K2NaMgVOF5 is Pb (Zr_0.50 Ti_0.48) O_3-derived structured and crystallizes in the triclinic P1 space group. There are two inequivalent K sites. In the first K site, K(1) is bonded in a 7-coordinate geometry to one O(1), one F(1), one F(2), one F(3), one F(4), and two equivalent F(5) atoms. In the second K site, K(2) is bonded in a 7-coordinate geometry to two equivalent O(1), one F(1), one F(2), one F(3), one F(4), and one F(5) atom. Na(1) is bonded to one O(1), one F(1), one F(2), and one F(5) atom to form distorted NaOF3 tetrahedra that share corners with four equivalent V(1)OF5 octahedra and corners with three equivalent Mg(1)OF4 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 3-70°. Mg(1) is bonded to one O(1), one F(1), one F(2), one F(3), and one F(4) atom to form distorted MgOF4 trigonal bipyramids that share corners with two equivalent V(1)OF5 octahedra, corners with three equivalent Na(1)OF3 tetrahedra, and  a faceface with one V(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 15-17°. V(1) is bonded to one O(1), one F(1), one F(2), one F(3), one F(4), and one F(5) atom to form VOF5 octahedra that share corners with four equivalent Na(1)OF3 tetrahedra, corners with two equivalent Mg(1)OF4 trigonal bipyramids, and  a faceface with one Mg(1)OF4 trigonal bipyramid. O(1) is bonded to one K(1), two equivalent K(2), one Na(1), one Mg(1), and one V(1) atom to form distorted OK3NaMgV octahedra that share corners with two equivalent O(1)K3NaMgV octahedra, corners with two equivalent F(5)K3NaV trigonal bipyramids, and edges with two equivalent F(5)K3NaV trigonal bipyramids. The corner-sharing octahedral tilt angles are 15°. There are five inequivalent F sites. In the first F site, F(1) is bonded in a 3-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 5-coordinate geometry to one K(1), one K(2), one Na(1), one Mg(1), and one V(1) atom. In the third F site, F(3) is bonded in a 2-coordinate geometry to one K(1), one K(2), one Mg(1), and one V(1) atom. In the fourth F site, F(4) is bonded in a 2-coordinate geometry to one K(1), one K(2), one Mg(1), and one V(1) atom. In the fifth F site, F(5) is bonded to one K(2), two equivalent K(1), one Na(1), and one V(1) atom to form distorted FK3NaV trigonal bipyramids that share corners with two equivalent O(1)K3NaMgV octahedra, corners with two equivalent F(5)K3NaV trigonal bipyramids, and edges with two equivalent O(1)K3NaMgV octahedra. The corner-sharing octahedral tilt angles range from 12-62°.
K2NaMgVOF5 is Pb (Zr_0.50 Ti_0.48) O_3-derived structured and crystallizes in the triclinic P1 space group. There are two inequivalent K sites. In the first K site, K(1) is bonded in a 7-coordinate geometry to one O(1), one F(1), one F(2), one F(3), one F(4), and two equivalent F(5) atoms. The K(1)-O(1) bond length is 2.52 Å. The K(1)-F(1) bond length is 3.03 Å. The K(1)-F(2) bond length is 3.01 Å. The K(1)-F(3) bond length is 3.04 Å. The K(1)-F(4) bond length is 3.09 Å. There is one shorter (2.91 Å) and one longer (2.93 Å) K(1)-F(5) bond length. In the second K site, K(2) is bonded in a 7-coordinate geometry to two equivalent O(1), one F(1), one F(2), one F(3), one F(4), and one F(5) atom. There is one shorter (2.92 Å) and one longer (2.94 Å) K(2)-O(1) bond length. The K(2)-F(1) bond length is 2.92 Å. The K(2)-F(2) bond length is 2.87 Å. The K(2)-F(3) bond length is 2.85 Å. The K(2)-F(4) bond length is 2.86 Å. The K(2)-F(5) bond length is 2.61 Å. Na(1) is bonded to one O(1), one F(1), one F(2), and one F(5) atom to form distorted NaOF3 tetrahedra that share corners with four equivalent V(1)OF5 octahedra and corners with three equivalent Mg(1)OF4 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 3-70°. The Na(1)-O(1) bond length is 2.25 Å. The Na(1)-F(1) bond length is 2.18 Å. The Na(1)-F(2) bond length is 2.18 Å. The Na(1)-F(5) bond length is 2.16 Å. Mg(1) is bonded to one O(1), one F(1), one F(2), one F(3), and one F(4) atom to form distorted MgOF4 trigonal bipyramids that share corners with two equivalent V(1)OF5 octahedra, corners with three equivalent Na(1)OF3 tetrahedra, and  a faceface with one V(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 15-17°. The Mg(1)-O(1) bond length is 1.92 Å. The Mg(1)-F(1) bond length is 2.09 Å. The Mg(1)-F(2) bond length is 2.10 Å. The Mg(1)-F(3) bond length is 1.96 Å. The Mg(1)-F(4) bond length is 1.96 Å. V(1) is bonded to one O(1), one F(1), one F(2), one F(3), one F(4), and one F(5) atom to form VOF5 octahedra that share corners with four equivalent Na(1)OF3 tetrahedra, corners with two equivalent Mg(1)OF4 trigonal bipyramids, and  a faceface with one Mg(1)OF4 trigonal bipyramid. The V(1)-O(1) bond length is 2.15 Å. The V(1)-F(1) bond length is 2.15 Å. The V(1)-F(2) bond length is 2.14 Å. The V(1)-F(3) bond length is 2.14 Å. The V(1)-F(4) bond length is 2.14 Å. The V(1)-F(5) bond length is 2.13 Å. O(1) is bonded to one K(1), two equivalent K(2), one Na(1), one Mg(1), and one V(1) atom to form distorted OK3NaMgV octahedra that share corners with two equivalent O(1)K3NaMgV octahedra, corners with two equivalent F(5)K3NaV trigonal bipyramids, and edges with two equivalent F(5)K3NaV trigonal bipyramids. The corner-sharing octahedral tilt angles are 15°. There are five inequivalent F sites. In the first F site, F(1) is bonded in a 3-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 5-coordinate geometry to one K(1), one K(2), one Na(1), one Mg(1), and one V(1) atom. In the third F site, F(3) is bonded in a 2-coordinate geometry to one K(1), one K(2), one Mg(1), and one V(1) atom. In the fourth F site, F(4) is bonded in a 2-coordinate geometry to one K(1), one K(2), one Mg(1), and one V(1) atom. In the fifth F site, F(5) is bonded to one K(2), two equivalent K(1), one Na(1), and one V(1) atom to form distorted FK3NaV trigonal bipyramids that share corners with two equivalent O(1)K3NaMgV octahedra, corners with two equivalent F(5)K3NaV trigonal bipyramids, and edges with two equivalent O(1)K3NaMgV octahedra. The corner-sharing octahedral tilt angles range from 12-62°.