K3W2(O2F3)2 crystallizes in the monoclinic C2/c space group. There are two inequivalent K sites. In the first K site, K(1) is bonded in a 7-coordinate geometry to one O(2), one F(3), two equivalent F(1), and three equivalent F(2) atoms. In the second K site, K(2) is bonded in a distorted body-centered cubic geometry to two equivalent O(2), two equivalent F(1), and four equivalent F(3) atoms. W(1) is bonded to one O(2), two equivalent O(1), one F(1), one F(2), and one F(3) atom to form edge-sharing WO3F3 octahedra. There are two inequivalent O sites. In the first O site, O(1) is bonded in an L-shaped geometry to two equivalent W(1) atoms. In the second O site, O(2) is bonded in a distorted single-bond geometry to one K(1), one K(2), and one W(1) atom. There are three inequivalent F sites. In the first F site, F(1) is bonded to one K(2), two equivalent K(1), and one W(1) atom to form a mixture of distorted corner and edge-sharing FK3W tetrahedra. In the second F site, F(2) is bonded to three equivalent K(1) and one W(1) atom to form a mixture of distorted corner and edge-sharing FK3W tetrahedra. In the third F site, F(3) is bonded to one K(1), two equivalent K(2), and one W(1) atom to form a mixture of distorted corner and edge-sharing FK3W tetrahedra.
K3W2(O2F3)2 crystallizes in the monoclinic C2/c space group. There are two inequivalent K sites. In the first K site, K(1) is bonded in a 7-coordinate geometry to one O(2), one F(3), two equivalent F(1), and three equivalent F(2) atoms. The K(1)-O(2) bond length is 2.93 Å. The K(1)-F(3) bond length is 2.69 Å. There is one shorter (2.68 Å) and one longer (2.70 Å) K(1)-F(1) bond length. There are a spread of K(1)-F(2) bond distances ranging from 2.65-2.73 Å. In the second K site, K(2) is bonded in a distorted body-centered cubic geometry to two equivalent O(2), two equivalent F(1), and four equivalent F(3) atoms. Both K(2)-O(2) bond lengths are 2.77 Å. Both K(2)-F(1) bond lengths are 2.71 Å. There are two shorter (2.69 Å) and two longer (2.98 Å) K(2)-F(3) bond lengths. W(1) is bonded to one O(2), two equivalent O(1), one F(1), one F(2), and one F(3) atom to form edge-sharing WO3F3 octahedra. The W(1)-O(2) bond length is 1.73 Å. Both W(1)-O(1) bond lengths are 1.94 Å. The W(1)-F(1) bond length is 2.00 Å. The W(1)-F(2) bond length is 2.02 Å. The W(1)-F(3) bond length is 2.04 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in an L-shaped geometry to two equivalent W(1) atoms. In the second O site, O(2) is bonded in a distorted single-bond geometry to one K(1), one K(2), and one W(1) atom. There are three inequivalent F sites. In the first F site, F(1) is bonded to one K(2), two equivalent K(1), and one W(1) atom to form a mixture of distorted corner and edge-sharing FK3W tetrahedra. In the second F site, F(2) is bonded to three equivalent K(1) and one W(1) atom to form a mixture of distorted corner and edge-sharing FK3W tetrahedra. In the third F site, F(3) is bonded to one K(1), two equivalent K(2), and one W(1) atom to form a mixture of distorted corner and edge-sharing FK3W tetrahedra.