K2NaVOF5 is (Cubic) Perovskite-derived structured and crystallizes in the orthorhombic Pmm2 space group. There are four inequivalent K sites. In the first K site, K(1) is bonded to two equivalent O(1); two equivalent F(1); and eight F(2,2) atoms to form KO2F10 cuboctahedra that share corners with twelve K(1,1)O2F10 cuboctahedra; faces with six K(1,1)O2F10 cuboctahedra; faces with four Na(1,1)OF5 octahedra; and faces with four V(1,1)OF5 octahedra. In the second K site, K(1) is bonded to two equivalent O(1); two equivalent F(1); and eight F(2,2) atoms to form KO2F10 cuboctahedra that share corners with twelve K(1,1)O2F10 cuboctahedra; faces with six K(1,1)O2F10 cuboctahedra; faces with four Na(1,1)OF5 octahedra; and faces with four V(1,1)OF5 octahedra. In the third K site, K(1) is bonded to two equivalent O(1); two equivalent F(1); and eight F(2,2) atoms to form KO2F10 cuboctahedra that share corners with twelve K(1,1)O2F10 cuboctahedra; faces with six K(1,1)O2F10 cuboctahedra; faces with four Na(1,1)OF5 octahedra; and faces with four V(1,1)OF5 octahedra. In the fourth K site, K(1) is bonded to two equivalent O(1); two equivalent F(1); and eight F(2,2) atoms to form KO2F10 cuboctahedra that share corners with twelve K(1,1)O2F10 cuboctahedra; faces with six K(1,1)O2F10 cuboctahedra; faces with four Na(1,1)OF5 octahedra; and faces with four V(1,1)OF5 octahedra. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(1), one F(1), and four equivalent F(2) atoms to form NaOF5 octahedra that share corners with six V(1,1)OF5 octahedra and faces with eight K(1,1,1,1)O2F10 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-8°. In the second Na site, Na(1) is bonded to one O(1), one F(1), and four equivalent F(2) atoms to form NaOF5 octahedra that share corners with six V(1,1)OF5 octahedra and faces with eight K(1,1,1,1)O2F10 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-8°. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one F(1), and four equivalent F(2) atoms to form VOF5 octahedra that share corners with six Na(1,1)OF5 octahedra and faces with eight K(1,1,1,1)O2F10 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-8°. In the second V site, V(1) is bonded to one O(1), one F(1), and four equivalent F(2) atoms to form VOF5 octahedra that share corners with six Na(1,1)OF5 octahedra and faces with eight K(1,1,1,1)O2F10 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-8°. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 2-coordinate geometry to four K(1,1); one Na(1); and one V(1) atom. In the second O site, O(1) is bonded in a 2-coordinate geometry to four K(1,1); one Na(1); and one V(1) atom. There are four inequivalent F sites. In the first F site, F(1) is bonded in a distorted linear geometry to four K(1,1); one Na(1); and one V(1) atom. In the second F site, F(1) is bonded in a distorted linear geometry to four K(1,1); one Na(1); and one V(1) atom. In the third F site, F(2) is bonded in a distorted linear geometry to four K(1,1,1,1); one Na(1); and one V(1) atom. In the fourth F site, F(2) is bonded in a distorted linear geometry to four K(1,1,1,1); one Na(1); and one V(1) atom.
