KTe3O6F crystallizes in the trigonal R-3 space group. K(1) is bonded to three equivalent O(1), three equivalent O(2), and one F(1) atom to form distorted KO6F pentagonal bipyramids that share corners with nine equivalent Te(1)O4F square pyramids and edges with three equivalent Te(1)O4F square pyramids. Te(1) is bonded to two equivalent O(1), two equivalent O(2), and one F(1) atom to form distorted TeO4F square pyramids that share corners with three equivalent K(1)O6F pentagonal bipyramids, corners with four equivalent Te(1)O4F square pyramids,  an edgeedge with one K(1)O6F pentagonal bipyramid, and  an edgeedge with one Te(1)O4F square pyramid. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to one K(1) and two equivalent Te(1) atoms. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one K(1) and two equivalent Te(1) atoms. F(1) is bonded in a trigonal pyramidal geometry to one K(1) and three equivalent Te(1) atoms.
KTe3O6F crystallizes in the trigonal R-3 space group. K(1) is bonded to three equivalent O(1), three equivalent O(2), and one F(1) atom to form distorted KO6F pentagonal bipyramids that share corners with nine equivalent Te(1)O4F square pyramids and edges with three equivalent Te(1)O4F square pyramids. All K(1)-O(1) bond lengths are 2.90 Å. All K(1)-O(2) bond lengths are 2.96 Å. The K(1)-F(1) bond length is 2.81 Å. Te(1) is bonded to two equivalent O(1), two equivalent O(2), and one F(1) atom to form distorted TeO4F square pyramids that share corners with three equivalent K(1)O6F pentagonal bipyramids, corners with four equivalent Te(1)O4F square pyramids,  an edgeedge with one K(1)O6F pentagonal bipyramid, and  an edgeedge with one Te(1)O4F square pyramid. There is one shorter (1.93 Å) and one longer (2.21 Å) Te(1)-O(1) bond length. There is one shorter (1.94 Å) and one longer (2.09 Å) Te(1)-O(2) bond length. The Te(1)-F(1) bond length is 2.49 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to one K(1) and two equivalent Te(1) atoms. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one K(1) and two equivalent Te(1) atoms. F(1) is bonded in a trigonal pyramidal geometry to one K(1) and three equivalent Te(1) atoms.