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

Rein FN, Chen W, Scott BL, Rocha RC - Acta Crystallogr E Crystallogr Commun (2015)

Bottom Line: The Ru-Cl distance is 2.3982 (16) Å.The crystal packing shows significant π-π stacking inter-actions based on tpy-tpy.The crystal structure reported here is the first for a tpy-tpy complex of ruthenium.

View Article: PubMed Central - HTML - PubMed

Affiliation: Los Alamos National Laboratory, Los Alamos, NM 87545, USA.

ABSTRACT
We report the structural characterization of [6',6''-bis-(pyridin-2-yl)-2,2':4',4'':2'',2'''-quaterpyridine](2,2'-bi-pyridine)-chlorido-ruthenium(II) hexa-fluorido-phosphate, [RuCl(C10H8N2)(C30H20N6)]PF6, which contains the bidentate ligand 2,2'-bi-pyridine (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 octa-hedral 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 inter-annular C-C bonds, with adjacent pyridyl rings being only approximately coplanar. The crystal packing shows significant π-π stacking inter-actions based on tpy-tpy. The crystal structure reported here is the first for a tpy-tpy complex of ruthenium.

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Two views of a 2×2×2 crystal packing diagram of 1·PF6. Displacement ellipsoids are drawn at the 50% probability level. H atoms are omitted for clarity.
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fig2: Two views of a 2×2×2 crystal packing diagram of 1·PF6. Displacement ellipsoids are drawn at the 50% probability level. H atoms are omitted for clarity.

Mentions: The hexa­fluorido­phosphate salt of the monocationic complex (1·PF6) crystallizes in the triclinic (P) space group. The structure of 1 is shown in Figs. 1 ▸ and 2 ▸, and selected data are summarized in Table 1 ▸. The complex has a distorted octa­hedral geometry at the metal due to the restricted bite angle of its meridionally coordinating tridendate ligand (a tpy moiety). The N1—Ru—N3 angle of 159.32 (16)° is very similar to those of bis-terpyridyl RuII complexes (Chen et al., 2013a ▸; Jude et al., 2013 ▸), and far from the ideal angle of 180°. The bidentate bpy ligand has a cis configuration, with the N4—Ru—N5 angle of 79.04 (16)° in agreement with those found in similar chlorido RuII-bpy complexes (Chen et al., 2011 ▸, 2013b ▸). The N4 atom of bpy is arranged trans to the chlorido ligand in a nearly linear N4—Ru—Cl fashion [172.92 (12)°]. The RuII atom and atoms N2, N4, N5, and Cl1 form an equatorial plane with a maximum deviation of 0.032 (4) Å. The Ru-bound tpy moiety and bpy are approximately planar [with maximum deviations of 0.086 (5) Å and 0.071 (5) Å, respectively] and their mean planes are essentially perpendicular to each other with a dihedral angle of 89.78 (11)° between planes. For the tridentate ligand, the mean Ru—N distance involving the outer N1 and N3 atoms trans to each other is 2.053 (8) Å, whereas the bond distance involving the central N2 is much shorter [1.936 (4) Å] as a result of the structural constraint imposed by these mer-arranged ligands (Chen et al., 2013a ▸; Jude et al., 2013 ▸). For the bidentate ligand, the Ru—N distance is 2.075 (4) Å for N5 but only 2.028 (4) Å for N4, reflecting the increased RuII→Nbpy π-backbonding inter­action at the coordinating atom trans to the π-donor Cl− ligand (Chen et al., 2013b ▸). The Ru—Cl distance of 2.3982 (16) Å is nearly the same as those observed previously (Chen et al., 2013b ▸; Jude et al., 2009 ▸). As expected, the free (uncoordinated) ‘half’ of tpy–tpy adopts a trans,trans conformation about the inter­annular C—C bonds (Constable et al., 1993 ▸). Unlike the coordinating half of tpy–tpy, the rings of the free tpy moiety are only approximately coplanar, with angles of 20.9 (3)° and 13.3 (3)° between adjacent rings.


