The crystal lattice of the three isostructural compounds , (C(6)H(8)N(2)H)(2)[M(C(3)H(2)O(4))(2)(H(2)O)(2)].4H(2)O (C(6)H(8)N(2)H = protonated 2-amino-4-picoline, M = Ni/Co/Mn, C(3)H(4)O(4) = malonate dianion; hereafter, malonate) is formed by supramolecular 2D layers. Hydrogen-bonding, pi...pi and lone pair...pi interactions play crucial role in organizing monomeric [M(II)(mal)(2)(H(2)O)(2)] units into 2D sheets along the ab plane, through the self-association between two different supramolecular building blocks, namely a tetrameric water cluster including metal-coordinated water molecules, and R(2)(2)(8) and R(2)(2)(7) hydrogen-bonded recognition synthons between 2-amino-4-picolinium and malonate. DFT calculations clearly show that the robust 2-amino-4-picolinium/malonate hydrogen-bonded motif drives the self-assembly of the supramolecular network observed.