Abstract
In the title compound, [Ru(C14H16N4)(C16H8N4)](PF6)2·1.422CH3CN, discrete dimers of complex cations, [Ru(L-N4H2)tape](2+) are formed {L-N4H2 = 2,11-di-aza-[3.3](2,6)pyridino-phane; tape = 1,6,7,12-tetra-aza-perylene}, held together by π-π stacking inter-actions via the tape ligand moieties with a centroid-centroid distance of 3.49 (2) Å, assisted by hydrogen bonds between the non-coordinating tape ligand α,α'-di-imine unit and the amine proton of a 2,11-di-aza-[3.3](2,6)-pyridino-phane ligand of the opposite complex cation. The combination of these inter-actions leads to an unusual nearly face-to-face π-π stacking mode. Additional weak C-H⋯N, C-H⋯F, N-H⋯F and P-F⋯π-ring (tape, py) (with F⋯centroid distances of 2.925-3.984 Å) inter-actions are found, leading to a three-dimensional architecture. The Ru(II) atom is coordinated in a distorted octa-hedral geometry, particularly manifested by the Namine-Ru-Namine angle of 153.79 (10)°. The counter-charge is provided by two hexa-fluorido-phosphate anions and the asymmetric unit is completed by aceto-nitrile solvent mol-ecules of crystallization. Disorder was observed for both the hexa-fluorido-phosphate anions as well as the aceto-nitrile solvate mol-ecules, with occupancies for the major moieties of 0.801 (6) for one of the PF6 anions, and a shared occupancy of 0.9215 (17) for the second PF6 anion and a partially occupied aceto-nitrile mol-ecule. A second CH3CN mol-ecule is fully occupied, but 1:1 disordered across a crystallographic inversion center.
Highlights
Centroid distance of 3.49 (2) Å, assisted by hydrogen bonds between the noncoordinating tape ligand,0 -diimine unit and the amine proton of a 2,11diaza[3.3](2,6)-pyridinophane ligand of the opposite complex cation
The counter-charge is provided by two hexafluoridophosphate anions and the asymmetric unit is completed by acetonitrile solvent molecules of crystallization
Disorder was observed for both the hexafluoridophosphate anions as well as the acetonitrile solvate molecules, with occupancies for the major moieties of 0.801 (6) for one of the PF6 anions, and a shared occupancy of 0.9215 (17) for the second PF6 anion and a partially occupied acetonitrile molecule
Summary
Heteroaromatic ligands with more than three fused rings are commonly called large-surface ligands. Such ligands have attracted attention due to their use as connecting building blocks for supramolecular assemblies. In order to study the properties of ruthenium complexes containing large-surface ligands, we have recently reported an easy entry to such complexes (Brietzke, Mickler, Kelling, Schilde et al, 2012). Therein, we formulated the advantages of the 2,11-dimethyl-2,11-diaza[3.3](2,6)-pyridinophane (L–N4Me2) macrocycle over bipyridine (bpy)-type ligands in saturating the coordination sphere of an octahedral ruthenium complex containing the large-surface ligand of interest. The microwave-assisted synthesis of the precursor [Ru(L–N4Me2)]2+, starting from [Ru(DMSO)4Cl2] and L–N4Me2, in an ethanolic solution finished within 30 min. [155.46 (9)–155.93 (17) ; Brietzke, Mickler, Kelling, Schilde et al, 2012]
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