The stereochemically flexible Cu(hfac)2 metal-ligand system when combined with polyfunctional nitroxides leads to a variety of solids with varying structure and composition. While investigating the products of Cu(hfaC)2 interaction with spin-labeled pyrazole 4,4,5,5-tetramethyl-2-(1-methyl-1 H-pyrazol-4-yl)-imidazoline-3-oxide-1-oxyl, we have isolated a family of (12) heterospin compounds differing in structure and composition in the solid state. In synthetic systems, these compounds often cocrystallize and must be separated mechanically. It is also shown that minor variation of the structure of the solid heterospin complex can substantially change the magnetic properties of compounds.