K2NaNbO2F4 is (Cubic) Perovskite-derived structured and crystallizes in the triclinic P1 space group. There are four inequivalent K sites. In the first K site, K(1) is bonded to one O(1), one O(2), one O(3), one O(4), one F(1), one F(4), one F(7), one F(8), two equivalent F(3), and two equivalent F(5) atoms to form KO4F8 cuboctahedra that share corners with four equivalent K(1)O4F8 cuboctahedra, corners with eight equivalent K(3)O4F8 cuboctahedra, faces with two equivalent K(4)O4F8 cuboctahedra, faces with four equivalent K(2)O4F8 cuboctahedra, faces with two equivalent Na(1)O2F4 octahedra, faces with two equivalent Na(2)O2F4 octahedra, faces with two equivalent Nb(1)O2F4 octahedra, and faces with two equivalent Nb(2)O2F4 octahedra. In the second K site, K(2) is bonded to one O(1), one O(2), one O(3), one O(4), one F(1), one F(4), one F(7), one F(8), two equivalent F(3), and two equivalent F(5) atoms to form KO4F8 cuboctahedra that share corners with four equivalent K(2)O4F8 cuboctahedra, corners with eight equivalent K(4)O4F8 cuboctahedra, faces with two equivalent K(3)O4F8 cuboctahedra, faces with four equivalent K(1)O4F8 cuboctahedra, faces with two equivalent Na(1)O2F4 octahedra, faces with two equivalent Na(2)O2F4 octahedra, faces with two equivalent Nb(1)O2F4 octahedra, and faces with two equivalent Nb(2)O2F4 octahedra. In the third K site, K(3) is bonded to one O(1), one O(2), one O(3), one O(4), one F(1), one F(4), one F(7), one F(8), two equivalent F(2), and two equivalent F(6) atoms to form KO4F8 cuboctahedra that share corners with four equivalent K(3)O4F8 cuboctahedra, corners with eight equivalent K(1)O4F8 cuboctahedra, faces with two equivalent K(2)O4F8 cuboctahedra, faces with four equivalent K(4)O4F8 cuboctahedra, faces with two equivalent Na(1)O2F4 octahedra, faces with two equivalent Na(2)O2F4 octahedra, faces with two equivalent Nb(1)O2F4 octahedra, and faces with two equivalent Nb(2)O2F4 octahedra. In the fourth K site, K(4) is bonded to one O(1), one O(2), one O(3), one O(4), one F(1), one F(4), one F(7), one F(8), two equivalent F(2), and two equivalent F(6) atoms to form KO4F8 cuboctahedra that share corners with four equivalent K(4)O4F8 cuboctahedra, corners with eight equivalent K(2)O4F8 cuboctahedra, faces with two equivalent K(1)O4F8 cuboctahedra, faces with four equivalent K(3)O4F8 cuboctahedra, faces with two equivalent Na(1)O2F4 octahedra, faces with two equivalent Na(2)O2F4 octahedra, faces with two equivalent Nb(1)O2F4 octahedra, and faces with two equivalent Nb(2)O2F4 octahedra. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(1), one O(4), one F(4), one F(5), one F(6), and one F(7) atom to form NaO2F4 octahedra that share corners with two equivalent Nb(2)O2F4 octahedra, corners with four equivalent Nb(1)O2F4 octahedra, faces with two equivalent K(1)O4F8 cuboctahedra, faces with two equivalent K(2)O4F8 cuboctahedra, faces with two equivalent K(3)O4F8 cuboctahedra, and faces with two equivalent K(4)O4F8 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-2°. In the second Na site, Na(2) is bonded to one O(2), one O(3), one F(1), one F(2), one F(3), and one F(8) atom to form NaO2F4 octahedra that share corners with two equivalent Nb(1)O2F4 octahedra, corners with four equivalent Nb(2)O2F4 octahedra, faces with two equivalent K(1)O4F8 cuboctahedra, faces with two equivalent K(2)O4F8 cuboctahedra, faces with two equivalent K(3)O4F8 cuboctahedra, and faces with two equivalent K(4)O4F8 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-2°. There are two inequivalent Nb sites. In the first Nb site, Nb(1) is bonded to one O(1), one O(4), one F(2), one F(3), one F(4), and one F(7) atom to form NbO2F4 octahedra that share corners with two equivalent Na(2)O2F4 octahedra, corners with four equivalent Na(1)O2F4 octahedra, faces