| Summary: | The synthesis, crystal structures, and magnetic properties of a new two-dimensional (2D) Hofmann-like series, Fe<sup>II</sup>(L)<sub>2</sub>[Ag<sup>I</sup>(CN)<sub>2</sub>]<sub>2</sub> (L = 3-cyano-4-methylpyridine (<b>1</b>), allyl isonicotinate (<b>2</b>), phenyl-isonicotinate (<b>3</b>), and benzyl nicotinate (<b>4</b>)) were studied. These compounds have a 2D sheet structure because of their strongly determinate self-assembly process. An octahedral Fe<sup>II</sup> ion is coordinated with the nitrogen atoms of[Ag<sup>I</sup>(CN)<sub>2</sub> linear units at equatorial positions and monodentate pyridine derivatives at the axial position. The layers construct a parallel stacking array. Compounds <b>1</b>−<b>3</b> show pairs of layers constructed by intermetallic Ag···Ag interactions. Compound <b>4</b> shows a mono-layer structure. The substituent bulk of the ligands affects the interlayer space. Compounds <b>1</b>−<b>4</b> undergo a 100% spin transition. However, compound <b>1</b>, incorporating a smaller group, has a relatively lower critical temperature (<i>T</i><sub>c</sub> = 182 K (<b>1</b>), <i>T</i><sub>c</sub> = 221 K (<b>2</b>), <i>T</i><sub>c</sub> = 227 (<b>3</b>) and <i>T</i><sub>c</sub><sup>1</sup> = 236 K, <i>T</i><sub>c</sub><sup>2</sup> = 215 K (<b>4</b>)). We investigated the correlations between our systematic crystal design, substituent size, and the spin crossover profiles.
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