Metal complexes of iminodiacetamide (imda) ligands and metal ions Zn(II), Cu(II), Ni(II), and Co(II) were prepared using eight imda ligands (L1-L8) substituted with groups of different steric and electronic properties on the central amine N atom (H atom, methyl, isopropyl, and benzyl) and the para position of the phenyl rings (nitro and dimethylamino). The effect of these substituents on the stoichiometry (ML and ML2), geometry, and stereochemistry (mer, trans-fac, cis-fac) of the complexes was studied in the solid state, in solution, and by density functional theory calculations. Single-crystal and powder X-ray diffraction, thermogravimetry, and IR spectroscopy showed that in the solid state imda ligands preferentially form trans-fac ML2 complexes, with the exception of the cis-fac complex 7Zn. NMR spectroscopy of diamagnetic Zn(II) and paramagnetic Co(II) complexes revealed the formation of both ML and ML2 complexes in solution, which was also confirmed by UV-vis titrations. Variable-temperature NMR was used to study the effect of the substituent on the central amine N atom on the Zn-N bond strength and nitrogen inversion. The relative stabilities of the isomers were rationalized by computations and the optimized structures used for geometry analysis.