An iron(III) complex [Fe(qsal)(2)](2)NP center dot CH3OH (1) (Hqsal: N-(8-quinolyl)salicylaldimine, and NP: nitroprusside) was synthesized and characterized by X-ray structure analysis, temperature-dependent magnetic susceptibility, and Mossbauer spectroscopy. The structures of 1 at 100 and 300 K were determined. X-ray crystallographic data revealed that the compound 1 was constructed by two [Fe(qsal)(2)](+) sites in the low-spin and high-spin states and a nitroprusside site at 100 K, and two [Fe(qsal)(2)](+) sites in the high-spin state and a nitroprusside site at 300 K. One site [Fe(qsal)(2)](+) in iron(III) complex exhibited spin-crossover behavior and LIESST effect.