KNa7V8O24 is (Cubic) Perovskite-derived structured and crystallizes in the cubic Pm-3m space group. K(1) is bonded to twelve equivalent O(1) atoms to form KO12 cuboctahedra that share corners with twelve equivalent Na(2)O12 cuboctahedra, faces with six equivalent Na(1)O12 cuboctahedra, and faces with eight equivalent V(1)O6 octahedra. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded to four equivalent O(2) and eight equivalent O(1) atoms to form NaO12 cuboctahedra that share corners with four equivalent Na(3)O12 cuboctahedra, corners with eight equivalent Na(1)O12 cuboctahedra, faces with two equivalent K(1)O12 cuboctahedra, faces with four equivalent Na(2)O12 cuboctahedra, and faces with eight equivalent V(1)O6 octahedra. In the second Na site, Na(2) is bonded to four equivalent O(1) and eight equivalent O(2) atoms to form NaO12 cuboctahedra that share corners with four equivalent K(1)O12 cuboctahedra, corners with eight equivalent Na(2)O12 cuboctahedra, faces with two equivalent Na(3)O12 cuboctahedra, faces with four equivalent Na(1)O12 cuboctahedra, and faces with eight equivalent V(1)O6 octahedra. In the third Na site, Na(3) is bonded to twelve equivalent O(2) atoms to form NaO12 cuboctahedra that share corners with twelve equivalent Na(1)O12 cuboctahedra, faces with six equivalent Na(2)O12 cuboctahedra, and faces with eight equivalent V(1)O6 octahedra. V(1) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form VO6 octahedra that share corners with six equivalent V(1)O6 octahedra,  a faceface with one K(1)O12 cuboctahedra,  a faceface with one Na(3)O12 cuboctahedra, faces with three equivalent Na(1)O12 cuboctahedra, and faces with three equivalent Na(2)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-1°. There are two inequivalent O sites. In the first O site, O(1) is bonded to one K(1), one Na(2), two equivalent Na(1), and two equivalent V(1) atoms to form a mixture of distorted edge, face, and corner-sharing OKNa3V2 octahedra. The corner-sharing octahedral tilt angles range from 0-60°. In the second O site, O(2) is bonded in a distorted linear geometry to one Na(1), one Na(3), two equivalent Na(2), and two equivalent V(1) atoms.
KNa7V8O24 is (Cubic) Perovskite-derived structured and crystallizes in the cubic Pm-3m space group. K(1) is bonded to twelve equivalent O(1) atoms to form KO12 cuboctahedra that share corners with twelve equivalent Na(2)O12 cuboctahedra, faces with six equivalent Na(1)O12 cuboctahedra, and faces with eight equivalent V(1)O6 octahedra. All K(1)-O(1) bond lengths are 2.69 Å. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded to four equivalent O(2) and eight equivalent O(1) atoms to form NaO12 cuboctahedra that share corners with four equivalent Na(3)O12 cuboctahedra, corners with eight equivalent Na(1)O12 cuboctahedra, faces with two equivalent K(1)O12 cuboctahedra, faces with four equivalent Na(2)O12 cuboctahedra, and faces with eight equivalent V(1)O6 octahedra. All Na(1)-O(2) bond lengths are 2.67 Å. All Na(1)-O(1) bond lengths are 2.67 Å. In the second Na site, Na(2) is bonded to four equivalent O(1) and eight equivalent O(2) atoms to form NaO12 cuboctahedra that share corners with four equivalent K(1)O12 cuboctahedra, corners with eight equivalent Na(2)O12 cuboctahedra, faces with two equivalent Na(3)O12 cuboctahedra, faces with four equivalent Na(1)O12 cuboctahedra, and faces with eight equivalent V(1)O6 octahedra. All Na(2)-O(1) bond lengths are 2.65 Å. All Na(2)-O(2) bond lengths are 2.67 Å. In the third Na site, Na(3) is bonded to twelve equivalent O(2) atoms to form NaO12 cuboctahedra that share corners with twelve equivalent Na(1)O12 cuboctahedra, faces with six equivalent Na(2)O12 cuboctahedra, and faces with eight equivalent V(1)O6 octahedra. All Na(3)-O(2) bond lengths are 2.67 Å. V(1) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form VO6 octahedra that share corners with six equivalent V(1)O6 octahedra,  a faceface with one K(1)O12 cuboctahedra,  a faceface with one Na(3)O12 cuboctahedra, faces with three equivalent Na(1)O12 cuboctahedra, and faces with three equivalent Na(2)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-1°. All V(1)-O(1) bond lengths are 1.89 Å. All V(1)-O(2) bond lengths are 1.89 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to one K(1), one Na(2), two equivalent Na(1), and two equivalent V(1) atoms to form a mixture of distorted edge, face, and corner-sharing OKNa3V2 octahedra. The corner-sharing octahedral tilt angles range from 0-60°. In the second O site, O(2) is bonded in a distorted linear geometry to one Na(1), one Na(3), two equivalent Na(2), and two equivalent V(1) atoms.