KVOPO4 crystallizes in the orthorhombic P2_12_12_1 space group. K(1) is bonded in a 9-coordinate geometry to one O(3), two equivalent O(1), two equivalent O(2), two equivalent O(4), and two equivalent O(5) atoms. V(1) is bonded to one O(1), one O(2), one O(3), one O(4), and one O(5) atom to form distorted VO5 trigonal bipyramids that share corners with two equivalent P(1)O4 tetrahedra and  an edgeedge with one P(1)O4 tetrahedra. P(1) is bonded to one O(1), one O(2), one O(3), and one O(5) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O5 trigonal bipyramids and  an edgeedge with one V(1)O5 trigonal bipyramid. There are five inequivalent O sites. In the first O site, O(1) is bonded in a 2-coordinate geometry to two equivalent K(1), one V(1), and one P(1) atom. In the second O site, O(2) is bonded in a 2-coordinate geometry to two equivalent K(1), one V(1), and one P(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one K(1), one V(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted single-bond geometry to two equivalent K(1) and one V(1) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to two equivalent K(1), one V(1), and one P(1) atom.
KVOPO4 crystallizes in the orthorhombic P2_12_12_1 space group. K(1) is bonded in a 9-coordinate geometry to one O(3), two equivalent O(1), two equivalent O(2), two equivalent O(4), and two equivalent O(5) atoms. The K(1)-O(3) bond length is 2.75 Å. There is one shorter (2.90 Å) and one longer (3.31 Å) K(1)-O(1) bond length. There is one shorter (2.82 Å) and one longer (3.10 Å) K(1)-O(2) bond length. There is one shorter (2.81 Å) and one longer (3.10 Å) K(1)-O(4) bond length. There is one shorter (2.78 Å) and one longer (2.93 Å) K(1)-O(5) bond length. V(1) is bonded to one O(1), one O(2), one O(3), one O(4), and one O(5) atom to form distorted VO5 trigonal bipyramids that share corners with two equivalent P(1)O4 tetrahedra and  an edgeedge with one P(1)O4 tetrahedra. The V(1)-O(1) bond length is 2.00 Å. The V(1)-O(2) bond length is 2.02 Å. The V(1)-O(3) bond length is 2.02 Å. The V(1)-O(4) bond length is 1.64 Å. The V(1)-O(5) bond length is 2.05 Å. P(1) is bonded to one O(1), one O(2), one O(3), and one O(5) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O5 trigonal bipyramids and  an edgeedge with one V(1)O5 trigonal bipyramid. The P(1)-O(1) bond length is 1.55 Å. The P(1)-O(2) bond length is 1.54 Å. The P(1)-O(3) bond length is 1.57 Å. The P(1)-O(5) bond length is 1.57 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded in a 2-coordinate geometry to two equivalent K(1), one V(1), and one P(1) atom. In the second O site, O(2) is bonded in a 2-coordinate geometry to two equivalent K(1), one V(1), and one P(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one K(1), one V(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted single-bond geometry to two equivalent K(1) and one V(1) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to two equivalent K(1), one V(1), and one P(1) atom.