with two equivalent K(1)O4F8 cuboctahedra, faces with two equivalent K(2)O4F8 cuboctahedra, faces with two equivalent K(3)O4F8 cuboctahedra, and faces with two equivalent K(4)O4F8 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-2°. In the second Nb site, Nb(2) is bonded to one O(2), one O(3), one F(1), one F(5), one F(6), and one F(8) atom to form NbO2F4 octahedra that share corners with two equivalent Na(1)O2F4 octahedra, corners with four equivalent Na(2)O2F4 octahedra, faces with two equivalent K(1)O4F8 cuboctahedra, faces with two equivalent K(2)O4F8 cuboctahedra, faces with two equivalent K(3)O4F8 cuboctahedra, and faces with two equivalent K(4)O4F8 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-2°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a 2-coordinate geometry to one K(1), one K(2), one K(3), one K(4), one Na(1), and one Nb(1) atom. In the second O site, O(2) is bonded in a distorted linear geometry to one K(1), one K(2), one K(3), one K(4), one Na(2), and one Nb(2) atom. In the third O site, O(3) is bonded in a 2-coordinate geometry to one K(1), one K(2), one K(3), one K(4), one Na(2), and one Nb(2) atom. In the fourth O site, O(4) is bonded in a distorted linear geometry to one K(1), one K(2), one K(3), one K(4), one Na(1), and one Nb(1) atom. There are eight inequivalent F sites. In the first F site, F(1) is bonded in a distorted linear geometry to one K(1), one K(2), one K(3), one K(4), one Na(2), and one Nb(2) atom. In the second F site, F(2) is bonded in a distorted linear geometry to two equivalent K(3), two equivalent K(4), one Na(2), and one Nb(1) atom. In the third F site, F(3) is bonded in a distorted linear geometry to two equivalent K(1), two equivalent K(2), one Na(2), and one Nb(1) atom. In the fourth F site, F(4) is bonded in a distorted linear geometry to one K(1), one K(2), one K(3), one K(4), one Na(1), and one Nb(1) atom. In the fifth F site, F(5) is bonded in a distorted linear geometry to two equivalent K(1), two equivalent K(2), one Na(1), and one Nb(2) atom. In the sixth F site, F(6) is bonded in a distorted linear geometry to two equivalent K(3), two equivalent K(4), one Na(1), and one Nb(2) atom. In the seventh F site, F(7) is bonded in a distorted linear geometry to one K(1), one K(2), one K(3), one K(4), one Na(1), and one Nb(1) atom. In the eighth F site, F(8) is bonded in a distorted linear geometry to one K(1), one K(2), one K(3), one K(4), one Na(2), and one Nb(2) atom.
K2NaNbO2F4 is (Cubic) Perovskite-derived structured and crystallizes in the triclinic P1 space group. There are four inequivalent K sites. In the first K site, K(1) is bonded to one O(1), one O(2), one O(3), one O(4), one F(1), one F(4), one F(7), one F(8), two equivalent F(3), and two equivalent F(5) atoms to form KO4F8 cuboctahedra that share corners with four equivalent K(1)O4F8 cuboctahedra, corners with eight equivalent K(3)O4F8 cuboctahedra, faces with two equivalent K(4)O4F8 cuboctahedra, faces with four equivalent K(2)O4F8 cuboctahedra, faces with two equivalent Na(1)O2F4 octahedra, faces with two equivalent Na(2)O2F4 octahedra, faces with two equivalent Nb(1)O2F4 octahedra, and faces with two equivalent Nb(2)O2F4 octahedra. The K(1)-O(1) bond length is 3.02 Å. The K(1)-O(2) bond length is 3.09 Å. The K(1)-O(3) bond length is 3.07 Å. The K(1)-O(4) bond length is 3.07 Å. The K(1)-F(1) bond length is 3.06 Å. The K(1)-F(4) bond length is 3.02 Å. The K(1)-F(7) bond length is 3.04 Å. The K(1)-F(8) bond length is 3.01 Å. There is one shorter (3.02 Å) and one longer (3.07 Å) K(1)-F(3) bond length. There is one shorter (3.01 Å) and one longer (3.08 Å) K(1)-F(5) bond length. In the second K site, K(2) is bonded to one O(1), one O(2), one O(3), one O(4), one F(1), one F(4), one F(7), one F(8), two equivalent F(3), and