Syntheses and Crystal Structures of Ammoniates with the Phenyl‐Substituted Polytin Anions Sn 2 Ph $\rm{_{\bf 4}^{{\bf 2} - } }$ , cyclo ‐Sn 4 Ph $\rm{_{\bf 4}^{{\bf 4} - } }$ , and Sn 6 Ph $\rm{_{{\bf 12}}^{{\bf 2} - } }$

The reaction of diphenyltin dichloride with the binary Zintl phase K 4 Sn 9 in the presence of excess lithium and 18‐crown‐6 in liquid ammonia led to the ammoniate [K(18‐crown‐6)(NH 3 ) 2 ] 2 Sn 2 Ph 4 ( 1 ). The analogous reaction with K 4 Ge 9 and potassium in the absence of further alkali metal ligands resulted in the compound [K 2 (NH 3 ) 12 ]Sn 6 Ph 12  ⋅ 4 NH 3 ( 3 ). Cs 6 [Sn 4 Ph 4 ](NH 2 ) 2  ⋅ 8 NH 3 ( 2 ) was prepared by reacting diphenyltin dichloride with a surplus of caesium in liquid ammonia. The low‐temperature single‐crystal structure determinations show all compounds to contain phenyl‐substituted polyanions of tin. Compound 1 is built from Sn 2 Ph $\rm{_4^{2 - } }$ anions consisting of Sn dumbbells with two Ph substituents at each Sn‐atom. Compound 2 contains cyclo ‐Sn 4 Ph $\rm{_4^{4 - } }$ anions formed by a four‐membered tin ring in butterfly conformation with one Ph substituent at each Sn‐atom in an (all‐ trans )‐configuration. Sn 6 Ph $\rm{_{12}^{2 - } }$ in 3 is a zig‐zag Sn 6 chain with two substituents at each of the Sn‐atoms. Both 1 and 3 have molecular counter cations, in the latter case the unprecedented dinuclear potassiumammine complex [K 2 (NH 3 ) 12 ] 2+ is observed. Compound 2 shows a complicated three‐dimensional network of CsSn interactions.