(η6-Isopropyl N-phenyl­carbamate)(η5-penta­methyl­cyclo­penta­dien­yl)ruthenium(II) tetra­phenyl­borate acetone monosolvate

Bradley T Loughrey; Michael L Williams; Peter C Healy

doi:10.1107/S1600536811031655

. 2011 Aug 11;67(Pt 9):m1231. doi: 10.1107/S1600536811031655

(η⁶-Isopropyl N-phenylcarbamate)(η⁵-pentamethylcyclopentadienyl)ruthenium(II) tetraphenylborate acetone monosolvate

Bradley T Loughrey ^a, Michael L Williams ^a, Peter C Healy ^b,^*

PMCID: PMC3200656 PMID: 22058857

Abstract

The title complex, [Ru(C₁₀H₁₅)(C₁₀H₁₃NO₂)](C₂₄H₂₀B)·C₃H₆O, is related to the analogous O-methyl complex. The average Ru—C distance to the pentamethylcyclopentadienyl (Cp*) group is 2.19 (3) Å, and 2.21 (1) Å to the ortho, meta and para C atoms of the arene ring. The Ru—C_ipso bond length of 2.272 (3) Å is significantly longer, reflecting movement of the Ru atom away from the C atoms with electronegative substituents attached. The amide H atom in the cation forms an intermolecular N—H⋯O hydrogen bond with the carbonyl O atom of the acetone solvent molecule. A C—H⋯O interaction also occurs.

Related literature

For the synthesis and crystal structures of related compounds, see: Loughrey et al. (2008 ▶, 2009 ▶, 2010 ▶).

Experimental

Crystal data

[Ru(C₁₀H₁₅)(C₁₀H₁₃NO₂)](C₂₄H₂₀B)·C₃H₆O
M _r = 792.79
Monoclinic,
a = 9.8697 (2) Å
b = 28.7953 (7) Å
c = 14.3384 (3) Å
β = 92.334 (2)°
V = 4071.61 (15) Å³
Z = 4
Mo Kα radiation
μ = 0.43 mm⁻¹
T = 200 K
0.49 × 0.48 × 0.33 mm

Data collection

Oxford Diffraction Gemini S Ultra diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 ▶) T _min = 0.818, T _max = 0.872
44079 measured reflections
9342 independent reflections
8506 reflections with I > 2σ(I)
R _int = 0.025

Refinement

R[F ² > 2σ(F ²)] = 0.048
wR(F ²) = 0.126
S = 1.15
9342 reflections
478 parameters
H-atom parameters constrained
Δρ_max = 1.18 e Å⁻³
Δρ_min = −1.20 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: TEXSAN (Molecular Structure Corporation, 2001 ▶) and SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: TEXSAN and SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: PLATON (Spek, 2009 ▶) and publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811031655/ng5208sup1.cif

e-67-m1231-sup1.cif^{(56KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811031655/ng5208Isup2.hkl

e-67-m1231-Isup2.hkl^{(456.9KB, 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
N1—H1⋯O3	0.88	2.07	2.890 (4)	154
C6—H6C⋯O1	0.95	2.56	3.512 (5)	174

Open in a new tab

Acknowledgments

We acknowledge support of this work by Griffith University, the Queensland University of Technology and the Eskitis Institute for Cell and Molecular Therapies.

supplementary crystallographic information

Comment

As part of our ongoing investigations into the structural chemistry of full-sandwich Cp*Ru(II) η⁶-arene π-bonded complex salts [Cp*Ru(II)-arene]⁺X^- (Loughrey et al., 2008, 2009, 2010), (Cp* = pentamethylcyclopentadiene) we have synthesized and determined the crystal structure of the title salt [Cp*Ru(η⁶-O-isopropyl N-phenylcarbamate)][BPh₄] as its acetone solvate (Figure 1). The crystal lattice for this compound is isostructural with the O-methyl complex (Loughrey et al., 2010) with cell dimensions for this latter complex a 9.8006 (8), b 27.610 (2), c 14.627 (1) Å, β 91.984 (7)°. The major difference in these parameters for the two compounds is the increase in the length of the b axis from 27.620 (2)Å to 28.7953 (7)Å in order to accomodate the increased steric bulk of the iso-propyl group.

