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The title compound, [Ru(C6H6NO2)2(C15H11N3)(H2O)]·CH3CN·H2O, is a transfer hydrogenation catalyst supported by nitro­gen-donor ligands. This octa­hedral RuII complex features rare monodentate coordination of 3-meth­oxy-2-pyridonate ligands and inter­ligand S(6)S(6) hydrogen bonding. Comparison of the title complex with a structural analog with unsubstituted 2-pyridonate ligands reveals subtle differences in the orientation of the ligand planes.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107004246/gz3063sup1.cif
Contains datablocks global, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270107004246/gz3063IIsup2.hkl
Contains datablock II

CCDC reference: 641788

Comment top

Transition metal catalysts for the transfer hydrogenation of alkanes and ketones have attracted considerable interest as a safe and economical alternative to traditional hydrogenation catalysts. Much of the effort devoted to developing these catalysts has focused on ligand design in RuII complexes (Fan et al., 2002; Naota et al., 1998; Noyori & Hashiguchi, 1997; Zassinovich et al., 1992). A vast majority of the reported systems were organometallic with inconvenient air (and often water) sensitivity. Nearly all reported transfer hydrogenation catalysts also required strong base co-catalysts for significant turnover rates. These base co-catalysts currently limit the application of these catalytic systems. Our laboratory has developed the only examples of well defined polypyridyl-supported RuII transfer hydrogenation catalysts that tolerate air and water. The structure and reactivity of one of these complexes, RuII(pyO)2(terpy)(OH2) (pyO is 2-pyridonate and terpy is 2,2':6',2"-terpyridine), (I), has been reported (Kelson & Phengsy, 2000). Complex (I) featured rare monodentate pyO ligands stabilized by hydrogen bonding between their carbonyl groups and an adjacent aqua ligand. Our mechanistic studies on complex (I) suggest that the intramolecular hydrogen bonding is important to formation of catalytic intermediates and proton transfer in the catalytic reaction. As part of our continuing development of the RuII(pyO)2(terpy)(OH2) system, the work presented here was concerned with the crystal structure of the newly synthesized complex from the reaction of RuIIICl3 with 3-methyl-2-pyridone (MeOpyOH) of the formula C27H25N5O5Ru·H2O·C2H3N, (II). The addition of the 3-methoxy substituent to the structure of complex (I) was expected to increase the basicity of the 2-pyridonate ligand and increase catalytic activity. However, complex (II) actually exhibited about half the activity of complex (I) toward the transfer hydrogenation of 2-adamantanone in 2-propanol, and no significant difference was observed in the pKb values of compounds (I) and (II) [8.76 (11) and 8.57 (14), respectively]. The crystal structures of (I) and (II) were compared to determine the structural influence of the 3-methoxy substitution on the catalysts.

Our analysis found that the structure of compound (II) consists of one molecule of RuII(MeOpyO)2(terpy)(OH2), one uncoordinated molecule of water and one uncoordinated molecule of acetonitrile. In the complex molecule, the Ru atom is surrounded by a distorted octahedral arrangement of donors from one tridentate terpy ligand, two MeOpyO ligands coordinated trans with respect to each other through their N atoms, and an aqua ligand (Fig. 1 and Table 1). The Ru—N and Ru—Oaqua distances typical for polypyridyl RuII complexes and the two easily located aqua H atoms confirm the RuII–aqua oxidation–protonation state of this complex (Hecker et al., 1991; Rasmussen et al., 1995; Grover et al., 1992). The geometry of the terpy ligand and its coordination are as expected. The alternating long–short C—C bond distances around the MeOpyO rings and the relatively short C16,C22—O distances are consistent with the pyridonate (versus the hydroxypyridinate) resonance form of MeOpyO. The solvent acetonitrile and disordered water molecules exhibit only weak interactions with other molecules within the unit cell and have no apparent impact on the structure of the complex. The lack of lattice interactions with the water molecule may be responsible for its disorder into three positions of 44.7 (12), 38.2 (11), and 17.1 (6)% occupation.

