate geometry to one K(1), one Na(1), one Na(2), one Mg(1), and one Mg(2) atom. In the third F site, F(3) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), one Na(3), one Mg(1), and one Mg(2) atom. In the fourth F site, F(4) is bonded in a 5-coordinate geometry to one K(1), one Na(2), one Na(3), one Mg(1), and one Mg(2) atom. In the fifth F site, F(5) is bonded in a 5-coordinate geometry to two equivalent K(1), one Na(1), and two equivalent Mg(2) atoms. In the sixth F site, F(6) is bonded in a 4-coordinate geometry to two equivalent K(1), one Na(1), and two equivalent Mg(1) atoms. In the seventh F site, F(7) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), and two equivalent Mg(2) atoms. In the eighth F site, F(8) is bonded in a distorted tetrahedral geometry to one Na(2), one Na(3), and two equivalent Mg(1) atoms.
KNa3Mg4F12 is Orthorhombic Perovskite-derived structured and crystallizes in the monoclinic Pm space group. K(1) is bonded in a 10-coordinate geometry to two equivalent F(1), two equivalent F(2), two equivalent F(4), two equivalent F(5), and two equivalent F(6) atoms. Both K(1)-F(1) bond lengths are 2.79 Å. Both K(1)-F(2) bond lengths are 2.56 Å. Both K(1)-F(4) bond lengths are 2.79 Å. There is one shorter (2.73 Å) and one longer (2.95 Å) K(1)-F(5) bond length. There is one shorter (2.58 Å) and one longer (2.99 Å) K(1)-F(6) bond length. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 8-coordinate geometry to one F(5), one F(6), two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms. The Na(1)-F(5) bond length is 2.40 Å. The Na(1)-F(6) bond length is 2.46 Å. Both Na(1)-F(1) bond lengths are 2.40 Å. Both Na(1)-F(2) bond lengths are 2.75 Å. Both Na(1)-F(3) bond lengths are 2.79 Å. In the second Na site, Na(2) is bonded in a 8-coordinate geometry to one F(7), one F(8), two equivalent F(2), two equivalent F(3), and two equivalent F(4) atoms. The Na(2)-F(7) bond length is 2.57 Å. The Na(2)-F(8) bond length is 2.38 Å. Both Na(2)-F(2) bond lengths are 2.65 Å. Both Na(2)-F(3) bond lengths are 2.67 Å. Both Na(2)-F(4) bond lengths are 2.44 Å. In the third Na site, Na(3) is bonded in a 8-coordinate geometry to one F(7), one F(8), two equivalent F(1), two equivalent F(3), and two equivalent F(4) atoms. The Na(3)-F(7) bond length is 2.37 Å. The Na(3)-F(8) bond length is 2.50 Å. Both Na(3)-F(1) bond lengths are 2.72 Å. Both Na(3)-F(3) bond lengths are 2.44 Å. Both Na(3)-F(4) bond lengths are 2.75 Å. There are two inequivalent Mg sites. In the first Mg site, Mg(1) is bonded to one F(1), one F(2), one F(3), one F(4), one F(6), and one F(8) atom to form corner-sharing MgF6 octahedra. The corner-sharing octahedral tilt angles range from 16-28°. The Mg(1)-F(1) bond length is 2.03 Å. The Mg(1)-F(2) bond length is 2.00 Å. The Mg(1)-F(3) bond length is 2.03 Å. The Mg(1)-F(4) bond length is 2.01 Å. The Mg(1)-F(6) bond length is 2.04 Å. The Mg(1)-F(8) bond length is 1.99 Å. In the second Mg site, Mg(2) is bonded to one F(1), one F(2), one F(3), one F(4), one F(5), and one F(7) atom to form corner-sharing MgF6 octahedra. The corner-sharing octahedral tilt angles range from 18-28°. The Mg(2)-F(1) bond length is 2.03 Å. The Mg(2)-F(2) bond length is 2.00 Å. The Mg(2)-F(3) bond length is 2.03 Å. The Mg(2)-F(4) bond length is 2.01 Å. The Mg(2)-F(5) bond length is 2.05 Å. The Mg(2)-F(7) bond length is 1.98 Å. There are eight inequivalent F sites. In the first F site, F(1) is bonded in a 5-coordinate geometry to one K(1), one Na(1), one Na(3), one Mg(1), and one Mg(2) atom. In the second F site, F(2) is bonded in a 5-coordinate geometry to one K(1), one Na(1), one Na(2), one Mg(1), and one Mg(2) atom. In the third F site, F(3) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), one Na(3), one Mg(1), and one Mg(2) atom. In the fourth F site, F(4) is bonded in a 5-coordinate geometry to one K(1), one Na(2), one Na(3), one Mg(1), and one Mg(2) atom. In the fifth F site, F(5) is bonded in a 5-coordinate geometry to two equivalent K(1), one Na(1), and two equivalent Mg(2) atoms. In the sixth F site, F(6) is bonded in a 4-coordinate geometry to two equivalent K(1), one Na(1), and two equivalent Mg(1) atoms. In the seventh F site, F(7) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), and two equivalent Mg(2) atoms. In the eighth F site, F(8) is bonded in a distorted tetrahedral geometry to one Na(2), one Na(3), and two equivalent Mg(1) atoms.