Abstract
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 tetra-hedrally (1) or trigonal-bipyramidally (2) coordinated to four or five terminal N-bonded thio-cyanate ligands, respectively, into discrete anionic complexes. The negative charge is compensated by two (1) or three (2) 4-(di-methyl-amino)-pyridinium cations, which are protonated at the pyridine N atom. The asymmetric unit of compound 1 consists of one anionic complex and two 4-(di-methyl-amino)-pyridinium cations, whereas that of compound 2 consists of two anionic complexes and six 4-(di-methyl-amino)-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 inter-actions between the 4-(di-methyl-amino)-pyridinium cations and the thio-cyanate ligands into three-dimensional network structures.
Highlights
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 Nbonded 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
Summary
Thiocyanate anions are versatile ligands that can be coordinated to metal cations in different ways. [Mn(NCS)2(4-(dimethylamino)pyridine)4], but in all cases obtained only the salt-like crystals 1 and 2, in which the MnII atom is solely coordinated by thiocyanate ligands, either in a tetrahedral (1) or trigonal–bipyramidal (2) configuration, and charge-balanced by 4-(dimethylamino)pyridinium cations. It should be mentioned that neither of the two compounds could be prepared in larger amounts as a pure crystalline phase, because mixtures were always obtained Both compounds are of interest from a structural point of view, because negatively charged manganate complexes with a fivefold coordination by thiocyanate ligands are scarce. In the structure of this compound, the MnII atom is octahedrally coordinated to four terminal N-bonded thiocyanate anions and two neutral 4-(dimethylamino)pyridine ligands, and the twofold negative charge is compensated by two 4-(dimethylamino)pyridinium cations. Charge of the anionic complexes in compounds 1 and 2 is compensated by two or six, respectively, crystallographically independent 4-(dimethylamino)pyridinium cations that are located in general positions (Figs. 2 and 4)
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