Crystal structure of bis-(tetra-methyl-thio-urea-κS)bis(thio-cyanato-κN)cobalt(II).

Aleksej Jochim,Christian Näther,Rastko Radulovic,Inke Jess

doi:10.1107/s205698902001021x

Aleksej Jochim, Christian Näther + Show 2 more

Open Access

https://doi.org/10.1107/s205698902001021x

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Abstract

In the course of systematic investigations on the synthesis of Co(NCS)2 coordination compounds with different thio-urea ligands, the title compound, [Co(NCS)2(C5H12N2S)2], was obtained. In this compound the CoII cations are coordinated by two crystallographically independent N-bonded thio-cyanate anions and two tetra-methyl-thio-urea ligands into discrete complexes that are located in general positions and show a strongly distorted tetra-hedral geometry. Inter-molecular C-H⋯S hydrogen bonds of different strength can be observed between the discrete complexes, which are connected by pairs of hydrogen bonds into zigzag-like chains that elongate in the b-axis direction. These chains are additionally linked by strong C-H⋯S hydrogen bonds along the a-axis direction, resulting in the formation of layers that are parallel to the ab plane. There is also one weak intra-molecular C-H⋯S hydrogen bond between two neighbouring thio-urea ligands within the complexes. Comparison of the experimental PXRD pattern with that calculated from the single-crystal data prove that a pure phase has been obtained. Thermoanalytical investigations reveal that this compound melts at 364 K and decomposes upon further heating.

Highlights

In the course of systematic investigations on the synthesis of Co(NCS)2 coordination compounds with different thiourea ligands, the title compound, [Co(NCS)2(C5H12N2S)2], was obtained
In this compound the CoII cations are coordinated by two crystallographically independent N-bonded thiocyanate anions and two tetramethylthiourea ligands into discrete complexes that are located in general positions and show a strongly distorted tetrahedral geometry
Intermolecular C—HÁ Á ÁS hydrogen bonds of different strength can be observed between the discrete complexes, which are connected by pairs of hydrogen bonds into zigzag-like chains that elongate in the b-axis direction

Summary

Chemical context

The thiocyanate anion is a very versatile ligand, which can coordinate in many different ways to metal cations, leading to compounds with a variety of coordination networks (Buckingham, 1994; Haasnoot et al, 1984; Barnett et al, 2002; Bhowmik et al, 2010; Abedi et al, 2016). For this composition a third structure type is known, in which the metal cations are tetrahedrally coordinated, forming discrete complexes with only N-terminally bonded thiocyanate anions (Neumann et al, 2018b). To investigate this in more detail, we used tetramethylthiourea as coligand and obtained crystals of the title compound Co(NCS)2(tetramethylthiourea)2 This compound consists of discrete complexes, in which the CoII cations are tetrahedrally coordinated, which is reflected in its IR spectra, where the C— N stretching vibration of the thiocyanate anion is observed at 2048 cmÀ1 (see Fig. S1 in the supporting information). The NMe2 groups of the same coligand are twisted against each other with angles of 45.74 (9) and 46.32 (8) for the two crystallographically independent tetramethylthiourea coligands

Supramolecular features

Database survey

Synthesis and crystallization

Refinement