K5Na3Nb8O24 is (Cubic) Perovskite-derived structured and crystallizes in the tetragonal P4/mmm space group. There are four inequivalent K sites. In the first K site, K(1) is bonded to four equivalent O(3) and eight equivalent O(1) atoms to form KO12 cuboctahedra that share corners with four equivalent K(3)O12 cuboctahedra, corners with eight equivalent Na(2)O12 cuboctahedra, faces with two equivalent Na(1)O12 cuboctahedra, faces with four equivalent K(2)O12 cuboctahedra, and faces with eight equivalent Nb(1)O6 octahedra. In the second K site, K(2) is bonded to four equivalent O(1), four equivalent O(2), and four equivalent O(3) atoms to form KO12 cuboctahedra that share corners with four equivalent K(2)O12 cuboctahedra, corners with four equivalent K(4)O12 cuboctahedra, corners with four equivalent Na(1)O12 cuboctahedra, faces with two equivalent K(1)O12 cuboctahedra, faces with two equivalent K(3)O12 cuboctahedra, faces with two equivalent Na(2)O12 cuboctahedra, and faces with eight equivalent Nb(1)O6 octahedra. In the third K site, K(3) is bonded to four equivalent O(3) and eight equivalent O(2) atoms to form KO12 cuboctahedra that share corners with four equivalent K(1)O12 cuboctahedra, corners with eight equivalent Na(2)O12 cuboctahedra, faces with two equivalent K(4)O12 cuboctahedra, faces with four equivalent K(2)O12 cuboctahedra, and faces with eight equivalent Nb(1)O6 octahedra. In the fourth K site, K(4) is bonded to four equivalent O(4) and eight equivalent O(2) atoms to form KO12 cuboctahedra that share corners with four equivalent Na(1)O12 cuboctahedra, corners with eight equivalent K(2)O12 cuboctahedra, faces with two equivalent K(3)O12 cuboctahedra, faces with four equivalent Na(2)O12 cuboctahedra, and faces with eight equivalent Nb(1)O6 octahedra. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to four equivalent O(4) and eight equivalent O(1) atoms to form NaO12 cuboctahedra that share corners with four equivalent K(4)O12 cuboctahedra, corners with eight equivalent K(2)O12 cuboctahedra, faces with two equivalent K(1)O12 cuboctahedra, faces with four equivalent Na(2)O12 cuboctahedra, and faces with eight equivalent Nb(1)O6 octahedra. In the second Na site, Na(2) is bonded to four equivalent O(1), four equivalent O(2), and four equivalent O(4) atoms to form NaO12 cuboctahedra that share corners with four equivalent K(1)O12 cuboctahedra, corners with four equivalent K(3)O12 cuboctahedra, corners with four equivalent Na(2)O12 cuboctahedra, faces with two equivalent K(2)O12 cuboctahedra, faces with two equivalent K(4)O12 cuboctahedra, faces with two equivalent Na(1)O12 cuboctahedra, and faces with eight equivalent Nb(1)O6 octahedra. Nb(1) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms to form NbO6 octahedra that share corners with six equivalent Nb(1)O6 octahedra,  a faceface with one K(1)O12 cuboctahedra,  a faceface with one K(3)O12 cuboctahedra,  a faceface with one K(4)O12 cuboctahedra,  a faceface with one Na(1)O12 cuboctahedra, faces with two equivalent K(2)O12 cuboctahedra, and faces with two equivalent Na(2)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-1°. There are four inequivalent O sites. In the first O site, O(3) is bonded to one K(1), one K(3), two equivalent K(2), and two equivalent Nb(1) atoms to form a mixture of distorted edge and corner-sharing OK4Nb2 octahedra. The corner-sharing octahedra are not tilted. In the second O site, O(4) is bonded in a distorted linear geometry to one K(4), one Na(1), two equivalent Na(2), and two equivalent Nb(1) atoms. In the third O site, O(1) is bonded in a distorted linear geometry to one K(1), one K(2), one Na(1), one Na(2), and two equivalent Nb(1) atoms. In the fourth O site, O(2) is bonded in a distorted linear geometry to one K(2), one K(3), one K(4), one Na(2), and two equivalent Nb(1) atoms.