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

Rein FN, Chen W, Scott BL, Rocha RC - Acta Crystallogr E Crystallogr Commun (2015)

Two views of a 2×2×2 crystal packing diagram of 1·PF6. Displacement ellipsoids are drawn at the 50% probability level. H atoms are omitted for clarity.
© Copyright Policy - open-access
Related In: Results  -  Collection

License
Show All Figures
getmorefigures.php?uid=PMC4555393&req=5

fig2: Two views of a 2×2×2 crystal packing diagram of 1·PF6. Displacement ellipsoids are drawn at the 50% probability level. H atoms are omitted for clarity.
Mentions: The hexa­fluorido­phosphate salt of the monocationic complex (1·PF6) crystallizes in the triclinic (P) space group. The structure of 1 is shown in Figs. 1 ▸ and 2 ▸, and selected data are summarized in Table 1 ▸. The complex has a distorted octa­hedral geometry at the metal due to the restricted bite angle of its meridionally coordinating tridendate ligand (a tpy moiety). The N1—Ru—N3 angle of 159.32 (16)° is very similar to those of bis-terpyridyl RuII complexes (Chen et al., 2013a ▸; Jude et al., 2013 ▸), and far from the ideal angle of 180°. The bidentate bpy ligand has a cis configuration, with the N4—Ru—N5 angle of 79.04 (16)° in agreement with those found in similar chlorido RuII-bpy complexes (Chen et al., 2011 ▸, 2013b ▸). The N4 atom of bpy is arranged trans to the chlorido ligand in a nearly linear N4—Ru—Cl fashion [172.92 (12)°]. The RuII atom and atoms N2, N4, N5, and Cl1 form an equatorial plane with a maximum deviation of 0.032 (4) Å. The Ru-bound tpy moiety and bpy are approximately planar [with maximum deviations of 0.086 (5) Å and 0.071 (5) Å, respectively] and their mean planes are essentially perpendicular to each other with a dihedral angle of 89.78 (11)° between planes. For the tridentate ligand, the mean Ru—N distance involving the outer N1 and N3 atoms trans to each other is 2.053 (8) Å, whereas the bond distance involving the central N2 is much shorter [1.936 (4) Å] as a result of the structural constraint imposed by these mer-arranged ligands (Chen et al., 2013a ▸; Jude et al., 2013 ▸). For the bidentate ligand, the Ru—N distance is 2.075 (4) Å for N5 but only 2.028 (4) Å for N4, reflecting the increased RuII→Nbpy π-backbonding inter­action at the coordinating atom trans to the π-donor Cl− ligand (Chen et al., 2013b ▸). The Ru—Cl distance of 2.3982 (16) Å is nearly the same as those observed previously (Chen et al., 2013b ▸; Jude et al., 2009 ▸). As expected, the free (uncoordinated) ‘half’ of tpy–tpy adopts a trans,trans conformation about the inter­annular C—C bonds (Constable et al., 1993 ▸). Unlike the coordinating half of tpy–tpy, the rings of the free tpy moiety are only approximately coplanar, with angles of 20.9 (3)° and 13.3 (3)° between adjacent rings.

Bottom Line: The Ru-Cl distance is 2.3982 (16) Å.The crystal packing shows significant π-π stacking inter-actions based on tpy-tpy.The crystal structure reported here is the first for a tpy-tpy complex of ruthenium.

View Article: PubMed Central - HTML - PubMed

Affiliation: Los Alamos National Laboratory, Los Alamos, NM 87545, USA.

ABSTRACT
We report the structural characterization of [6',6''-bis-(pyridin-2-yl)-2,2':4',4'':2'',2'''-quaterpyridine](2,2'-bi-pyridine)-chlorido-ruthenium(II) hexa-fluorido-phosphate, [RuCl(C10H8N2)(C30H20N6)]PF6, which contains the bidentate ligand 2,2'-bi-pyridine (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 octa-hedral 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 inter-annular C-C bonds, with adjacent pyridyl rings being only approximately coplanar. The crystal packing shows significant π-π stacking inter-actions based on tpy-tpy. The crystal structure reported here is the first for a tpy-tpy complex of ruthenium.

No MeSH data available.


Related in: MedlinePlus