fac-Aqua­dichloridotris(tetra­methyl­ene sulfoxide-κS)ruthenium(II)

Radhey S Srivastava; Carlos F Gonzales; Frank R Fronczek

doi:10.1107/S1600536809000439

. 2009 Jan 10;65(Pt 2):m170. doi: 10.1107/S1600536809000439

fac-Aquadichloridotris(tetramethylene sulfoxide-κS)ruthenium(II)

Radhey S Srivastava ^a, Carlos F Gonzales ^a, Frank R Fronczek ^b,^*

PMCID: PMC2968404 PMID: 21581777

Abstract

The title molecule, [RuCl₂(C₄H₈OS)₃(H₂O)], is the isomer with the two chloride ligands cis and the three S-coordinated tetramethylene sulfoxide ligands facial relative to the Ru(II) center. The Ru—Cl distances are 2.4161 (7) and 2.4317 (7) Å, the Ru—O distance is 2.1540 (19) Å, and the Ru—S distances are in the range 2.2254 (8)–2.2657 (7) Å, with the shortest being that trans to the aqua ligand. The coordinated water molecule forms intermolecular hydrogen bonds with Cl and sulfoxide O atoms.

Related literature

For background literature, see: Aldinucci et al. (2007 ▶). For related structures, see: Srivastava & Fronczek (2003 ▶); Srivastava et al. (2004 ▶); Allen (2002 ▶). For hydrogen-bonding patterns, see: Etter (1990 ▶).

Experimental

Crystal data

[RuCl₂(C₄H₈OS)₃(H₂O)]
M _r = 502.48
Monoclinic,
a = 14.302 (3) Å
b = 7.7877 (15) Å
c = 17.248 (3) Å
β = 109.917 (9)°
V = 1806.2 (6) Å³
Z = 4
Mo Kα radiation
μ = 1.52 mm⁻¹
T = 90.0 (5) K
0.22 × 0.10 × 0.05 mm

Data collection

Nonius KappaCCD diffractometer (with an Oxford Cryosystems Cryostream cooler)
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997 ▶) T _min = 0.731, T _max = 0.928
25916 measured reflections
5982 independent reflections
4610 reflections with I > 2σ(I)
R _int = 0.045

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.076
S = 1.02
5982 reflections
199 parameters
H-atom parameters constrained
Δρ_max = 0.87 e Å⁻³
Δρ_min = −1.12 e Å⁻³

Data collection: COLLECT (Nonius, 2000 ▶); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO (Otwinowski & Minor, 1997 ▶) and SCALEPACK; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809000439/pv2128sup1.cif

e-65-0m170-sup1.cif^{(21.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809000439/pv2128Isup2.hkl

e-65-0m170-Isup2.hkl^{(286.9KB, 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
O4—H41⋯O1ⁱ	0.80	1.99	2.785 (3)	169
O4—H42⋯Cl2ⁱⁱ	0.80	2.37	3.116 (2)	156

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

Acknowledgments

Financial support provided by the Research Corporation (Cottrell College Science Award, #CC 6234 to RSS) and the BoR, Louisiana, is greatly appreciated. The purchase of the diffractometer was made possible by grant No. LEQSF (1999–2000)-ENH-TR-13, administered by the Louisiana Board of Regents.

supplementary crystallographic information

Comment

During the course of our studies on ruthenium-DMSO/TMSO complexes, mer-RuCl₃(TMSO)₃ was refluxed with methyl-p-tolylsulfide in absolute ethanol for 1 h. In view of anticancer properties of Ru-DMSO/TMSO complexes, we envision to interact mer-RuCl₃(TMSO)₃, (1) with sulfur donor ligands, because sulfur-containing ligands are able to bind the metal center strongly and prevent interactions with sulfur-containing enzymes (Aldinucci et al., 2007). In fact, these reactions are believed to be responsible for the nephrotoxicity induced by the platinum (II)-based drugs. However, the compound (2) was hydrolyzed on long standing in solution, and finally the title compound, fac-[RuCl₂(TMSO)₃(H₂O)] (3) was isolated. A plausible mechanism of the formation of (3) is shown in scheme 2.

There are three geometrical isomers of the title compound: trans,mer; cis,mer; and fac. The reported structure is found to be the latter, with chloro groups cis and TMSO groups facial, as shown in Fig. 1. More isomers are possible, considering that the TMSO ligands may be coordinated to Ru through either S or O in the same complex, (Srivastava & Fronczek, 2003; Srivastava et al., 2004); however, all are S-coordinated here. Relevant bond distances are given in the supplementary Tables. Most noteworthy is that the Ru—S3 distance, trans to water, is 0.03–0.04 Å shorter than the two Ru—S distances trans to Cl. While a search of the Cambridge Structural Database (version 5.29, Jan. 2008; Allen, 2002) for Ru complexes with S-bonded TMSO trans to water produced no hits, eleven examples of such DMSO complexes were found, refcodes AQAXIZ, AQAXOF, AQAXUL, BINBAC, CECSUZ, QUDRUC, TEXMOZ, TEXNEQ, TEXNIU, WOHNEM, AND WOHNIQ. Those have mean Ru—O distance 2.142 Å and mean Ru—S distance 2.256 Å. Our Ru—O distance, 2.1540 (19) Å, is near the high end of that sample, and our Ru—S distance, Ru1 S3 2.2254 (8) Å, is shorter than any in that sample.

The coordinated water molecule donates an intermolecular hydrogen bond to sulfoxide O and another to Cl, on two different molecules related by unit translation in the b direction. Thus, rings of graph set (Etter, 1990) symbol R²₂(9) form chains along [010], propagated by the 2₁ axis, as shown in Fig. 2.

Experimental

mer-RuCl₃(TMSO)₃ (0.166 g, 0.233 mmol) was refluxed with methyl-p-tolylsulfide (73 µl, 0.533 mmol) in absolute ethanol (15 ml) for 2 h, followed by cooling to room temperature. Upon standing for eight months, colorless needles of the title compound formed.