K5Na3Nb8O24 is (Cubic) Perovskite-derived structured and crystallizes in the tetragonal P4/mmm space group. There are four inequivalent K sites. In the first K site, K(1) is bonded to four equivalent O(3) and eight equivalent O(1) atoms to form KO12 cuboctahedra that share corners with four equivalent K(3)O12 cuboctahedra, corners with eight equivalent Na(2)O12 cuboctahedra, faces with two equivalent Na(1)O12 cuboctahedra, faces with four equivalent K(2)O12 cuboctahedra, and faces with eight equivalent Nb(1)O6 octahedra. All K(1)-O(3) bond lengths are 2.85 Å. All K(1)-O(1) bond lengths are 2.88 Å. In the second K site, K(2) is bonded to four equivalent O(1), four equivalent O(2), and four equivalent O(3) atoms to form KO12 cuboctahedra that share corners with four equivalent K(2)O12 cuboctahedra, corners with four equivalent K(4)O12 cuboctahedra, corners with four equivalent Na(1)O12 cuboctahedra, faces with two equivalent K(1)O12 cuboctahedra, faces with two equivalent K(3)O12 cuboctahedra, faces with two equivalent Na(2)O12 cuboctahedra, and faces with eight equivalent Nb(1)O6 octahedra. All K(2)-O(1) bond lengths are 2.88 Å. All K(2)-O(2) bond lengths are 2.86 Å. All K(2)-O(3) bond lengths are 2.86 Å. In the third K site, K(3) is bonded to four equivalent O(3) and eight equivalent O(2) atoms to form KO12 cuboctahedra that share corners with four equivalent K(1)O12 cuboctahedra, corners with eight equivalent Na(2)O12 cuboctahedra, faces with two equivalent K(4)O12 cuboctahedra, faces with four equivalent K(2)O12 cuboctahedra, and faces with eight equivalent Nb(1)O6 octahedra. All K(3)-O(3) bond lengths are 2.86 Å. All K(3)-O(2) bond lengths are 2.88 Å. In the fourth K site, K(4) is bonded to four equivalent O(4) and eight equivalent O(2) atoms to form KO12 cuboctahedra that share corners with four equivalent Na(1)O12 cuboctahedra, corners with eight equivalent K(2)O12 cuboctahedra, faces with two equivalent K(3)O12 cuboctahedra, faces with four equivalent Na(2)O12 cuboctahedra, and faces with eight equivalent Nb(1)O6 octahedra. All K(4)-O(4) bond lengths are 2.88 Å. All K(4)-O(2) bond lengths are 2.85 Å. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to four equivalent O(4) and eight equivalent O(1) atoms to form NaO12 cuboctahedra that share corners with four equivalent K(4)O12 cuboctahedra, corners with eight equivalent K(2)O12 cuboctahedra, faces with two equivalent K(1)O12 cuboctahedra, faces with four equivalent Na(2)O12 cuboctahedra, and faces with eight equivalent Nb(1)O6 octahedra. All Na(1)-O(4) bond lengths are 2.84 Å. All Na(1)-O(1) bond lengths are 2.83 Å. In the second Na site, Na(2) is bonded to four equivalent O(1), four equivalent O(2), and four equivalent O(4) atoms to form NaO12 cuboctahedra that share corners with four equivalent K(1)O12 cuboctahedra, corners with four equivalent K(3)O12 cuboctahedra, corners with four equivalent Na(2)O12 cuboctahedra, faces with two equivalent K(2)O12 cuboctahedra, faces with two equivalent K(4)O12 cuboctahedra, faces with two equivalent Na(1)O12 cuboctahedra, and faces with eight equivalent Nb(1)O6 octahedra. All Na(2)-O(1) bond lengths are 2.83 Å. All Na(2)-O(2) bond lengths are 2.83 Å. All Na(2)-O(4) bond lengths are 2.86 Å. Nb(1) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms to form NbO6 octahedra that share corners with six equivalent Nb(1)O6 octahedra,  a faceface with one K(1)O12 cuboctahedra,  a faceface with one K(3)O12 cuboctahedra,  a faceface with one K(4)O12 cuboctahedra,  a faceface with one Na(1)O12 cuboctahedra, faces with two equivalent K(2)O12 cuboctahedra, and faces with two equivalent Na(2)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-1°. The Nb(1)-O(3) bond length is 2.03 Å. The Nb(1)-O(4) bond length is 2.01 Å. Both Nb(1)-O(1) bond lengths are 2.02 Å. Both Nb(1)-O(2) bond lengths are 2.02 Å. There are four inequivalent O sites. In the first O site, O(3) is bonded to one K(1), one K(3), two equivalent K(2), and two equivalent Nb(1) atoms to form a mixture of distorted edge and corner-sharing OK4Nb2 octahedra. The corner-sharing octahedra are not tilted. In the second O site, O(4) is bonded in a distorted linear geometry to one K(4), one Na(1), two equivalent Na(2), and two equivalent Nb(1) atoms. In the third O site, O(1) is bonded in a distorted linear geometry to one K(1), one K(2), one Na(1), one Na(2), and two equivalent Nb(1) atoms. In the fourth O site, O(2) is bonded in a distorted linear geometry to one K(2), one K(3), one K(4), one Na(2), and two equivalent Nb(1) atoms.