Interligand hydrogen bonds between the MeOpyO carbonyl O atoms and the aqua ligands (Table 2) close a pair of fused six-membered metallocycles. This concerted S(6)S(6) interaction appears to be responsible for stabilizing the rare monodentate coordination of the MeOpyO ligands and aligning their planes to a nearly eclipsed dihedral angle of 12.66 (4) Å. The strong hydrogen bonds to the aqua ligand also appear to tip the MeOpyO planes toward the hydrogen bond vectors, resulting in a mean dihedral angle of 84.33 (6)° with the equatorial plane. Compounds (I) and (II) appear to be rare examples of clean S(6)S(6) interligand hydrogen bonding in transition metal complexes. Among the few monodentate pyO complexes reported only [Pt(NH3)2(pyO)Cl3] has S(6) intramolecular hydrogen bonding confirmed crystallographically, but this interaction is considered secondary to intermolecular hydrogen bonding to donors in adjacent molecules (Hollis & Lippard, 1983). Intramolecular hydrogen bonds are also implied by short N—O distances within trans-[(CH3NH2)2Pt(pyO)(pyOH)](NO3), but the protons were not located and the structure is dominated by intermolecular hydrogen bonding between ambiguously averaged pyO and pyOH ligands (Schreiber, et al., 1994). Interligand S(6) hydrogen bonding has also been reported in a tetraacetate ruthenium(III) dimer where capping 7-azaindole ligands interact through N—H bonds with proximal acetate O atoms (Bland et al., 2005). Again, these intramolecular interactions are considered secondary to intermolecular hydrogen bonds to PF6- counter-ions.

Though bond distances and angles are experimentally indistinguishable between the structure of complex (II) and that reported for complex (I), the two compounds exhibit significant differences in the orientations of the pyO and MeOpyO rings. The MeOpyO ligands of complex (II) are rotated by a mean angle of 39.6 (2)° away from the pseudo-plane bisecting the terpy ligand, as compared with the slightly smaller mean angle of 35.1 (2)° for the pyO ligands of complex (I). The MeOpyO ligands of complex (II) were also tipped slightly further from perpendicularity with the equatorial plane than the pyO ligands of complex (I) [84.33 (6) versus 85.41 (5)°, respectively]. The ligand conformation differences may reflect a stronger S(6)S(6) interaction in complex (II) owing to greater basicity of the MeOpyO versus pyO ligands. The ligand conformations may also have electronic consequences on the complex. The larger rotation angle for the MeOpyO ligand could subtly shift ligand–metal π-interactions from one coordinate axis toward the other, and the larger tip in the MeOpyO plane could encourage stronger orbital overlap between the ligand π-system and ruthenium center. An ab-initio investigation is underway to confirm the electronic significance of the ligand conformations and their importance to the catalytic reaction.

Related literature top

For related literature, see: Bland et al. (2005); Fan et al. (2002); Grover et al. (1992); Hecker et al. (1991); Hollis & Lippard (1983); Kelson & Phengsy (2000); Naota et al. (1998); Noyori & Hashiguchi (1997); Rasmussen et al. (1995); Schreiber et al. (1994); Zassinovich et al. (1992).

Experimental top

The title compound was prepared by refluxing RuIII(terpy)Cl3 (0.10 g) with 3-methoxy-2-pyridinol (0.13 g) in a mixture of ethanol (38 ml) and 0.30 M aqueous sodium hydroxide (19 ml) for 1 h followed by crystallization upon rotoevaporation to 6 ml volume. The 1H NMR spectrum of the product at 400 MHz in acetone-d6 was consistent with the title formulation with the following signals in p.p.m. (integration, multiplicity): 9.34 (2H, d, 5.6 Hz), 8.50 (2H, d, 8.4 Hz), 8.44 (2H, d, 8.0 Hz), 7.90 (2H, m), 7.80 (1H, t, 8.0 Hz), 7.64 (2H, t, 6.0 Hz), 6.32 (2H, dd, 7.2, 1.6 Hz), 5.42 (2H, m), 5.36 (2H, m), 3.47 (6H, s). Addition of hexane to an acetonitrile solution of the product afforded black irregular crystals of the title compound that grew over several days at room temperature.