K2NaVOF5 is (Cubic) Perovskite-derived structured and crystallizes in the orthorhombic Pmm2 space group. There are four inequivalent K sites. In the first K site, K(1) is bonded to two equivalent O(1); two equivalent F(1); and eight F(2,2) atoms to form KO2F10 cuboctahedra that share corners with twelve K(1,1)O2F10 cuboctahedra; faces with six K(1,1)O2F10 cuboctahedra; faces with four Na(1,1)OF5 octahedra; and faces with four V(1,1)OF5 octahedra. Both K(1)-O(1) bond lengths are 3.02 Å. Both K(1)-F(1) bond lengths are 3.00 Å. There are four shorter (2.91 Å) and four longer (3.05 Å) K(1)-F(2,2) bond lengths. In the second K site, K(1) is bonded to two equivalent O(1); two equivalent F(1); and eight F(2,2) atoms to form KO2F10 cuboctahedra that share corners with twelve K(1,1)O2F10 cuboctahedra; faces with six K(1,1)O2F10 cuboctahedra; faces with four Na(1,1)OF5 octahedra; and faces with four V(1,1)OF5 octahedra. Both K(1)-O(1) bond lengths are 3.02 Å. Both K(1)-F(1) bond lengths are 3.00 Å. There are four shorter (2.92 Å) and four longer (3.06 Å) K(1)-F(2,2) bond lengths. In the third K site, K(1) is bonded to two equivalent O(1); two equivalent F(1); and eight F(2,2) atoms to form KO2F10 cuboctahedra that share corners with twelve K(1,1)O2F10 cuboctahedra; faces with six K(1,1)O2F10 cuboctahedra; faces with four Na(1,1)OF5 octahedra; and faces with four V(1,1)OF5 octahedra. Both K(1)-O(1) bond lengths are 3.01 Å. Both K(1)-F(1) bond lengths are 3.01 Å. There are four shorter (2.92 Å) and four longer (3.05 Å) K(1)-F(2,2) bond lengths. In the fourth K site, K(1) is bonded to two equivalent O(1); two equivalent F(1); and eight F(2,2) atoms to form KO2F10 cuboctahedra that share corners with twelve K(1,1)O2F10 cuboctahedra; faces with six K(1,1)O2F10 cuboctahedra; faces with four Na(1,1)OF5 octahedra; and faces with four V(1,1)OF5 octahedra. Both K(1)-O(1) bond lengths are 3.01 Å. Both K(1)-F(1) bond lengths are 3.01 Å. There are four shorter (2.92 Å) and four longer (3.05 Å) K(1)-F(2,2) bond lengths. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(1), one F(1), and four equivalent F(2) atoms to form NaOF5 octahedra that share corners with six V(1,1)OF5 octahedra and faces with eight K(1,1,1,1)O2F10 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-8°. The Na(1)-O(1) bond length is 2.37 Å. The Na(1)-F(1) bond length is 2.28 Å. All Na(1)-F(2) bond lengths are 2.28 Å. In the second Na site, Na(1) is bonded to one O(1), one F(1), and four equivalent F(2) atoms to form NaOF5 octahedra that share corners with six V(1,1)OF5 octahedra and faces with eight K(1,1,1,1)O2F10 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-8°. The Na(1)-O(1) bond length is 2.38 Å. The Na(1)-F(1) bond length is 2.27 Å. All Na(1)-F(2) bond lengths are 2.28 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one F(1), and four equivalent F(2) atoms to form VOF5 octahedra that share corners with six Na(1,1)OF5 octahedra and faces with eight K(1,1,1,1)O2F10 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-8°. The V(1)-O(1) bond length is 1.68 Å. The V(1)-F(1) bond length is 2.04 Å. All V(1)-F(2) bond lengths are 1.97 Å. In the second V site, V(1) is bonded to one O(1), one F(1), and four equivalent F(2) atoms to form VOF5 octahedra that share corners with six Na(1,1)OF5 octahedra and faces with eight K(1,1,1,1)O2F10 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-8°. The V(1)-O(1) bond length is 1.69 Å. The V(1)-F(1) bond length is 2.04 Å. All V(1)-F(2) bond lengths are 1.97 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 2-coordinate geometry to four K(1,1); one Na(1); and one V(1) atom. In the second O site, O(1) is bonded in a 2-coordinate geometry to four K(1,1); one Na(1); and one V(1) atom. There are four inequivalent F sites. In the first F site, F(1) is bonded in a distorted linear geometry to four K(1,1); one Na(1); and one V(1) atom. In the second F site, F(1) is bonded in a distorted linear geometry to four K(1,1); one Na(1); and one V(1) atom. In the third F site, F(2) is bonded in a distorted linear geometry to four K(1,1,1,1); one Na(1); and one V(1) atom. In the fourth F site, F(2) is bonded in a distorted linear geometry to four K(1,1,1,1); one Na(1); and one V(1) atom.