[(1R)-3-Benzoyl-1,7,7-trimethyl­bicyclo­[2.2.1]heptan-2-onato-κ2 O,O′]chlorido(η6-p-cymene)ruthenium(II)

Mohamed Anouar Harrad; Pedro Valerga; M Carmen Puerta; Mustapha Ait Ali; Larbi El Firdoussi; Abdellah Karim

doi:10.1107/S1600536810005015

. 2010 Feb 13;66(Pt 3):m281. doi: 10.1107/S1600536810005015

[(1R)-3-Benzoyl-1,7,7-trimethylbicyclo[2.2.1]heptan-2-onato-κ² O,O′]chlorido(η⁶-p-cymene)ruthenium(II)

Mohamed Anouar Harrad ^a, Pedro Valerga ^b,^*, M Carmen Puerta ^b, Mustapha Ait Ali ^a, Larbi El Firdoussi ^a, Abdellah Karim ^a

PMCID: PMC2983648 PMID: 21580227

Abstract

The asymmetric unit of the title compound, [RuCl(C₁₀H₁₄)(C₁₇H₁₉O₂)], contains two diastereomers. In both, the Ru^II ion has a tetrahedral coordination, formed by two O atoms of the camphor-derived ligand and the p-cymene and Cl ligands. In the crystal structure, weak intermolecular C—H⋯Cl interactions link the molecules into columns propagated along [010].

Related literature

For camphor-derived 1,3-diketonato ligands, see: Togni (1990 ▶); Togni et al. (1993 ▶). For applications of their transition metal complexes as therapeutic drugs, see: Guo & Sadler (1999 ▶). For related structures, see: Ait Ali et al. (2006 ▶); Spannenberg et al. (2002 ▶).

Experimental

Crystal data

[RuCl(C₁₀H₁₄)(C₁₇H₁₉O₂)]
M _r = 526.05
Triclinic,
a = 9.833 (2) Å
b = 10.572 (2) Å
c = 12.785 (3) Å
α = 108.13 (3)°
β = 97.62 (3)°
γ = 102.54 (3)°
V = 1203.9 (6) Å³
Z = 2
Mo Kα radiation
μ = 0.78 mm⁻¹
T = 100 K
0.56 × 0.31 × 0.24 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ▶) T _min = 0.762, T _max = 0.961
10110 measured reflections
7861 independent reflections
7619 reflections with I > 2σ(I)
R _int = 0.020

Refinement

R[F ² > 2σ(F ²)] = 0.031
wR(F ²) = 0.087
S = 1.06
7861 reflections
547 parameters
3 restraints
H-atom parameters constrained
Δρ_max = 0.95 e Å⁻³
Δρ_min = −1.34 e Å⁻³
Absolute structure: Flack (1983 ▶), 2564 Friedel pairs
Flack parameter: 0.03 (4)

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810005015/cv2696sup1.cif

e-66-0m281-sup1.cif^{(36.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810005015/cv2696Isup2.hkl

e-66-0m281-Isup2.hkl^{(384.5KB, 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
C43—H43⋯Cl1	0.95	2.69	3.605 (7)	162
C14—H14⋯Cl2	0.95	2.78	3.731 (7)	178

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Acknowledgments

The authors thank the SCCYT (Universidad de Cádiz) for the X-ray data collection and the Consejería de Innovación, Ciencia y Empresa de la Junta de Andalucía for financial support.

supplementary crystallographic information

Comment

Camphor-derived 1,3-diketonato ligands are a potentially attractive class of ligands in organometallic development, because these compounds are readily synthesized, easily varied (Togni et al., 1990, 1993) and some of their corresponding transition metal complexes can be used as therapeutic drugs (Guo et al., 1999). The crystallographic study of these compounds is of great interest in view of search for structure–activity relationships. This paper is a continuation of our X-ray crystal structure studies on rhodium and ruthenium complexes incorporating camphor-derived 1,3-diketonato ligands (Spannenberg et al., 2002; Ait Ali et al., 2006).

The title complex (I) was synthesized by addition of [RuCl₂(p-cymene)]₂ to a mixture of (1R)-3-Benzoyl-1,7,7-trimethyl-bicyclo[2.2.1]heptan-2-one, also named (1R)-3-benzoyl-camphor, and Na₂CO₃ in anhydrous THF. The neutral complex [RuCl(η⁶-p-cymene){κ²O,O'-(1R)-3-benzoyl- camphor}] was obtained. The metal centre shows tetrahedral coordination formed by two O atoms of the camphor-derived ligand, and the p-cymene and Cl ligands. Two independent molecules in the unit cell have opposite configuration at the metallic centre (R and S), but both of them keep the initial configuration at the two chiral carbon atoms in the (1R)-3-benzoyl-camphor free ligand being, consequently, diasteomers and only partially enantiomers.

In the crystal structure, weak intermolecular C—H···Cl interactions (Table 2) link the molecules into columns propagated in direction [010].

Experimental

A solution of [RuCl₂(p-cymene)]₂ (100 mg, 0.163 mmol) in 10 ml of THF was added to a suspension of (1R)-(+)-3-benzoyl-camphor (83.13 mg, 0.326 mmol) and Na₂CO₃ (103 mg, 0.978 mmol) in 10 ml of THF. The mixture was stirred for 3 h at room temperature. It was then evaporated to dryness under reduced pressure. The residue was extracted with CH₂Cl₂. The recovered filtrate was evaporated to dryness and lead to an orange solid with an output of 90%. The solid was recrystallized in diethylether. ¹H NMR (δ, p.p.m.): 0.76 (s, 6H), 0.9 (s, 1H), 1.22 (d, 6H), 1.23–1.3 (m, 4H), 2.2 (s, 3H), 2.5 (d, 1H), 2.8 (m, 1H), 5.11 (d, 2H), 5.34 (d, 2H), 7.18–7.47 (m, 5H, Ar). ¹³C{¹H} NMR (δ, p.p.m.): 9.8, 10.23, 17.93, 18.4, 19.28, 20.1, 20.4, 22.74, 27.47, 28.59,(28.71), 30.80, 31.09, (31.17), 50.20, 52.23, 58.35, 78.88, 82.74, 98.82, 99.16, 112.71, 113.68, 128.7, 129.16, 140.03, 174.11, 200.48, 201.01