K3V(VO4)2 crystallizes in the monoclinic C2/m space group. There are two inequivalent K sites. In the first K site, K(1) is bonded to two equivalent O(3), four equivalent O(2), and six equivalent O(1) atoms to form KO12 cuboctahedra that share edges with six equivalent K(1)O12 cuboctahedra, edges with six equivalent V(2)O4 tetrahedra, and faces with two equivalent V(1)O6 octahedra. In the second K site, K(2) is bonded in a 10-coordinate geometry to one O(1), three equivalent O(3), and six equivalent O(2) atoms. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form VO6 octahedra that share corners with six equivalent V(2)O4 tetrahedra and faces with two equivalent K(1)O12 cuboctahedra. In the second V site, V(2) is bonded to one O(1), one O(3), and two equivalent O(2) atoms to form VO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra and edges with three equivalent K(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 15-16°. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted linear geometry to one K(2), three equivalent K(1), and one V(2) atom. In the second O site, O(2) is bonded in a 2-coordinate geometry to one K(1), three equivalent K(2), one V(1), and one V(2) atom. In the third O site, O(3) is bonded in a 2-coordinate geometry to one K(1), three equivalent K(2), one V(1), and one V(2) atom.
K3V(VO4)2 crystallizes in the monoclinic C2/m space group. There are two inequivalent K sites. In the first K site, K(1) is bonded to two equivalent O(3), four equivalent O(2), and six equivalent O(1) atoms to form KO12 cuboctahedra that share edges with six equivalent K(1)O12 cuboctahedra, edges with six equivalent V(2)O4 tetrahedra, and faces with two equivalent V(1)O6 octahedra. Both K(1)-O(3) bond lengths are 2.99 Å. All K(1)-O(2) bond lengths are 2.99 Å. All K(1)-O(1) bond lengths are 3.26 Å. In the second K site, K(2) is bonded in a 10-coordinate geometry to one O(1), three equivalent O(3), and six equivalent O(2) atoms. The K(2)-O(1) bond length is 2.57 Å. There are two shorter (2.83 Å) and one longer (3.01 Å) K(2)-O(3) bond length. There are a spread of K(2)-O(2) bond distances ranging from 2.82-3.02 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form VO6 octahedra that share corners with six equivalent V(2)O4 tetrahedra and faces with two equivalent K(1)O12 cuboctahedra. Both V(1)-O(3) bond lengths are 2.00 Å. All V(1)-O(2) bond lengths are 2.00 Å. In the second V site, V(2) is bonded to one O(1), one O(3), and two equivalent O(2) atoms to form VO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra and edges with three equivalent K(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 15-16°. The V(2)-O(1) bond length is 1.66 Å. The V(2)-O(3) bond length is 1.75 Å. Both V(2)-O(2) bond lengths are 1.75 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted linear geometry to one K(2), three equivalent K(1), and one V(2) atom. In the second O site, O(2) is bonded in a 2-coordinate geometry to one K(1), three equivalent K(2), one V(1), and one V(2) atom. In the third O site, O(3) is bonded in a 2-coordinate geometry to one K(1), three equivalent K(2), one V(1), and one V(2) atom.