Crystal Structures and Intercalation Reactions of Three‐Dimensional Coordination Polymers [M(H 2 O) 2 ] 2 [Mo(CN) 8 ]·4H 2 O (M = Co, Mn)

Two coordination polymers [MII(H2O)2]2[MoIV(CN)8]·4H2O [MII = Co (1), Mn (2)] were prepared as monocrystals and structurally characterised. These compounds crystallise in the tetragonal systems I4/m (1) and I4/mcm (2) and form three-dimensional networks containing channels occupied by two types of water molecules, i.e. coordinated to MII and crystallised ones. The dehydration of these materials occurs topochemically to give [MII(H2O)]2[MoIV(CN)8] compounds having an open metal coordination site on the MII ions that may be accessible to coordination by other species and serve as a reaction site. The intercalation of water, ammonia and amines has been studied. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)