Lamellar copper(I) thiocyanate-based coordination polymers containing the alkali cation ligating thiacrown ether 1,10-dithia-18-crown-6

The lamellar coordination polymer (2)(infinity)[(CuSCN)(2)-(mu -1,10DT18C6) ] (1,10DTI8C6 = 1,10-dithia-18-crown-6), in which staircase-Like CuSCN doub le chains are bridged by thiacrown ether ligands, may be prepared in two tr iclinic modifications 1 a and 1 b by reaction of CuSCN with 1,10DT18C6 in r espectively benzonitrile or water. Performing the reaction in acetonitrile in the presence of an equimolar quantity of KSCN leads, in contrast, to for mation of the K+ ligating 2-dimensional thiocyanatocuprate(I) net (2)(infin ity)[(Cu-2(SCN)(3))(-)] of 2, half of whose Cu(I) atoms are connected by 1, 10T18C6 macrocycles. The potassium cations in (2)(infinity)[(K(CH3CN)][Cu-2 (SCN)(3)(mu -1,10DT18C6))] (2) are coordinated by all six potential donor a toms of a single thiacrown ether in addition to a thiocyanate S and an acet onitrile N atom. Under similar conditions, reaction of CuI, NaSCN and 1,10D T18C6 affords (2)(infinity)[Na(CH3CN)(2))(Cu4I4-(SCN)(mu -1,10DT18C6))] (3) , which contains distorted Cu4I4 cubes as characteristic molecular building units. These are bridged by thiocyanate and thiacrown ether Ligands into c orrugated Na+ ligating sheets. In the presence of divalent Ba2+ cations, ch arge compensation requirements lead to formation of discrete [Cu(SCN)(3)(1, 10DT18C6-kappaS)](2-) anions in (2)(infinity)[Ba(Cu(SCN)(3)(1,10DT18C6-kapp aS)](2-) (4).