Dichlorido[1-(2-chloroethyl)-3-(pyridin-4-ylmethyl-jN)urea](g 6 -hexamethyl-benzene) ruthenium(II) chloroform monosolvate Mathieu Auzias, Georg Su ¨ss-Fink and Bruno Therrien* Institut de Chimie, Universite ´ de Neucha ˆtel, Avenue de Bellevaux 51, CH-2000 Neucha ˆtel, Switzerland Correspondence e-mail: [email protected]Key indicators: single-crystal X-ray study; T = 173 K; mean (C–C) = 0.006 A ˚ ; R factor = 0.037; wR factor = 0.088; data-to-parameter ratio = 18.1. The Ru II atom in the title compound, [RuCl 2 (C 12 H 18 )- (C 9 H 12 ClN 3 O)]CHCl 3 , exhibits a typical piano-stool coordi- nation, defined by a hexamethylbenzene ligand, two chloride ligands and a pyridylurea ligand coordinated through the pyridine N atom. In the crystal, a dimeric structure is observed due to two strong N—HCl interactions between the NH groups of urea and the two chloride ligands of neighbouring molecules. In addition, the C O group of the urea moiety interacts with the solvent molecule through weak C—HO interactions. Related literature For the synthesis of 1-(chloroethyl)-3-(pyridin-4-ylmethyl)- urea, see: Nakao et al. (1974). For a review on arene ruthenium chemistry, see: Therrien (2009). For a review on arene ruthe- nium complexes as anticancer agents, see: Su ¨ ss-Fink (2010). For a review on multi-functional arene ruthenium complexes, see: Therrien & Smith (2011). For related structures, see: Auzias et al. (2008, 2009); Govender et al. (2009); Therrien et al. (2004); Therrien & Su ¨ ss-Fink (2004). Experimental Crystal data [RuCl 2 (C 12 H 18 )(C 9 H 12 ClN 3 O)]- CHCl 3 M r = 667.27 Monoclinic, P2 1 =c a = 15.0947 (16) A ˚ b = 13.3402 (10) A ˚ c = 15.4847 (16) A ˚ = 116.026 (11) V = 2801.9 (5) A ˚ 3 Z =4 Mo Kradiation = 1.15 mm 1 T = 173 K 0.18 0.16 0.15 mm Data collection Bruker SMART CCD diffractometer Absorption correction: refined from F (Walker & Stuart, 1983) T min = 0.457, T max = 0.822 21527 measured reflections 5514 independent reflections 3710 reflections with I >2(I) R int = 0.065 Refinement R[F 2 >2(F 2 )] = 0.037 wR(F 2 ) = 0.088 S = 0.89 5514 reflections 304 parameters H-atom parameters constrained max = 0.85 e A ˚ 3 min = 0.64 e A ˚ 3 Table 1 Hydrogen-bond geometry (A ˚ , ). D—HA D—H HA DA D—HA N2—H2aCl2 i 0.86 2.62 3.270 (3) 133 N3—H3aCl1 i 0.86 2.49 3.226 (4) 144 C22—H22O1 ii 0.98 1.95 2.908 (5) 165 Symmetry codes: (i) x; y þ 2; z þ 1; (ii) x þ 1; y þ 2; z þ 1. 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. A generous loan of ruthenium chloride hydrate from the Johnson Matthey Technology Centre is gratefully acknowl- edged. References Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115–119. Auzias, M., Gueniat, J., Therrien, B., Su ¨ ss-Fink, G., Renfrew, A. K. & Dyson, P. J. (2009). J. Organomet. Chem. 694, 855–861. Auzias, M., Therrien, B., Su ¨ ss-Fink, G., S ˇ te ˇ pnic ˇka, P., Ang, W. H. & Dyson, P. J. (2008). Inorg. Chem. 47, 578–583. Bruker (1999). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Govender, P., Antonels, N. C., Mattsson, J., Renfrew, A. K., Dyson, P. J., Moss, J. R., Therrien, B. & Smith, G. S. (2009). J. Organomet. Chem. 694, 3470– 3476. Nakao, H., Fukushima, M., Shimizu, F. & Arakawa, M. (1974). Yakugaku Zasshi, 94, 1032–1037. Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Su ¨ss-Fink, G. (2010). Dalton Trans. 39, 1673–1688. Therrien, B. (2009). Coord. Chem. Rev. 253, 493–519. Therrien, B. & Smith, G. S. (2011). Dalton Trans. 40, 10793–10800. Therrien, B. & Su ¨ss-Fink, G. (2004). Inorg. Chim. Acta, 357, 219–224. Therrien, B., Vieille-Petit, L., Jeanneret-Gris, J., S ˇ te ˇ pnic ˇka, P. & Su ¨ss-Fink, G. (2004). J. Organomet. Chem. 689, 2456–2463. Walker, N. & Stuart, D. (1983). Acta Cryst. A39, 158–166. 1
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SHELXTL; software used to prepare material for publication:
SHELXTL.
A generous loan of ruthenium chloride hydrate from the
Johnson Matthey Technology Centre is gratefully acknowl-
edged.
References
Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C.,Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J.Appl. Cryst. 32, 115–119.
Auzias, M., Gueniat, J., Therrien, B., Suss-Fink, G., Renfrew, A. K. & Dyson, P.J. (2009). J. Organomet. Chem. 694, 855–861.
