AbstractA number of compounds with general formula M2+(MPZ)n(anion)2 is reported, in which M = Mn, Fe, Co, Ni, Cu, Zn and Cd; MPZ = 3(5)‐methylpyrazole, n = 2–7, and the anions are ClO4, −, BF4, −, NO3, −, CNS−, Cl−, Br−, I−.The compounds are characterized by chemical analyses, X‐ray powder diagrams, ligand‐field spectra, paramagnetic susceptibility and resonance measurements, and vibrational spectra.The ligand MPZ is found to coordinate via the imino lone pair electrons, with the methyl group most probably located in the 5‐position, trans to the coordinated metal ion.With respect to the same anion, groups of isomorphous compounds were found according to the X‐ray powder patterns. Ligand‐field spectra of the coloured transition‐metal ion complexes indicate that MPZ is a stronger coordinating ligand than the unsubstituted pyrazole. This is confirmed by the magnetic susceptibility measurements and the paramagnetic resonance spectra.Fairly regular octahedral groups M(MPZ)6 2+ are found for the compounds with perchlorate and tetrafluoroborate anions (except for Cu2+), whereas strongly distorted tetragonal groups M(MPZ)4(anion)2 are found for the compounds containing the other anions (and for the Cu2+ compounds with BF4 − and ClO4 − anions). Infrared spectra of these latter compounds confirm the coordination of the ClO4, −, BF4− and NO3− anions, since split anion absorptions are found.