Refinement top

The H atoms bound to carbon were positioned with idealized geometry (Csp2—H 0.93 Å, Csp3—H 0.96 Å), and assigned isotropic displacement parameters equal to 1.2 Ueq or 1.5 Ueq of the sp2 or sp3 parent carbon atoms, respectively. Hydrogen atoms on the aqua ligand and lattice water molecule were found in difference Fourier synthesis and were first refined without restraints and resulted in a large electron density peak (approximately 2.60 e Å-3) 0.88 Å from the lattice water oxygen. The lattice water was remodeled as disordered between two orientations where the hydrogen atoms for the new position were initially located by Fourier synthesis. To obtain satisfactory behavior for the two disordered lattice water positions, the O—H bond lengths were fixed at 0.83 (2) Å, 1,3 H—H distances fixed at 1.31 (4) Å, isotropic oxygen displacement parameters were allowed to refine, and isotropic hydrogen displacement parameters were assigned equal to 1.5 Ueq of the correspondingly oxygen. The model converged to a 71 (2)/29 (2)% occupation of the two orientations with a large residual electron density peak (approximately 1.33 e Å-3) 0.08 Å from a lattice water hydrogen. The lattice water was remodeled as disordered between the two existing orientations and a third oxygen positioned on the large residual electron density peak. Attempts to refine the isotropic displacement parameter on the third lattice water oxygen and locate its H atoms were unsuccessful. The isotropic displacement parameters for the three lattice water O atoms were refined as a single variable, and the model converged to a 44.7 (12)/38.2 (11)/17.1 (6)% occupation of the three orientations. The final difference map was relatively flat with its residual maximum of 1.88 e Å-3 and minimum -0.75 e Å-3 in the close proximity (0.71 and 0.65 Å, respectively) from Ru1.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 and WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. ORTEP diagram of the ruthenium complex of (II), drawn with 50% probability displacement ellipsoids. Solvent molecules are not shown. The hydrogen bonds are depicted with dashed lines.
Aquabis(3-methoxy-2-pyridonato)(2,2':6',2''- terpyridine)ruthenium(II)–acetonitrile–water (1/1/1) top
Crystal data top
[Ru(C6H6NO2)2(C15H11N3)(H2O)]·C2H3N·H2OF(000) = 1352
Mr = 659.66Dx = 1.514 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2855 reflections
a = 9.5695 (10) Åθ = 2.1–20.7°
b = 13.8950 (16) ŵ = 0.60 mm1
c = 22.229 (3) ÅT = 100 K
β = 101.720 (9)°Irregular, black
V = 2894.1 (6) Å30.4 × 0.2 × 0.1 mm
Z = 4
Data collection top
Oxford Diffraction Sapphire 3CCD
diffractometer
8112 independent reflections
Radiation source: fine-focus sealed tube7939 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.036
ϕ and ω scansθmax = 30°, θmin = 3.9°
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2006)
h = 1313
Tmin = 0.863, Tmax = 0.944k = 1919
55112 measured reflectionsl = 3131
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.057Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.115H atoms treated by a mixture of independent and constrained refinement
S = 1.09 w = 1/[σ2(Fo2) + (0.0261P)2 + 10.7726P]
where P = (Fo2 + 2Fc2)/3
8112 reflections(Δ/σ)max = 0.001
406 parametersΔρmax = 1.88 e Å3
9 restraintsΔρmin = 0.75 e Å3
Crystal data top
[Ru(C6H6NO2)2(C15H11N3)(H2O)]·C2H3N·H2OV = 2894.1 (6) Å3
Mr = 659.66Z = 4
Monoclinic, P21/cMo Kα radiation
a = 9.5695 (10) ŵ = 0.60 mm1
b = 13.8950 (16) ÅT = 100 K
c = 22.229 (3) Å0.4 × 0.2 × 0.1 mm
β = 101.720 (9)°
Data collection top
Oxford Diffraction Sapphire 3CCD
diffractometer
8112 independent reflections
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2006)
7939 reflections with I > 2σ(I)
Tmin = 0.863, Tmax = 0.944Rint = 0.036
55112 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0579 restraints
wR(F2) = 0.115H atoms treated by a mixture of independent and constrained refinement
S = 1.09 w = 1/[σ2(Fo2) + (0.0261P)2 + 10.7726P]
where P = (Fo2 + 2Fc2)/3
8112 reflectionsΔρmax = 1.88 e Å3
406 parametersΔρmin = 0.75 e Å3
Special details top

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 matrix. 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; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimated e.s.d.'s involving l.s. planes.

Mean-plane data from final SHELXL refinement run:-

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

2.8206 (0.0073) x + 0.0489 (0.0112) y + 19.4673 (0.0091) z = 17.6296 (0.0101)

* -0.0144 (0.0009) Ru1 * -0.0025 (0.0012) N1 * 0.0110 (0.0014) N2 * -0.0031 (0.0012) N3 * 0.0090 (0.0009) O1

Rms deviation of fitted atoms = 0.0092

2.7037 (0.0036) x - 0.0136 (0.0050) y + 19.6028 (0.0051) z = 17.6707 (0.0061)

Angle to previous plane (with approximate e.s.d.) = 0.78 (0.07)

* -0.0900 (0.0023) N1 * -0.1311 (0.0027) C1 * -0.0269 (0.0028) C2 * 0.1488 (0.0029) C3 * 0.1638 (0.0029) C4 * 0.0240 (0.0027) C5 * -0.0417 (0.0023) N2 * -0.0059 (0.0027) C6 * -0.0269 (0.0027) C7 * -0.0581 (0.0027) C8 * -0.0526 (0.0028) C9 * -0.0374 (0.0028) C10 * -0.0429 (0.0023) N3 * -0.0132 (0.0027) C11 * 0.0521 (0.0028) C12 * 0.0936 (0.0028) C13 * 0.0557 (0.0026) C14 * -0.0112 (0.0026) C15

