cis,trans-1,3,5-Triaminocyclohexane (trans-tach) has been shown to be an excellent ligand in the synthesis of discrete complexes, molecular clusters, and infinite architectures. Herein, we report the Schiff-base derivitization of trans-tach to form cis,trans-1,3,5-tris (pyridine-2-carboxaldimino) cyclohexane (ttop), and the complexation of this ligand with copper(II) salts. The complexation reaction leads to the crystallization of transition-metal complexes with nuclearities of 1, 2, and 4, and the formation of the complexes can be followed stepwise, in real time, using electrospray mass spectrometry.