The 2-dimensional coordination polymers 2.[{(CuI)2(Mepyz)2} • Mepyz] (la), (2)[CuX(Mepyz)] (2a, X = Br; 2b, X = Cl) and ^[(C uX^M epyz)] (3a, X = I;3b, X = Br) may be prepared by reaction of the appropriate copper(I) halide with 2-methylpyrazine (Mepyz) either in acetonitrile solution at 130 °C (2a/2b, 3a/3b) or without solvent at 20 °C (la). Mepyz ligands bridge (Culh rhomboid dimers in the chiral network of la, whose resulting 24-membered rings are large enough to accomodate an Mepyz guest molecule, la rapidly loses these guests to afford a crystalline powder (lb), that can reversibly imbibe benzonitrile molecules into its open channels. In contrast to la, the sheets of 2a/2b contain zigzag infinite CuX chains, those of 3a/3b staircase ^[C uX ] double chains as their characteristic substructures. Helical JJC ul] single chains in the 3-dimensional network of ^[C uL M epip)^ are bridged by R-2-methylpiperazine (Mepip) ligands in a second example of

The discrete complex [(Cul)2 (pyzCN)4] (1) and the coordination polymers ^ [CuI(pyzCN)] (2) and 3 [(CuX)3 (pyzCN)2] (3, 4; X = Br, Cl) may be prepared from the respective copper(I) halide CuX and 2-cyanopyrazine (pyzCN) by self-assembly in acetonitrile solution at 100-120°C. Whereas 2 exhibits 1 [Cul] staircase double chains as its characteristic substructure, the three-dimensional netwo'rks of 3 and 4 contain single zigzag CuX strings. The influence of the copper(I) halide on both the connectivity pattern and the dimensionality of a resulting coordination network is particularly apparent for the 1:1 complexes ^ [CuI(pymMe)] (5), 3 [(CuBr)3(pymMe)_3] (6) and ^ [CuCl(pymMe)] (7), which were generated by reaction of öaX with 4-methylpyrimidine (pymMe) under reaction conditions similar to those above.

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