A one-dimensional cyanide-bridged coordination polymer, poly[[aquadi-μ-cyanido-κ4C:N-hexacyanido-κ6C-(dimethylformamide-κO)bis(3,4,7,8-tetramethyl-1,10-phenanthroline-κ2N,N′)terbium(III)molybdate(V)] 4.5-hydrate], [MoTb(CN)8(C16H16N2)2(C3H7NO)(H2O)]·4.5H2O}n, has been prepared and characterized through IR spectroscopy, elemental analysis and single-crystal X-ray diffraction. The compound consists of one-dimensional chains in which cationic [Tb(tmphen)2(DMF)(H2O)]3+(tmphen is 3,4,7,8-tetramethyl-1,10-phenanthroline) and anionic [MoV(CN)8]3−units are linked in an alternating fashion through bridging cyanide ligands. Neighbouring chains are connected by three types of hydrogen bonds (O—H...O, O—H...N and C—H...O) and by π–π interactions to form a three-dimensional supramolecular structure. In addition, magnetic investigations show that ferromagnetic interactions exist in the compound.
