Several reactions between manganese(II) chloride (tetrahydrate and dihydrate) and non-substituted 2-, 3- and 4-hydroxymethylpyridine were performed, with different molar ratios of reactants. Chosen reactions which led to new compounds at room temperature, were repeated in solvothermal conditions. Four new compounds were prepared, among them, one was identified in three polymorph phases; we also prepared a known compound through a modified synthesis path and determined the crystal structure of the 4hmp ligand: Compounds 1 and 4 are mononuclear complexes, compound 2 is the already known binuclear complex, compounds 3 and 5 are coordination polymers and compound 6 is the crystallized ligand 4hmp. Additionally for compounds 1, 2, 4 and 6, Hirshfeld surface analysis was performed.
The 2hmp ligand was coordinated in bidentate chelating manner in the structure of compound 1; we were able to prepare three polymorphs of the aforementioned molecular species. The bidentate chelating manner of hmp ligands was also observed in the structures of compound 2 and 3, while in compound 4, the 3hmp ligand coordinated in a monodentate manner. In all cases, the smaller units in the structure are linked by O–H⸱⸱⸱O or O–H⸱⸱⸱Cl-type of hydrogen bonds (or both). Under the selected synthesis parameters, we were unable to prepare compounds with 4hmp as the ligand.
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