The spin-crossover compound [Fe(bbtr)3](ClO4)2 (bbtr = 1,4-di(1,2,3-triazol-1-yl)butane) forms a polymeric hexagonal sheet structure. It shows an abrupt thermal spin transition with 13 K wide hysteresis around 105 K, as evidenced by single crystal optical spectroscopy. The transition temperature for the thermal high-spin→low-spin transition on cooling as well as the relaxation kinetics just below Tc↓ depend upon the history of the sample. This is typical for a nucleation and growth mechanism and domain formation. In contrast, the high-spin→low-spin relaxation following the light-induced population of the high-spin state at low temperatures is governed by the intersystem crossing process.