K2LiVPO6 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent K sites. In the first K site, K(1) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(3), one O(4), and one O(6) atom. In the second K site, K(2) is bonded in a 7-coordinate geometry to one O(2), one O(4), one O(5), two equivalent O(1), and two equivalent O(6) atoms. Li(1) is bonded to one O(2), one O(6), and two equivalent O(3) atoms to form distorted LiO4 trigonal pyramids that share corners with two equivalent V(1)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and  an edgeedge with one Li(1)O4 trigonal pyramid. V(1) is bonded to one O(1), one O(3), one O(4), and one O(5) atom to form distorted VO4 tetrahedra that share corners with two equivalent P(1)O4 tetrahedra and corners with two equivalent Li(1)O4 trigonal pyramids. P(1) is bonded to one O(2), one O(4), one O(5), and one O(6) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O4 tetrahedra and corners with two equivalent Li(1)O4 trigonal pyramids. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one K(1), two 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(1), one K(2), one Li(1), and one P(1) atom. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one K(1), two equivalent Li(1), and one V(1) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one K(1), one K(2), one V(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one K(2), one V(1), and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted bent 150 degrees geometry to one K(1), two equivalent K(2), one Li(1), and one P(1) atom.
K2LiVPO6 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent K sites. In the first K site, K(1) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(3), one O(4), and one O(6) atom. The K(1)-O(1) bond length is 2.61 Å. The K(1)-O(2) bond length is 2.84 Å. The K(1)-O(3) bond length is 2.68 Å. The K(1)-O(4) bond length is 2.74 Å. The K(1)-O(6) bond length is 2.79 Å. In the second K site, K(2) is bonded in a 7-coordinate geometry to one O(2), one O(4), one O(5), two equivalent O(1), and two equivalent O(6) atoms. The K(2)-O(2) bond length is 2.79 Å. The K(2)-O(4) bond length is 2.85 Å. The K(2)-O(5) bond length is 2.72 Å. There is one shorter (2.83 Å) and one longer (2.98 Å) K(2)-O(1) bond length. There is one shorter (2.98 Å) and one longer (3.14 Å) K(2)-O(6) bond length. Li(1) is bonded to one O(2), one O(6), and two equivalent O(3) atoms to form distorted LiO4 trigonal pyramids that share corners with two equivalent V(1)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and  an edgeedge with one Li(1)O4 trigonal pyramid. The Li(1)-O(2) bond length is 2.05 Å. The Li(1)-O(6) bond length is 2.01 Å. There is one shorter (1.96 Å) and one longer (2.33 Å) Li(1)-O(3) bond length. V(1) is bonded to one O(1), one O(3), one O(4), and one O(5) atom to form distorted VO4 tetrahedra that share corners with two equivalent P(1)O4 tetrahedra and corners with two equivalent Li(1)O4 trigonal pyramids. The V(1)-O(1) bond length is 1.71 Å. The V(1)-O(3) bond length is 1.75 Å. The V(1)-O(4) bond length is 1.97 Å. The V(1)-O(5) bond length is 1.98 Å. P(1) is bonded to one O(2), one O(4), one O(5), and one O(6) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O4 tetrahedra and corners with two equivalent Li(1)O4 trigonal pyramids. The P(1)-O(2) bond length is 1.54 Å. The P(1)-O(4) bond length is 1.60 Å. The P(1)-O(5) bond length is 1.57 Å. The P(1)-O(6) bond length is 1.54 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one K(1), two 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(1), one K(2), one Li(1), and one P(1) atom. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one K(1), two equivalent Li(1), and one V(1) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one K(1), one K(2), one V(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one K(2), one V(1), and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted bent 150 degrees geometry to one K(1), two equivalent K(2), one Li(1), and one P(1) atom.