Three new complexes based on the neutral pseudo-macrocyclic complex bis(dimethylglyoximato)copper(II) and the substituted pyridines, 4-phenylpyridine, 3-pyridin-4-ylpropan-1-ol and isonicotinamide, which occupy a fifth coordination site on the copper, are described. The usefulness of such complexes in building supra-molecular arrays is examined. The complex containing 3-pyridin-4-ylpropan-1-ol forms hydrogen-bonded chains that, lying across one another, form layers within the crystal. The isonicotinamide-containing complex yields a host-guest assembly that incorporates channels containing guest molecules. The prospect of 'tuning' the size of the channel is discussed.