AbstractReaction of manganese (II) thiocyanate with 2,5-dimethylpyrazine leads to the formation of three new coordination compounds of compositions Mn(NCS)2(2,5-dimethylpyrazine)2(H2O)2 (1), Mn(NCS)2(H2O)2(MeOH)2-tris(2,5-dimethylpyrazine) solvate (2), and Mn(NCS)2 (H2O)4-tetrakis(2,5-dimethylpyrazine) solvate (3) that were characterized by single crystal X-ray diffraction. In their crystal structures, the Mn(II) cations are sixfold coordinated by two terminally N-bonded thiocyanato anions and two water molecules as well as by two 2,5-dimethylpyrazine ligands (1), two ethanol (2), or two water molecules (3), within slightly distorted octahedra. In compounds 2 and 3, additional 2,5-dimethylpyrazine ligands are located in the cavities of the structures as solvate molecules. X-ray powder diffraction has shown that compounds 1 and 2 cannot be prepared as pure phases and that batches of compound 3 contain only minor traces of a contamination. Differential thermoanalysis and thermogravimetry have revealed that upon heating of compound 3, an intermediate of composition Mn(NCS)2(2,5-dimethylpyrazine) (4) is formed, which cannot be obtained from solution. To mimic the structure of 4, single crystals of a Cd compound of the same composition (5) were prepared from the liquid phase, and single crystal X-ray analysis has shown that it is isotypic to 4.