Summary: | The crystal structures of the title salts, (C7H11N2)2[Mn(NCS)4] (1) and (C7H11N2)3[Mn(NCS)5] (2), consist of manganese(II) cations that are tetrahedrally (1) or trigonal–bipyramidally (2) coordinated to four or five terminal N-bonded thiocyanate ligands, respectively, into discrete anionic complexes. The negative charge is compensated by two (1) or three (2) 4-(dimethylamino)pyridinium cations, which are protonated at the pyridine N atom. The asymmetric unit of compound 1 consists of one anionic complex and two 4-(dimethylamino)pyridinium cations, whereas that of compound 2 consists of two anionic complexes and six 4-(dimethylamino)pyridinium cations, all of them located in general positions. These complexes are linked by N—H...S, C—H...S and C—H...N hydrogen-bonding interactions between the 4-(dimethylamino)pyridinium cations and the thiocyanate ligands into three-dimensional network structures.
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