Auzias, M., Therrien, B., Suss-Fink, G., Stepnicka, P., Ang, W. H. & Dyson, P. J.(2008). Inorg. Chem. 47, 578–583.
Bruker (1999). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin,USA.
Govender, P., Antonels, N. C., Mattsson, J., Renfrew, A. K., Dyson, P. J., Moss,J. R., Therrien, B. & Smith, G. S. (2009). J. Organomet. Chem. 694, 3470–3476.
Nakao, H., Fukushima, M., Shimizu, F. & Arakawa, M. (1974). YakugakuZasshi, 94, 1032–1037.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.Suss-Fink, G. (2010). Dalton Trans. 39, 1673–1688.Therrien, B. (2009). Coord. Chem. Rev. 253, 493–519.Therrien, B. & Smith, G. S. (2011). Dalton Trans. 40, 10793–10800.Therrien, B. & Suss-Fink, G. (2004). Inorg. Chim. Acta, 357, 219–224.Therrien, B., Vieille-Petit, L., Jeanneret-Gris, J., Stepnicka, P. & Suss-Fink, G.
(2004). J. Organomet. Chem. 689, 2456–2463.Walker, N. & Stuart, D. (1983). Acta Cryst. A39, 158–166.
Introduction of biologically active components into arene ruthenium(II) complexes, promising new class of metal-baseddrugs (Süss-Fink, 2010), is often performed by coordination of functionalized ligands. Therefore, it is not surprising thatpyridyl-functionalized ligands have been coupled to arene ruthenium(II) units to generate multi-functional metallo-drugs(Therrien & Smith, 2011). In this respect, the pyridyl-functionalized ligand 1-(chloroethyl)-3-(pyridin-4-ylmethyl)urea,
an antileukemic agent (Nakao et al., 1974), has been coordinated to (η6-hexamethylbenzene)RuCl2 unit (Scheme 1). The
single-crystal X-ray structure analysis of the neutral complex dichlorido{1-(chloroethyl)-3-(pyridin-4-ylmethyl)urea-κN}
(η6-hexamethylbenzene)ruthenium(II) is presented.
The complex shows a three-legged piano-stool geometry with the RuII metal center being surrounded by a hexamethyl-benzene ligand, two terminal chlorido and a N-coordinated pyridyl urea ligand, see Fig. 1. The pyridyl-functionalized lig-and, 1-(chloroethyl)-3-(pyridin-4-ylmethyl)urea, acts as a monodentate ligand and the Ru—N distance at 2.137 (3) Å is
comparable to those found in analogous (η6-arene)RuCl2(pyridyl-functionalized) complexes (Govender et al., 2009; Auzi-
as et al., 2008; Auzias et al., 2009). The aromatic ring of the hexamethylbenzene is planar and the Ru-centroid distanceis 1.670 Å (centroid being defined by C10 to C15). Otherwise, the Ru—Cl distances are 2.4066 (11) and 2.4173 (10) Å,respectively, which are similar to those found in other dichlorido arene ruthenium complexes (Therrien & Süss-Fink, 2004;Therrien et al., 2004).
In the crystal packing, both chlorido ligands are involved in H-bonded interaction with the NH moieties of a neighbouringmolecule, thus forming a symmetry-related dimeric structure (Fig. 2). The N—Cl separations are respectively 3.270 (3)Å (N—H···Cl = 133.0°) for N(2)—Cl(2) and 3.226 (4) Å (N—H···Cl = 144.3°) for N(3)—Cl(1). In addition, the carbonylgroup of urea interacts with chloroform: The O—C distance being 2.908 (5) Å with a C(22)—H(22)···O(1) angle of 165.3°.
Experimental
Crystals suitable for X-ray diffraction analysis were obtained, after days, by slow diffusion of diethyl ether into a chloroformsolution of the title complex.
Refinement
All H atoms were included in calculated positions (C—H = 0.93 Å for Carom, 0.98 for Å CH, 0.97 Å for CH2, 0.96 Å for CH3;
N—H = 0.86 Å for NH2) and treated as riding atoms with the constraint Uiso(H) = 1.2 (1.5 for methyl) Ueq(carrier) applied.
Fig. 1. The molecular structure of (η6-C12H18)RuCl2(C9H12N3OCl-κN), CHCl3 being omit-ted for clarity. Displacement ellipsoids are drawn at the 50% probability level.
Fig. 2. Dimeric structures observed in the crystal (symmetry code: (i) -x, 2 - y, 1 - z).
Refinement on F2 Primary atom site location: structure-invariant directmethods
Least-squares matrix: full Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.037Hydrogen site location: inferred from neighbouringsites
wR(F2) = 0.088 H-atom parameters constrained
S = 0.89w = 1/[σ2(Fo
2) + (0.0508P)2]where P = (Fo
2 + 2Fc2)/3
5514 reflections (Δ/σ)max = 0.001
304 parameters Δρmax = 0.85 e Å−3
0 restraints Δρmin = −0.64 e Å−3
Special details
Experimental. A crystal was mounted at 173 K on a Bruker SMART CCD PLATFORM using Mo Kα graphite monochromated radi-ation. Image plate distance 70 mm, φ oscillation scans 0 - 200°, step Δφ = 1.2°, 3 minutes per frame.
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance mat-rix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlationsbetween e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment ofcell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, convention-
al R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-
factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as largeas those based on F, and R- factors based on ALL data will be even larger.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)