[Bis­(2-pyrid­yl-κN)amine]chlorido(η6-hexa­methyl­benzene)­ruthenium(II) hexa­fluorido­phosphate dichloro­methane solvate

Gajendra Gupta; Bruno Therrien; Jinkwon Kim

doi:10.1107/S1600536811011640

. 2011 Apr 7;67(Pt 5):m548. doi: 10.1107/S1600536811011640

[Bis(2-pyridyl-κN)amine]chlorido(η⁶-hexamethylbenzene)ruthenium(II) hexafluoridophosphate dichloromethane solvate

Gajendra Gupta ^a, Bruno Therrien ^b, Jinkwon Kim ^a,^*

PMCID: PMC3089226 PMID: 21754285

Abstract

In the title half-sandwich complex, [RuCl(η⁶-C₁₂H₁₈)(C₁₀H₉N₃)]PF₆·CH₂Cl₂, the ruthenium(II) ion is four-coordinated by a chloro, a hexamethylbenzene and a bidentate N,N′-chelating di(pyridin-2-yl)amine ligand. In the crystal, the amino N—H group forms a hydrogen bond with the chloro ligand of a neighbouring complex, thus forming chains along the b axis. Weak intermolecular C—H⋯F and C—H⋯ Cl contacts are also observed.

Related literature

For related structures with the same N,N′-chelating ligand coordinated to arene ruthenium moieties, see: Romain et al. (2010 ▶); Gupta et al. (2011 ▶); Singh et al. (2004 ▶). For the synthesis, see: Romain et al. (2010 ▶); Gupta et al. (2010 ▶).

Experimental

Crystal data

[RuCl(C₁₂H₁₈)(C₁₀H₉N₃)]PF₆·CH₂Cl₂
M _r = 699.88
Monoclinic,
a = 15.5241 (4) Å
b = 9.1644 (2) Å
c = 18.9108 (5) Å
β = 93.621 (1)°
V = 2685.05 (12) Å³
Z = 4
Mo Kα radiation
μ = 1.00 mm⁻¹
T = 173 K
0.20 × 0.17 × 0.16 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.738, T _max = 0.871
31923 measured reflections
9327 independent reflections
7812 reflections with I > 2σ(I)
R _int = 0.030

Refinement

R[F ² > 2σ(F ²)] = 0.033
wR(F ²) = 0.087
S = 1.06
9327 reflections
344 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.77 e Å⁻³
Δρ_min = −0.78 e Å⁻³

Data collection: SMART (Bruker, 1999 ▶); cell refinement: SMART and SAINT (Bruker, 1999 ▶); data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXTL (Sheldrick, 2008 ▶); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811011640/om2411sup1.cif

e-67-0m548-sup1.cif^{(33.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811011640/om2411Isup2.hkl

e-67-0m548-Isup2.hkl^{(456.2KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯Cl1ⁱ	0.85 (3)	2.51 (3)	3.3493 (17)	170 (3)
C3—H3⋯F3ⁱⁱ	0.95	2.52	3.351 (3)	146
C8—H8⋯F5ⁱ	0.95	2.55	3.435 (3)	155
C20—H20A⋯Cl3ⁱⁱⁱ	0.98	2.78	3.626 (2)	144
C20—H20B⋯F2^iv	0.98	2.54	3.424 (3)	151

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) .

Acknowledgments

This work was supported by the Korea Research Foundation (KRF 313-2008-2-C00444).

supplementary crystallographic information

Comment

The title complex shows typical three legged piano-stool geometry with the ruthenium(II) atom being coordinated by a hexamethylbenzene ligand occupying one face of the octahedron, a terminal chloro and a bidentate N,N'-chelating ligand, see Fig. 1. The di(pyridin-2-yl)amine ligand acts as a bidentate chelating ligand through its two pyridyl groups, and the Ru-N distances are essentially equivalent at 2.099 (2) and 2.098 (2) Å. The aromatic ring of the hexamethylbenzene is planar and the Ru-centroid distance is 1.690 (2) Å. The Ru-Cl distance is 2.4108 (4) Å, similar to that found in other chloro arene ruthenium complexes (Singh et al., 2004; Gupta et al., 2011).

In the crystal packing, the N-H amino group is involved in a H-bonded interaction with the chloro ligand of a neighbouring complex, thus forming infinite one-dimensional chains along the b axis. Moreover, there are weak intermolecular contacts of the type C—H···F and C—H··· Cl.

Experimental

The synthesis of the title compound has been reported (Romain et al., 2010; Gupta et al., 2011). Yellow-orange crystals for X-ray diffraction analysis were obtained by slow diffusion of hexane into a dichloromethane solution of the title complex.