Crystal structure of a mononuclear Ru(II) complex with a back-to-back terpyridine ligand: [RuCl(bpy)(tpy–tpy)](+)

We report the structural characterization of [6′,6′′-bis­(pyridin-2-yl)-2,2′:4′,4′′:2′′,2′′′-quaterpyridine](2,2′-bi­pyridine)­chlorido­ruthenium(II) hexa­fluorido­phosphate, [RuCl(C(10)H(8)N(2))(C(30)H(20)N(6))]PF(6), which contains the bidentate ligand 2,2′-bi­pyridine (bpy) and the tridendate ligand 6′,6′′-bis­(pyridin-2-yl)-2,2′:4′,4′′:2′′,2′′′-quaterpyridine (tpy–tpy). The [RuCl(bpy)(tpy–tpy)](+) monocation has a distorted octa­hedral geometry at the central Ru(II) ion due to the restricted bite angle [159.32 (16)°] of the tridendate ligand. The Ru-bound tpy and bpy moieties are nearly planar and essentially perpendicular to each other with a dihedral angle of 89.78 (11)° between the least-squares planes. The lengths of the two Ru—N bonds for bpy are 2.028 (4) and 2.075 (4) Å, with the shorter bond being opposite to Ru—Cl. For tpy–tpy, the mean Ru—N distance involving the outer N atoms trans to each other is 2.053 (8) Å, whereas the length of the much shorter bond involving the central N atom is 1.936 (4) Å. The Ru—Cl distance is 2.3982 (16) Å. The free uncoordinated moiety of tpy–tpy adopts a trans,trans conformation about the inter­annular C—C bonds, with adjacent pyridyl rings being only approximately coplanar. The crystal packing shows significant π–π stacking inter­actions based on tpy–tpy. The crystal structure reported here is the first for a tpy–tpy complex of ruthenium.