two equivalent F(5) atoms to form KO4F8 cuboctahedra that share corners with four equivalent K(2)O4F8 cuboctahedra, corners with eight equivalent K(4)O4F8 cuboctahedra, faces with two equivalent K(3)O4F8 cuboctahedra, faces with four equivalent K(1)O4F8 cuboctahedra, faces with two equivalent Na(1)O2F4 octahedra, faces with two equivalent Na(2)O2F4 octahedra, faces with two equivalent Nb(1)O2F4 octahedra, and faces with two equivalent Nb(2)O2F4 octahedra. The K(2)-O(1) bond length is 3.04 Å. The K(2)-O(2) bond length is 3.04 Å. The K(2)-O(3) bond length is 3.07 Å. The K(2)-O(4) bond length is 3.02 Å. The K(2)-F(1) bond length is 3.03 Å. The K(2)-F(4) bond length is 3.02 Å. The K(2)-F(7) bond length is 3.08 Å. The K(2)-F(8) bond length is 3.09 Å. Both K(2)-F(3) bond lengths are 3.04 Å. There is one shorter (2.99 Å) and one longer (3.10 Å) K(2)-F(5) bond length. In the third K site, K(3) is bonded to one O(1), one O(2), one O(3), one O(4), one F(1), one F(4), one F(7), one F(8), two equivalent F(2), and two equivalent F(6) atoms to form KO4F8 cuboctahedra that share corners with four equivalent K(3)O4F8 cuboctahedra, corners with eight equivalent K(1)O4F8 cuboctahedra, faces with two equivalent K(2)O4F8 cuboctahedra, faces with four equivalent K(4)O4F8 cuboctahedra, faces with two equivalent Na(1)O2F4 octahedra, faces with two equivalent Na(2)O2F4 octahedra, faces with two equivalent Nb(1)O2F4 octahedra, and faces with two equivalent Nb(2)O2F4 octahedra. The K(3)-O(1) bond length is 3.11 Å. The K(3)-O(2) bond length is 3.05 Å. The K(3)-O(3) bond length is 3.01 Å. The K(3)-O(4) bond length is 3.05 Å. The K(3)-F(1) bond length is 3.04 Å. The K(3)-F(4) bond length is 3.11 Å. The K(3)-F(7) bond length is 3.05 Å. The K(3)-F(8) bond length is 3.08 Å. There is one shorter (3.03 Å) and one longer (3.06 Å) K(3)-F(2) bond length. There is one shorter (3.04 Å) and one longer (3.05 Å) K(3)-F(6) bond length. In the fourth K site, K(4) is bonded to one O(1), one O(2), one O(3), one O(4), one F(1), one F(4), one F(7), one F(8), two equivalent F(2), and two equivalent F(6) atoms to form KO4F8 cuboctahedra that share corners with four equivalent K(4)O4F8 cuboctahedra, corners with eight equivalent K(2)O4F8 cuboctahedra, faces with two equivalent K(1)O4F8 cuboctahedra, faces with four equivalent K(3)O4F8 cuboctahedra, faces with two equivalent Na(1)O2F4 octahedra, faces with two equivalent Na(2)O2F4 octahedra, faces with two equivalent Nb(1)O2F4 octahedra, and faces with two equivalent Nb(2)O2F4 octahedra. The K(4)-O(1) bond length is 3.03 Å. The K(4)-O(2) bond length is 3.07 Å. The K(4)-O(3) bond length is 3.13 Å. The K(4)-O(4) bond length is 3.06 Å. The K(4)-F(1) bond length is 3.10 Å. The K(4)-F(4) bond length is 3.03 Å. The K(4)-F(7) bond length is 3.00 Å. The K(4)-F(8) bond length is 3.05 Å. There is one shorter (3.01 Å) and one longer (3.08 Å) K(4)-F(2) bond length. There is one shorter (3.01 Å) and one longer (3.08 Å) K(4)-F(6) bond length. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(1), one O(4), one F(4), one F(5), one F(6), and one F(7) atom to form NaO2F4 octahedra that share corners with two equivalent Nb(2)O2F4 octahedra, corners with four equivalent Nb(1)O2F4 octahedra, faces with two equivalent K(1)O4F8 cuboctahedra, faces with two equivalent K(2)O4F8 cuboctahedra, faces with two equivalent K(3)O4F8 cuboctahedra, and faces with two equivalent K(4)O4F8 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-2°. The Na(1)-O(1) bond length is 2.40 Å. The Na(1)-O(4) bond length is 2.39 Å. The Na(1)-F(4) bond length is 2.26 Å. The Na(1)-F(5) bond length is 2.26 Å. The Na(1)-F(6) bond length is 2.30 Å. The Na(1)-F(7) bond length is 2.27 Å. In the second Na site, Na(2) is bonded to one O(2), one O(3), one F(1), one F(2), one F(3), and one F(8) atom to