KCu3P3(O4F3)2 crystallizes in the monoclinic C2/c space group. K(1) is bonded in a 10-coordinate geometry to two equivalent O(1), two equivalent O(3), two equivalent F(1), and four equivalent F(3) atoms. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one O(1), one O(2), one O(3), one O(4), and two equivalent F(2) atoms to form distorted CuO4F2 octahedra that share  a cornercorner with one Cu(2)O4F2 octahedra, corners with two equivalent Cu(1)O4F2 octahedra,  a cornercorner with one P(1)O2F2 tetrahedra, corners with three equivalent P(2)O3F tetrahedra, and  a faceface with one Cu(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 49-62°. In the second Cu site, Cu(2) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent F(2) atoms to form distorted CuO4F2 octahedra that share corners with two equivalent Cu(1)O4F2 octahedra, corners with four equivalent P(2)O3F tetrahedra, and faces with two equivalent Cu(1)O4F2 octahedra. The corner-sharing octahedral tilt angles are 49°. There are two inequivalent P sites. In the first P site, P(1) is bonded to two equivalent O(1) and two equivalent F(3) atoms to form PO2F2 tetrahedra that share corners with two equivalent Cu(1)O4F2 octahedra. The corner-sharing octahedral tilt angles are 41°. In the second P site, P(2) is bonded to one O(2), one O(3), one O(4), and one F(1) atom to form PO3F tetrahedra that share corners with two equivalent Cu(2)O4F2 octahedra and corners with three equivalent Cu(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 45-54°. There are four inequivalent O sites. In the first O site, O(2) is bonded in a 3-coordinate geometry to one Cu(1), one Cu(2), and one P(2) atom. In the second O site, O(3) is bonded in a distorted trigonal planar geometry to one K(1), one Cu(1), and one P(2) atom. In the third O site, O(4) is bonded in a 3-coordinate geometry to one Cu(1), one Cu(2), and one P(2) atom. In the fourth O site, O(1) is bonded in a 2-coordinate geometry to one K(1), one Cu(1), and one P(1) atom. There are three inequivalent F sites. In the first F site, F(2) is bonded in a 3-coordinate geometry to one Cu(2) and two equivalent Cu(1) atoms. In the second F site, F(3) is bonded in a single-bond geometry to two equivalent K(1) and one P(1) atom. In the third F site, F(1) is bonded in a single-bond geometry to one K(1) and one P(2) atom.
KCu3P3(O4F3)2 crystallizes in the monoclinic C2/c space group. K(1) is bonded in a 10-coordinate geometry to two equivalent O(1), two equivalent O(3), two equivalent F(1), and four equivalent F(3) atoms. Both K(1)-O(1) bond lengths are 3.08 Å. Both K(1)-O(3) bond lengths are 2.73 Å. Both K(1)-F(1) bond lengths are 3.01 Å. There are two shorter (3.01 Å) and two longer (3.22 Å) K(1)-F(3) bond lengths. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one O(1), one O(2), one O(3), one O(4), and two equivalent F(2) atoms to form distorted CuO4F2 octahedra that share  a cornercorner with one Cu(2)O4F2 octahedra, corners with two equivalent Cu(1)O4F2 octahedra,  a cornercorner with one P(1)O2F2 tetrahedra, corners with three equivalent P(2)O3F tetrahedra, and  a faceface with one Cu(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 49-62°. The Cu(1)-O(1) bond length is 2.01 Å. The Cu(1)-O(2) bond length is 1.99 Å. The Cu(1)-O(3) bond length is 1.97 Å. The Cu(1)-O(4) bond length is 2.01 Å. There is one shorter (2.16 Å) and one longer (2.50 Å) Cu(1)-F(2) bond length. In the second Cu site, Cu(2) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent F(2) atoms to form distorted CuO4F2 octahedra that share corners with two equivalent Cu(1)O4F2 octahedra, corners with four equivalent P(2)O3F tetrahedra, and faces with two equivalent Cu(1)O4F2 octahedra. The corner-sharing octahedral tilt angles are 49°. Both Cu(2)-O(2) bond lengths are 2.45 Å. Both Cu(2)-O(4) bond lengths are 2.06 Å. Both Cu(2)-F(2) bond lengths are 1.88 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to two equivalent O(1) and two equivalent F(3) atoms to form PO2F2 tetrahedra that share corners with two equivalent Cu(1)O4F2 octahedra. The corner-sharing octahedral tilt angles are 41°. Both P(1)-O(1) bond lengths are 1.49 Å. Both P(1)-F(3) bond lengths are 1.58 Å. In the second P site, P(2) is bonded to one O(2), one O(3), one O(4), and one F(1) atom to form PO3F tetrahedra that share corners with two equivalent Cu(2)O4F2 octahedra and corners with three equivalent Cu(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 45-54°. The P(2)-O(2) bond length is 1.52 Å. The P(2)-O(3) bond length is 1.52 Å. The P(2)-O(4) bond length is 1.54 Å. The P(2)-F(1) bond length is 1.61 Å. There are four inequivalent O sites. In the first O site, O(2) is bonded in a 3-coordinate geometry to one Cu(1), one Cu(2), and one P(2) atom. In the second O site, O(3) is bonded in a distorted trigonal planar geometry to one K(1), one Cu(1), and one P(2) atom. In the third O site, O(4) is bonded in a 3-coordinate geometry to one Cu(1), one Cu(2), and one P(2) atom. In the fourth O site, O(1) is bonded in a 2-coordinate geometry to one K(1), one Cu(1), and one P(1) atom. There are three inequivalent F sites. In the first F site, F(2) is bonded in a 3-coordinate geometry to one Cu(2) and two equivalent Cu(1) atoms. In the second F site, F(3) is bonded in a single-bond geometry to two equivalent K(1) and one P(1) atom. In the third F site, F(1) is bonded in a single-bond geometry to one K(1) and one P(2) atom.