Three picolinamide complexes of nickel(II) (1), zinc(II) (2), and cadmium(II) (3) have been prepared and their solid state structures were determined by single-crystal X-ray diffraction analysis. Their structures in DMSO solutions as well as the structure of similar mercury(II) complex, Hg(NO 3 )(pia) 2 (NO 3 ) (4), have been elucidated by 1 H and 13 C NMR spectra. The picolinamide is bound through the N,O-donors in all four complexes in solid state, but only in 4 it is in solution state. In nickel (1), zinc (2), and cadmium (3) complexes the pia-N coordination in solution is suggested. The X-ray analysis revealed that isomorphous nickel (1) and zinc (2) crystal structures comprise the centrosymmetrical trans-M(H 2 O) 2 (pia) 2 2+ (M = Ni, Zn; pia = picolinamide) and nitrate. The crystal lattices also contain two non-coordinated H 2 O molecules. In 3, each cadmium(II) is N,O-chelated by two cis-oriented pia ligands, while remaining coordination sites of the capped pentagonal bipyramid are occupied by three oxygen atoms from two nitrates. Crystal structures are dominated by O/N/C-H···O hydrogen bonds. The carboxamide moieties in 1 and 2 do not form any head-to-head or catemeric supramolecular synthons, but participate in the formation of (12) motifs with solely the amide nitrogen atoms as double hydrogen bond donors. In 3, neighboring molecules are linked into head-to-head amide dimers. The biological effect of picolinamide and Zn(pia) 2 (H 2 O) 2 (NO 3 ) 2 on ingestion and intracellular microbicidal capacities of human peripheral blood phagocytes was also assessed.