KCu2P2H3(O4F)2 crystallizes in the monoclinic C2/m space group. K(1) is bonded to two equivalent O(1), four equivalent O(2), and two equivalent F(1) atoms to form distorted KO6F2 hexagonal bipyramids that share corners with four equivalent P(1)O3F tetrahedra, edges with four equivalent Cu(1)O6 octahedra, and edges with two equivalent P(1)O3F tetrahedra. Cu(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form CuO6 octahedra that share corners with four equivalent P(1)O3F tetrahedra, edges with two equivalent K(1)O6F2 hexagonal bipyramids, and edges with two equivalent Cu(1)O6 octahedra. P(1) is bonded to one O(1), two equivalent O(2), and one F(1) atom to form PO3F tetrahedra that share corners with two equivalent K(1)O6F2 hexagonal bipyramids, corners with four equivalent Cu(1)O6 octahedra, and  an edgeedge with one K(1)O6F2 hexagonal bipyramid. The corner-sharing octahedral tilt angles range from 48-57°. There are two inequivalent H sites. In the first H site, H(1) is bonded in a linear geometry to two equivalent O(3) atoms. In the second H site, H(2) is bonded in a single-bond geometry to one O(3) atom. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one K(1), two equivalent Cu(1), and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one K(1), one Cu(1), and one P(1) atom. In the third O site, O(3) is bonded to two equivalent Cu(1), one H(1), and one H(2) atom to form distorted corner-sharing OCu2H2 tetrahedra. F(1) is bonded in a single-bond geometry to one K(1) and one P(1) atom.
KCu2P2H3(O4F)2 crystallizes in the monoclinic C2/m space group. K(1) is bonded to two equivalent O(1), four equivalent O(2), and two equivalent F(1) atoms to form distorted KO6F2 hexagonal bipyramids that share corners with four equivalent P(1)O3F tetrahedra, edges with four equivalent Cu(1)O6 octahedra, and edges with two equivalent P(1)O3F tetrahedra. Both K(1)-O(1) bond lengths are 2.73 Å. All K(1)-O(2) bond lengths are 2.82 Å. Both K(1)-F(1) bond lengths are 2.90 Å. Cu(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form CuO6 octahedra that share corners with four equivalent P(1)O3F tetrahedra, edges with two equivalent K(1)O6F2 hexagonal bipyramids, and edges with two equivalent Cu(1)O6 octahedra. Both Cu(1)-O(1) bond lengths are 2.45 Å. Both Cu(1)-O(2) bond lengths are 1.96 Å. Both Cu(1)-O(3) bond lengths are 2.05 Å. P(1) is bonded to one O(1), two equivalent O(2), and one F(1) atom to form PO3F tetrahedra that share corners with two equivalent K(1)O6F2 hexagonal bipyramids, corners with four equivalent Cu(1)O6 octahedra, and  an edgeedge with one K(1)O6F2 hexagonal bipyramid. The corner-sharing octahedral tilt angles range from 48-57°. The P(1)-O(1) bond length is 1.51 Å. Both P(1)-O(2) bond lengths are 1.53 Å. The P(1)-F(1) bond length is 1.63 Å. There are two inequivalent H sites. In the first H site, H(1) is bonded in a linear geometry to two equivalent O(3) atoms. Both H(1)-O(3) bond lengths are 1.22 Å. In the second H site, H(2) is bonded in a single-bond geometry to one O(3) atom. The H(2)-O(3) bond length is 0.98 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one K(1), two equivalent Cu(1), and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one K(1), one Cu(1), and one P(1) atom. In the third O site, O(3) is bonded to two equivalent Cu(1), one H(1), and one H(2) atom to form distorted corner-sharing OCu2H2 tetrahedra. F(1) is bonded in a single-bond geometry to one K(1) and one P(1) atom.