K2NaMgVOF5 crystallizes in the orthorhombic Imm2 space group. There are two inequivalent K sites. In the first K site, K(1) is bonded in a 9-coordinate geometry to one Mg(1), two equivalent O(1), two equivalent F(2), and four equivalent F(1) atoms. In the second K site, K(2) is bonded in a 6-coordinate geometry to two equivalent O(1) and four equivalent F(1) atoms. Na(1) is bonded in a 5-coordinate geometry to one O(1) and four equivalent F(1) atoms. Mg(1) is bonded in a rectangular see-saw-like geometry to one K(1) and four equivalent F(1) atoms. V(1) is bonded in an octahedral geometry to one O(1), one F(2), and four equivalent F(1) atoms. O(1) is bonded in a 2-coordinate geometry to two equivalent K(1), two equivalent K(2), one Na(1), and one V(1) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a 5-coordinate geometry to one K(1), one K(2), one Na(1), one Mg(1), and one V(1) atom. In the second F site, F(2) is bonded in a distorted T-shaped geometry to two equivalent K(1) and one V(1) atom.
K2NaMgVOF5 crystallizes in the orthorhombic Imm2 space group. There are two inequivalent K sites. In the first K site, K(1) is bonded in a 9-coordinate geometry to one Mg(1), two equivalent O(1), two equivalent F(2), and four equivalent F(1) atoms. The K(1)-Mg(1) bond length is 3.28 Å. Both K(1)-O(1) bond lengths are 3.27 Å. Both K(1)-F(2) bond lengths are 2.86 Å. All K(1)-F(1) bond lengths are 2.96 Å. In the second K site, K(2) is bonded in a 6-coordinate geometry to two equivalent O(1) and four equivalent F(1) atoms. Both K(2)-O(1) bond lengths are 2.86 Å. All K(2)-F(1) bond lengths are 2.99 Å. Na(1) is bonded in a 5-coordinate geometry to one O(1) and four equivalent F(1) atoms. The Na(1)-O(1) bond length is 2.18 Å. All Na(1)-F(1) bond lengths are 2.26 Å. Mg(1) is bonded in a rectangular see-saw-like geometry to one K(1) and four equivalent F(1) atoms. All Mg(1)-F(1) bond lengths are 1.92 Å. V(1) is bonded in an octahedral geometry to one O(1), one F(2), and four equivalent F(1) atoms. The V(1)-O(1) bond length is 2.05 Å. The V(1)-F(2) bond length is 2.15 Å. All V(1)-F(1) bond lengths are 2.16 Å. O(1) is bonded in a 2-coordinate geometry to two equivalent K(1), two equivalent K(2), one Na(1), and one V(1) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a 5-coordinate geometry to one K(1), one K(2), one Na(1), one Mg(1), and one V(1) atom. In the second F site, F(2) is bonded in a distorted T-shaped geometry to two equivalent K(1) and one V(1) atom.