Alkali Cation Ligating Chains and Sheets of the Macrocycle 1, 7‐Dithia‐18‐Crown‐6 with Bridging Iodo‐ and Thiocyanatocuprate(I) Units

Treatment of an acetonitrile solution of CuI with 1, 7‐dithia‐18‐crown‐6 (1, 7‐DT18C6) at 100°C affords the coordination polymer 1 [(CuI) 2 (1, 7‐DT18C6) 2 ] ( 1 ) in which 1, 7‐DT18C6 ligands bridge (CuI) 2 rings into double chains. 1D polymers of the type 1 [M{(Cu 3 I 4 )(1, 7‐DT18C6)}] (M = K, 2 ; M = Cs, 3 ) can be isolated under similar conditions in the presence of respectively KI and CsI. Both contain bridging heptacyclic [Cu 6 I 8 ] 2— units but crystallise in different space groups, namely P 1 and C 2/ m. The cesium cation of 3 is markedly displaced from the best plane through the thiacrown ether donor atoms. Reaction of 1, 7‐DT18C6 with CuSCN in the presence of NaSCN yields 2 [{Na(CH 3 CN) 2 } {(CuSCN) 2 (1, 7‐DT18C6)}][Cu(SCN) 2 ] ( 4 ), in which 1 [(CuSCN) 2 ] double chains are linked through macrocycles into sheets. Infinite 1 [{Cu(SCN) 2 } — ] chains compensate the charge of the Na + cations. Complex 1 can imbibe 0.90 mol CsNO 3 per mol of 1, 7‐DT18C6 pairs.