Diaza Crown Ethers and Cryptants as Bridging Ligands in Lamellar Copper(I) Coordination Polymers

Abstract

AbstractCuX‐based coordination polymers (X = I, CN, SCN) with diazacrown ethers or cryptands as bridging ligands have been prepared by reaction of CuX with appropriate macrocycle in acetonnitrile/hexane solution at 100 °C. Whereas [CuI (1, 7‐DA12C4)] (1) and [CuI(1, 10‐DA18C6)] (2) (1, 7‐DA12C4 = 1, 7‐diaza‐12‐crown‐4, 1, 10‐DA18C6 = 1, 10‐diaza‐18‐crown‐6) are both monomeric, [(CuI)2(1, 10‐DA18C6)] (3) contains infinite chains in which (CuI)2 rings are linked in a μ‐N1, N10 manner by thiacrown ether moieties. The distorted tetrahedral coordination of the CuI atoms in 3 is completed by a weak Cu…O interaction (2.393(7)Å) to a 1, 10‐DA18C6 oxygen atom. [(Cu4I4)(1, 10‐DAcrypt)2] (4), (1, 10DAcrypt = 1, 10‐diaza‐cryptand [2.2.2]), [{(CuCN)6(1, 7‐DA12C4)4]·2CH3CN (5) and [(CuSCN)2 (1, 10‐DA18C6] (6) all exhibit lamellar networks with respectively Cu4I4 cubes, (CuCN)6 hexagons and [(CuSCN)2] double chains as their CuX substructures. 4 can imbibe up to 0.64 mol KNO3/mol cryptand and 6 up to 0.35 mol KNO3/mol 1, 10‐DA18C6 as a guest lattice. Crystal structures are reported for 1‐6, thermal analysis data (TG/DTA) for complexes 2, 3 and 5.