A cyanide-bridged Fe2Co 2D sheet exhibiting electron transfer coupled spin transition (ETCST) with co-existence of magnetic ordering below 50 K is reported. The complex exhibits single-chain magnet behaviour where the uncoordinated water molecules act as an exchange-breaking impurity by allowing only a fraction of the molecule to undergo a spin state change. The paramagnetic centres prevail throughout the chain on desolvation, thereby increasing the number of correlated units in the chain.