RESUMEN
A novel two-dimensional (2D) Hofmann-type coordination polymer, {FeII(PyHbim)2[Pd(CN)4]}·2CH3OH [1·2CH3OH, PyHbim = 2-(4-pyridyl)benzimidazole], has been synthesized, which can undergo a spontaneous guest exchange, transforming to 1·2H2O in a single-crystal-to-single-crystal (SCSC) manner, shifting from orthorhombic Cmmm to monoclinic C2/m involving the displacement of 2D layers. The solvent-induced SCSC transformation process was reversible and verified through powder X-ray diffraction (PXRD) and single-crystal X-ray crystallography analyses. Both 1·2CH3OH and 1·2H2O exhibit complete and abrupt spin crossover (SCO) behaviors in two steps, while their SCO temperature ranges drastically shift by ca.100 K, spanning room temperature, owing to different intermolecular interactions resulting from diverse interlayer packing manners and host-guest interactions. Besides, a structural phase transition is observed in 1·2CH3OH, contributing to the two-step spin transition.