K3ScV2O8 crystallizes in the trigonal P-3m1 space group. There are two inequivalent K sites. In the first K site, K(1) is bonded in a 10-coordinate geometry to one O(1) and nine equivalent O(2) atoms. In the second K site, K(2) is bonded to six equivalent O(1) and six equivalent O(2) atoms to form distorted KO12 cuboctahedra that share edges with six equivalent K(2)O12 cuboctahedra, edges with six equivalent V(1)O4 tetrahedra, and faces with two equivalent Sc(1)O6 octahedra. Sc(1) is bonded to six equivalent O(2) atoms to form ScO6 octahedra that share corners with six equivalent V(1)O4 tetrahedra and faces with two equivalent K(2)O12 cuboctahedra. V(1) is bonded to one O(1) and three equivalent O(2) atoms to form VO4 tetrahedra that share corners with three equivalent Sc(1)O6 octahedra and edges with three equivalent K(2)O12 cuboctahedra. The corner-sharing octahedral tilt angles are 16°. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted linear geometry to one K(1), three equivalent K(2), and one V(1) atom. In the second O site, O(2) is bonded in a 2-coordinate geometry to one K(2), three equivalent K(1), one Sc(1), and one V(1) atom.
K3ScV2O8 crystallizes in the trigonal P-3m1 space group. There are two inequivalent K sites. In the first K site, K(1) is bonded in a 10-coordinate geometry to one O(1) and nine equivalent O(2) atoms. The K(1)-O(1) bond length is 2.58 Å. There are six shorter (2.92 Å) and three longer (3.08 Å) K(1)-O(2) bond lengths. In the second K site, K(2) is bonded to six equivalent O(1) and six equivalent O(2) atoms to form distorted KO12 cuboctahedra that share edges with six equivalent K(2)O12 cuboctahedra, edges with six equivalent V(1)O4 tetrahedra, and faces with two equivalent Sc(1)O6 octahedra. All K(2)-O(1) bond lengths are 3.37 Å. All K(2)-O(2) bond lengths are 3.01 Å. Sc(1) is bonded to six equivalent O(2) atoms to form ScO6 octahedra that share corners with six equivalent V(1)O4 tetrahedra and faces with two equivalent K(2)O12 cuboctahedra. All Sc(1)-O(2) bond lengths are 2.13 Å. V(1) is bonded to one O(1) and three equivalent O(2) atoms to form VO4 tetrahedra that share corners with three equivalent Sc(1)O6 octahedra and edges with three equivalent K(2)O12 cuboctahedra. The corner-sharing octahedral tilt angles are 16°. The V(1)-O(1) bond length is 1.68 Å. All V(1)-O(2) bond lengths are 1.77 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted linear geometry to one K(1), three equivalent K(2), and one V(1) atom. In the second O site, O(2) is bonded in a 2-coordinate geometry to one K(2), three equivalent K(1), one Sc(1), and one V(1) atom.