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The use of 2-pyridyl oximes in metal complexes chemistry has been extensively investigated in the last few decades as a fruitful source of species with interesting magnetic properties. In this work, the initial combination of pyridine-2-amidoxime (pyaoxH₂) and 2-methyl pyridyl ketoxime (mpkoH) with isonicotinic acid (HINA) and 3,5-pyrazole dicarboxylic acid (H₃pdc) has provided access to three new compounds, [Ni₄(INA)₂(pyaox)₂(pyaoxH)₂(DMF)₂] (<b>1</b>), [Co₅(mpko)₆(mpkoH)₂(OMe)₂(H₂O)](ClO₄)₆ (<b>2</b>), and [Co₅(OH)(Hpdc)₅(H₂pdc)] (<b>3</b>). <b>1</b> displays a square-planar metal topology, being the first example that bears simultaneously HINA and pyaoxH₂ in their neutral or ionic form. The neighbouring Ni₄ units in <b>1</b> are held together through strong intermolecular hydrogen bonding interactions, forming a three-dimensional supramolecular framework. <b>2</b> and <b>3</b> are mixed-valent Co₄^IIICo^II and Co₂^IIICo^II₃ compounds with a bowtie and trigonal bipyramidal metal topology, accordingly. Direct current and alternate current magnetic susceptibility studies revealed that the exchange interactions between the Ni^II ions in <b>1</b> are ferromagnetic (<i>J</i> = 1.79(4) cm⁻¹), while <b>2</b> exhibits weak AC signals in the presence of a magnetic field. The syntheses, crystal structures, and magnetic properties of <b>1–3</b> are discussed in detail.