The hexa-gonal host-guest title compound, poly[hexa-kis-[[di-methyl-tin(IV)]-di-μ-fluorido] potassium iodide], {[Sn(CH3)2F2]6·KI} n or (Me2SnF2)6·KI, represents a layer structure of distorted {Me2SnF4/2} octa-hedra corner-linked via μ2-bonding fluorine atoms. Distortion of the octa-hedra concerns not only bond lengths [d(Sn-C) = 2.089 (2) Å, d(Sn-F) = 2.077 (1)/2.080 (1), 2.252 (1)/2.266 (1) Å] but also bond angles [〈(C-Sn-C) = 162.2 (1)°, 〈(F-Sn-F) = 77.11 (7)-119.57 (5)°] giving rise to a irregular quadrilateral, pseudo-equatorial plane of fluorine atoms around the central tin atom. In the planar (001) layers, the octa-hedra are arranged according to a snub hexa-gonal tiling (sr{3,6}) resulting in small trigonal and larger hexa-gonal pores. The latter are occupied by potassium ions [d(F⋯K) = 2.702 (2) Å, 6×], which in turn form linear rods with iodine ions [d(K⋯I) = 3.6702 (2) Å, 2×) perpendicular to adjacent layers.
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