CuX-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, â1[(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) Ã
) to a 1,10-DA18C6 oxygen atom. â 2[(Cu4I4)(1,10-DAcrypt)2] (4), (1,10-DAcrypt = 1,10-diaza-cryptand [2.2.2]), â 2[{(CuCN)6(1,7-DA12C4)4]·2CH 3CN (5) and â2[(CuSCN)2 (1,10-DA18C6] (6) all exhibit lamellar networks with respectively Cu 4I4 cubes, (CuCN)6 hexagons and â1[(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.