[Fe(phen)₃](I₃)₂·(solvent) has been crystallised in four different crystal lattices, 1–4, specifically 1-CH₂Cl₂, 1-acetone, 2-CH₃CN, 3-toluene, 4-H₂O. Three different types of layers of embracing [Fe(phen)₃]²⁺ complexes occur in 1, 2 and 3, with different placements of I₃⁻ ions on the surfaces of the layers. A filled box motif, {[Fe(phen)₃]²⁺(CH₃CN)₂[Fe(phen)₃]²⁺}, occurs in 2-CH₃CN. In 4 there are chains of embracing [Fe(phen)₃]²⁺ complexes surrounded by I₃^–. Multiple I⋯H–C(aryl-edge) and I⋯aryl-face interactions occur. These are hydrophobic molecular crystals, demonstrating crystal packing isomerism (polymorphism). The solvents appear to be functioning as space-fillers, and logical connections between crystallisation conditions and crystal compositions and motifs are elusive. The different polymorphic crystal structure occurring in [Mn(phen)₃](I₃)₂ is described: this high symmetry solvent-free crystal does not contain the extended sequences of embracing [Fe(phen)₃]²⁺ complexes characteristic of 1–4.