We synthesized a cyanido-bridged MnÀ Nb metal assembly possessing large-sized bridging ligands with disulfide bonds, [Mn(dpds) 2 ] 2 [Nb(CN) 8 ] • 6H 2 O (MnNb, dpds: 4,4'-dipyridyldisulfide). MnNb has a three-dimensional coordination framework in which the Mn and Nb sites are bridged by cyanides, while the Mn sites are combined by dpds ligands. The two crystallographically independent dpds ligands are bent around the disulfide bond with large C(pyridine)À SÀ SÀ C(pyridine) dihedral angles of 105.4(5)°and 102.2(5)°, respectively. For moleculebased magnets, dpds is a relatively large bridging ligand, but it is compatible with the limited space of the cyanido-bridged MnÀ Nb coordination framework due to the bent structure. Additionally, antiferromagnetic coupling in MnNb of À 13 cm À 1 between Mn II (S = 5/2, g = 2) and Nb IV (S = 1/2, g = 2) induces ferrimagnetism with a critical temperature of 46 K.

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