Crystal structure of fac-tricarbonyl-chlorido-bis(para-N’,N’-dimethyl-κ- N-pyridyl)rhenium(I) toluene (1:1), C24H28ClN4O3Re

Abstract

Source of materialThecompoundwas obtained upon reacting Re(CO) 5 Cl with the pyridine-derived ligand in toluene. Crystals suitable for the diffraction study were obtained upon free evaporation of the solvent at ambient conditions. Experimental detailsCarbon-bound Hatomswere placed in calculated positions (C-H 0.95 Å) and were included in the refinement in the riding model approximation, with U iso (H) setto1.2U eq (C). The Hatoms of the methyl groups were allowed to rotate with afixed angle around the C-C bond to best fit the experimental electron density (HFIX 137 in the SHELX program suite [10]), with U iso (H) sett o 1.5U eq (C). The disorder among the chlorine and carbonyl ligands was modelled applying SADI instructions. DiscussionNext to cardiovascular diseases, cancer has become one of the main fatal diseases in industrialized countries. Apart from classicalsurgery,chemo-and radiotherapeutic treatments have entered the arsenal of possible cures for certain types of cancer. All methods, however, suffer from theirown setofproblematic side-effects and, as ac onsequence, the development of radiopharmaceuticals -combining the advantages of chemotherapy as well as radiation methods while at the sametimeavoiding their unique respective undesiredside-effects -has been atopic of research [1,2].T ailoring andf ine-tuning of thee nvisionedr adiopharmaceuticals' properties such as lipophilicityand,inparticular, inertness is of paramountimportancewithrespect to possible future in vivo applications in contemporary medicine and requires sound knowledge about structural parameters of the ligands applied if a more heuristic approach in the synthesis is to triumph over pure trial-and-error as it is encountered in this specific field of coordination chemistry up to the present day. In addition, the spatial requirements of pharmaceuticals are of importance as this factor influences on their interaction with enzymatic systems and, as a consequence,t he pathway and rate of conjugation, functionalization and secretion from the body. In continuation of our ongoing research on the field of rhenium coordination compounds, the title compound was synthesized and its molecular and crystal structure were elucidated [3]. Thec rystal structures of severalo ther rheniumcoordinationc ompounds featuring parasubstituted pyridine derivatives in the ligand sphere are apparent in the literature [4][5][6][7][8] next to thec ompound derivedf rom unsubstituted pyridine [7]. The title compound is arhenium(I) coordination compound. The central atom is hexacoordinate. The octahedral coordination sphere is comprised of one chlorido ligand and three carbonyl groups in fac configuration as well as two pyridine-derived ligands bearing dimethylamino-substituents in para position to the respective intracyclic nitrogen atom. The coordination of the latter two ligands is effected by the two nitrogen atomsofthe aromatic moieties. The chlorido as well as its trans-configured carbonyl ligand show positional disorder in a ratio of approximately 0.55:0.45. The le...

Human Rights Obligations of the Territorial State in the Cyberspace of Areas Outside Its Effective Control

“…94 Related to an area outside the state's effective control, this type of jurisdiction might lead to various scenarios. Under 'objective jurisdiction', the cyber activity originates abroad, but is completed in the area concerned 95 and the territorial state would be entitled, for instance, to exercise its criminal jurisdiction over the perpetrators of the cybercrime by way of mutual legal assistance. Under 'subjective territorial jurisdiction', the state can exercise jurisdiction over any cyber activity originating from the area outside its effective control, such as online recruitment of terrorist fighters or hate speech diffused from the area concerned.…”