Diaza crown ethers and cryptants as bridging ligands in lamellar copper(I) coordination polymers

CuX-based coordination polymers (X = 1, CN, SCN) with diazacrown ethers or cryptands as bridging ligands have been prepared by reaction of CuX with appropriate macrocycle in acetormitrile/hexane solution at 100 degreesC. Whereas [CuI (1,7-DA12C4)] (1) and [CuI(1,10-DA18C6)] (2) (1,7-DA12C4 = 1,7-diaza-12crown-4, 1,10-DA18C6 = 1,10-diaza-18-crown-6) are both monomeric, 1/infinity[(CuI)(2)(1,10-DA18C6)] (3) contains infinite chains in which (CuI)(2) rings are linked in a mu-N1,N10 manner by thiacrown ether moieties. The distorted tetrahedral coordination of the Cu-I atoms in 3 is completed by a weak Cu...O interaction (2.393(7) Angstrom) to a 1,10-DA18C6 oxygen atom. 2/infinity [(Cu4I4)(1,10-DAcryPt)(2)] (4), (1,10-DAcrypt = 1,10-diaza-cryptand [2.2.2]), 2/infinity[{(CuCN)(6)(1,7-DA12C4)4].2CH(3)CN (5) and 2/infinity[(CuSCN)(2) (1,10-DA18C6] (6) all exhibit lamellar networks with respectively Cu4I4 cubes, (CuCN)(6) hexagons and 1/infinity[(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.