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The discrete complex [(Cul) 2  (pyzCN) 4 ] (1) and the coordination polymers  1  ∞  [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 networks 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  1  ∞  [CuI(pymMe)] (5),  3  ∞  [(CuBr) 3 (pymMe) 3 ] (6) and  2  ∞  [CuCl(pymMe)] (7), which were generated by reaction of CuX with 4-methylpyrimidine (pymMe) under reaction conditions similar to those above.

Three-dimensional Copper(I) Halide Based Coordination Networks with Asymmetrically Substituted Bridging N-Donor Ligands