In the cation, the average Ru—C distance to the Cp* group is 2.19 (3)Å and 2.21 (1)Å to the ortho, meta and para carbon atoms C12 - C16 of the arene group; in accord with results reported for other Cp*Ru(arene) sandwich complexes (Loughrey et al., 2010 and references therein). The Ru—C_ipso bond length of 2.272 (3)Å is, as observed for the other O-alkyl structures, significantly longer, reflecting movement of the Ru atom away from carbon atoms with electronegative substituents attached.

The carbamate group in the arene ligand adopts a trans conformation. The bond distances N1—C17 = 1.387 (5) Å, C17—O1 = 1.207 (5) Å, and C17—O2 = 1.339 (5) Å, are 0.02 - 0.03Å longer than the corresponding distances in the O-methyl, O-ethyl and O-propyl complexes (Loughrey et al., 2010). The –NH—C(=O)—O—C– fragment is twisted out of the plane of the phenyl ring with the C17—O2—C11—C16 torsion angle 9.3 (5)°. The amide proton forms an intermolecular N—H···O hydrogen bond with the carbonyl oxygen of the acetone solvate.

The phenyl ring C11n (n = 1–6) of the [BPh₄]^- anion and the arene ring are perpendicular to each other and form a head-to-tail polymeric array along the crystallographic a axis, with the ortho and meta protons of the arene ring 3.0Å above and below the plane of ring C11n. The methyl groups of the isopropyl substitutent and acetone solvate interact with the remaining three phenyl rings of the anion through C—H···π interactions (Figure 2).

Experimental

Ruthenium trichloride hydrate (0.20 g,0.76 mmol) was transfered into a reaction vessel using iso-propanol (20 ml) and the solution heated at reflux until all starting material had dissolved. Phenylisocyanate (0.09 µL, 0.76 mmol) and pentamethylcyclopentadiene (0.30 ml, 1.88 mmol) were added to the reaction mixture and the resulting solution heated under reflux conditions for a further 10 h. The solvent was concentrated under vacuum and the remaining residue dissolved in a water/diethyl ether partition mixture (20:20 ml). The aqueous portion was retained and washed with a further three portions of diethyl ether (20 ml). The aqueous layer was then mixed slowly with a solution of NaB(C₆H₅)_4(aq) (5 mL, 0.30 M) resulting in the formation of a white, crystalline precipitate. This material was filtered from solution, redissolved in a minimum quantity of acetone and filtered through a short alumina column (neutral, 150 mesh, acetone eluent). The eluent was concentrated under vacuum and the product recrystallized by allowing the acetone solvent to slowly evaporate. This process yielded crystals of the acetone solvate suitable for X-ray diffraction studies.

Yield = 0.241 g, 43.1%. ESMS (m/z): +ve ion, calcd m/z for [(η⁵-C₅(CH₃)₅)Ru(η⁶-C₆H₅NHCO₂CH(CH₃)₂)]⁺]: 415.56, found: 416.14 (100%), -ve ion,calcd m/z for B(C₆H₅)₄^-: 319.25,found: 319.18 (100%); NMR: ¹H (d₆DMSO), d 1.27 (d, 6H, CH(CH₃)₂),1.85 (s, 15H, C₅(C₅H₁₅)), 3.33 (s,1H, CH(CH₃)₂),5.74–5.76 (m, 1H, aromatic), 5.87–5.90 (m, 2H, aromatic), 6.24–6.26 (m, 2H, aromatic),6.76–6.80 (m, 4H, B(C₆H₅)₄para), 6.90–6.94 (m, 8H, B(C₆H₅)₄meta), 7.17–7.19 (m, 8H, B(C₆H₅)₄ortho), 9.78 (s, br, 1H, NH); ¹³C (d₆DMSO),δ 9.81(C₅(C₅H₁₅)), 21.66 (CH(CH₃)₂), 30.65 (CH(CH₃)₂), 77.25(aromatic), 85.24 (aromatic), 85.95 (aromatic), 95.13 (C₅(C₅H₁₅), 110.01(C-NH), 121.49(4CH, B(C₆H₅)₄^-), 125.27 (8CH, B(C₆H₅)₄^-), 135.53 (8CH, B(C₆H₅)₄)^-, 153.21 (NHCO₂), 162.62, 163.11, 163.60, 164.09 (4CH, B(C₆H₅)₄), Signals Split by ¹¹B).