form NaO2F4 octahedra that share corners with two equivalent Nb(1)O2F4 octahedra, corners with four equivalent Nb(2)O2F4 octahedra, faces with two equivalent K(1)O4F8 cuboctahedra, faces with two equivalent K(2)O4F8 cuboctahedra, faces with two equivalent K(3)O4F8 cuboctahedra, and faces with two equivalent K(4)O4F8 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-2°. The Na(2)-O(2) bond length is 2.38 Å. The Na(2)-O(3) bond length is 2.41 Å. The Na(2)-F(1) bond length is 2.27 Å. The Na(2)-F(2) bond length is 2.29 Å. The Na(2)-F(3) bond length is 2.28 Å. The Na(2)-F(8) bond length is 2.25 Å. There are two inequivalent Nb sites. In the first Nb site, Nb(1) is bonded to one O(1), one O(4), one F(2), one F(3), one F(4), and one F(7) atom to form NbO2F4 octahedra that share corners with two equivalent Na(2)O2F4 octahedra, corners with four equivalent Na(1)O2F4 octahedra, faces with two equivalent K(1)O4F8 cuboctahedra, faces with two equivalent K(2)O4F8 cuboctahedra, faces with two equivalent K(3)O4F8 cuboctahedra, and faces with two equivalent K(4)O4F8 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-2°. The Nb(1)-O(1) bond length is 1.90 Å. The Nb(1)-O(4) bond length is 1.91 Å. The Nb(1)-F(2) bond length is 2.03 Å. The Nb(1)-F(3) bond length is 2.04 Å. The Nb(1)-F(4) bond length is 2.03 Å. The Nb(1)-F(7) bond length is 2.04 Å. In the second Nb site, Nb(2) is bonded to one O(2), one O(3), one F(1), one F(5), one F(6), and one F(8) atom to form NbO2F4 octahedra that share corners with two equivalent Na(1)O2F4 octahedra, corners with four equivalent Na(2)O2F4 octahedra, faces with two equivalent K(1)O4F8 cuboctahedra, faces with two equivalent K(2)O4F8 cuboctahedra, faces with two equivalent K(3)O4F8 cuboctahedra, and faces with two equivalent K(4)O4F8 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-2°. The Nb(2)-O(2) bond length is 1.90 Å. The Nb(2)-O(3) bond length is 1.91 Å. The Nb(2)-F(1) bond length is 2.04 Å. The Nb(2)-F(5) bond length is 2.04 Å. The Nb(2)-F(6) bond length is 2.03 Å. The Nb(2)-F(8) bond length is 2.04 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a 2-coordinate geometry to one K(1), one K(2), one K(3), one K(4), one Na(1), and one Nb(1) atom. In the second O site, O(2) is bonded in a distorted linear geometry to one K(1), one K(2), one K(3), one K(4), one Na(2), and one Nb(2) atom. In the third O site, O(3) is bonded in a 2-coordinate geometry to one K(1), one K(2), one K(3), one K(4), one Na(2), and one Nb(2) atom. In the fourth O site, O(4) is bonded in a distorted linear geometry to one K(1), one K(2), one K(3), one K(4), one Na(1), and one Nb(1) atom. There are eight inequivalent F sites. In the first F site, F(1) is bonded in a distorted linear geometry to one K(1), one K(2), one K(3), one K(4), one Na(2), and one Nb(2) atom. In the second F site, F(2) is bonded in a distorted linear geometry to two equivalent K(3), two equivalent K(4), one Na(2), and one Nb(1) atom. In the third F site, F(3) is bonded in a distorted linear geometry to two equivalent K(1), two equivalent K(2), one Na(2), and one Nb(1) atom. In the fourth F site, F(4) is bonded in a distorted linear geometry to one K(1), one K(2), one K(3), one K(4), one Na(1), and one Nb(1) atom. In the fifth F site, F(5) is bonded in a distorted linear geometry to two equivalent K(1), two equivalent K(2), one Na(1), and one Nb(2) atom. In the sixth F site, F(6) is bonded in a distorted linear geometry to two equivalent K(3), two equivalent K(4), one Na(1), and one Nb(2) atom. In the seventh F site, F(7) is bonded in a distorted linear geometry to one K(1), one K(2), one K(3), one K(4), one Na(1), and one Nb(1) atom. In the eighth F site, F(8) is bonded in a distorted linear geometry to one K(1), one K(2), one K(3), one K(4), one Na(2), and one Nb(2) atom.