Crystal structure of (2,11-diaza[3.3](2,6)pyridinophane-κ4N,N′,N′′,N′′′)(1,6,7,12-tetraazaperylene-κ2N1,N12)ruthenium(II) bis(hexafluoridophosphate) acetonitrile 1.422-solvate

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-diaza[3.3](2,6)pyridinophane; tape = 1,6,7,12-tetraazaperylene}, held together by π–π stacking interactions 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′-diimine unit and the amine proton of a 2,11-diaza[3.3](2,6)-pyridinophane ligand of the opposite complex cation. The combination of these interactions 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) interactions are found, leading to a three-dimensional architecture. The RuII atom is coordinated in a distorted octahedral geometry, particularly manifested by the Namine—Ru—Namine angle of 153.79 (10)°. 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. A second CH3CN molecule is fully occupied, but 1:1 disordered across a crystallographic inversion center.

Keywords

• crystal structure
• coordination compound
• ruthenium
• stacking