| Summary: | In this paper, we report on the synthesis, crystal structure, and photomagnetic properties of the spin-crossover salt of formula [Fe(bpp)<sub>2</sub>](C<sub>6</sub>H<sub>4</sub>NO<sub>2</sub>)<sub>2</sub>·4H<sub>2</sub>O (<b>1</b>·4H<sub>2</sub>O) (bpp = 2,6-bis(pyrazol-3-yl)pyridine; C<sub>6</sub>H<sub>4</sub>NO<sub>2</sub><sup>−</sup> = nicotinate anion). This compound exhibits a 3D supramolecular architecture built from hydrogen bonds between iron(II) complexes, nicotinate anions, and water molecules. As synthesized, the hydrated material is low-spin and desolvation triggers a low-spin (LS) to high-spin (HS) transformation. Anhydrous phase <b>1</b> undergoes a partial spin crossover (<i>T</i><sub>1/2</sub>= 281 K) and a LS to HS photomagnetic conversion with a <i>T</i>(LIESST) value of 56 K.
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