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In the solid-state structure of K(dioxane) 2 PPh 2  ( 1 ), prepared from potassium and PPh 3  in dioxane, each K ion is surrounded by four bridging dioxane molecules in a plane, and the P atom of the PPh 2  anion occupies an axial position. A  π  interaction between the K ion and an aryl ring of a PPh 2  anion of a neighbouring plane generates a three-dimensional network.  1  crystallises in the monoclinic space group  P 2 1 / n  (no. 14),  T  = 200(2) K, with  a  = 8.854(1) Å,  b  = 15.904(2) Å,  c  = 15.740(2) Å,  β  = 99.16(1)°,  V  = 2188.1(5) Å 3  and  Z  = 4. The refinement converged to  R 1 = 0.0372,  wR 2 = 0.0949 (for reflections with  I  &gt; 2 σ ( I )),  R 1 = 0.0871,  wR 2 = 0.1125 (all data).

Solid-state structure of [K(dioxane) 2 PPh 2 ] n : Formation of a three-dimensional network via anion-cation-interaction