One‐ to Three‐Dimensional CuI and CuCN Based Coordination Polymers containing the Alkali Cation Ligating Thiacrown Ether 1, 10‐Dithia‐18‐Crown‐6

Treatment of an acetonitrile solution of CuI with 1, 10‐dithia‐18‐crown‐6 (1, 10DT18C6) in the presence of Rb₂CO₃ leads to formation of the lamellar coordination polymer [Rb{Cu₄I₅(1, 10DT18C6)₂}] ( 1 ).The anionic network of 1 is composed of parallel [(Cu₄I₅)^—] chains linked by bridging thiacrown ether ligands, pairs of which coordinate the Rb⁺ counter cations. [Cs{Cu₅I₆(1, 10DT18C6)₂}] ( 2 ) can be prepared under similar conditions but contains separated helical anionic chains. In this case 1, 10DT18C6 ligands bridge copper atoms of individual chains in an intrastrand manner. In contrast the coordination networks in [(CuCN)₂(1, 10DT18C6)] ( 3 ) and [K₂{Cu₁₂(CN)₁₄(1, 10DT18C6)₃} · CH₃CN] ( 4 ) are both three‐dimensional and based on CuCN‐containing sheets bridged by 1, 10DT18C6 ligands. In the latter compound pairs of K⁺ cations are coordinated by groups of three thiacrown ether molecules. The neutral network of 3 can imbibe up to 31 % KNO₃ per 1, 10DT18C6 pair without loss of lattice integrity.