Abstract
Four novel copper(I) cyanide complexes of three isomeric oligopyridine ligands, namely 2‐amino‐4,6‐bis(2‐pyridyl)pyrimidine (L^1^), 2‐amino‐4‐(2‐pyridyl)‐6‐(4‐pyridyl)pyrimidine (L^2^), 2‐amino‐4‐(2‐pyridyl)‐6‐(3‐pyridyl)pyrimidine (L^3^) have been hydrothermally synthesized. These complexes have one‐ and two‐dimensional structures, as determined by single‐crystal X‐ray diffraction. The structural dimensionalities and motifs of complexes 1–4 are directed by the coordination modes of the ligands. Thus, L^1^ acts as a bis‐chelating ligand in complex 1 to join the adjacent 1D {CuCN}~n~ chains into a two‐dimensional corrugated layer. Complexes 2 and 4 both consist of one‐dimensional zigzag chains where the ligands (L^2^ for complex 2 and L^3^ for complex 4) occupy the terminal positions and N**···**NH~2~ hydrogen bonds play an important role in the assembly of the supramolecular network. Complex 3 (another product isolated from the L^3^‐Cu‐CN reaction system) is a two‐dimensional network in which L^3^ acts as a bridging ligand and the cyanide groups exhibit both μ~2~ and μ~3~ linking modes. Further investigation shows that the thermal stability of complexes 1–4 is in the order 1 > 3 > 2 > 4. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)