Rms deviation of fitted atoms = 0.0754

0.2857 (0.0081) x + 13.8000 (0.0027) y - 2.5912 (0.0221) z = 9.6795 (0.0223)

Angle to previous plane (with approximate e.s.d.) = 84.22 (0.06)

* 0.0288 (0.0022) N4 * 0.0070 (0.0026) C16 * 0.0091 (0.0029) C17 * -0.0092 (0.0030) C18 * -0.0200 (0.0029) C19 * 0.0027 (0.0026) C20 * -0.0346 (0.0020) O2 * 0.0163 (0.0021) O3

Rms deviation of fitted atoms = 0.0191

1.7324 (0.0076) x + 13.6495 (0.0031) y + 0.2139 (0.0198) z = 12.7794 (0.0125)

Angle to previous plane (with approximate e.s.d.) = 12.66 (0.04)

* 0.0406 (0.0020) N5 * 0.0133 (0.0026) C22 * 0.0131 (0.0028) C23 * -0.0169 (0.0025) C24 * -0.0288 (0.0025) C25 * 0.0057 (0.0023) C26 * -0.0530 (0.0019) O4 * 0.0260 (0.0020) O5

Rms deviation of fitted atoms = 0.0288

2.7037 (0.0036) x - 0.0136 (0.0050) y + 19.6028 (0.0051) z = 17.6707 (0.0061)

Angle to previous plane (with approximate e.s.d.) = 84.51 (0.06)

* -0.0900 (0.0023) N1 * -0.1311 (0.0027) C1 * -0.0269 (0.0028) C2 * 0.1488 (0.0029) C3 * 0.1638 (0.0029) C4 * 0.0240 (0.0027) C5 * -0.0417 (0.0023) N2 * -0.0059 (0.0027) C6 * -0.0269 (0.0027) C7 * -0.0581 (0.0027) C8 * -0.0526 (0.0028) C9 * -0.0374 (0.0028) C10 * -0.0429 (0.0023) N3 * -0.0132 (0.0027) C11 * 0.0521 (0.0028) C12 * 0.0936 (0.0028) C13 * 0.0557 (0.0026) C14 * -0.0112 (0.0026) C15

Rms deviation of fitted atoms = 0.0754

0.2857 (0.0081) x + 13.8000 (0.0027) y - 2.5912 (0.0221) z = 9.6795 (0.0223)

Angle to previous plane (with approximate e.s.d.) = 84.22 (0.06)

* 0.0288 (0.0022) N4 * 0.0070 (0.0026) C16 * 0.0091 (0.0029) C17 * -0.0092 (0.0030) C18 * -0.0200 (0.0029) C19 * 0.0027 (0.0026) C20 * -0.0346 (0.0020) O2 * 0.0163 (0.0021) O3

Rms deviation of fitted atoms = 0.0191

2.8206 (0.0073) x + 0.0489 (0.0112) y + 19.4673 (0.0091) z = 17.6296 (0.0101)

Angle to previous plane (with approximate e.s.d.) = 84.52 (0.08)

* -0.0144 (0.0009) Ru1 * -0.0025 (0.0012) N1 * 0.0110 (0.0014) N2 * -0.0031 (0.0012) N3 * 0.0090 (0.0009) O1

Rms deviation of fitted atoms = 0.0092

1.7324 (0.0076) x + 13.6495 (0.0031) y + 0.2139 (0.0198) z = 12.7794 (0.0125)

Angle to previous plane (with approximate e.s.d.) = 84.14 (0.07)

* 0.0406 (0.0020) N5 * 0.0133 (0.0026) C22 * 0.0131 (0.0028) C23 * -0.0169 (0.0025) C24 * -0.0288 (0.0025) C25 * 0.0057 (0.0023) C26 * -0.0530 (0.0019) O4 * 0.0260 (0.0020) O5

Rms deviation of fitted atoms = 0.0288

Refinement. All of the non-hydrogen atoms, except for the oxygen atom for the disordered lattice water, were refined with anisotropic displacement coefficients. Hydrogen atoms on the aqua ligand and lattice water molecule were initially located by difference map and refined isotropically. All other hydrogen atoms were assigned isotropic displacement coefficients U(H) = 1.2U(C) or 1.5U(Cmethyl), and their coordinates were allowed to ride on their respective carbons using SHELXL97. Refinement of this early model resulted a large electron density peak (approximately 2.60 e Å-3) 0.88 Å from the lattice water oxygen. The lattice water was remodeled as disordered between two orientations where the hydrogen atoms for the new position were initially located by Fourier synthesis. To obtain satisfactory behavior for the two disordered lattice water positions, the O—H bond lengths were fixed at 0.83 (2) Å, 1,3 H—H distances fixed at 1.31 (4) Å, isotropic oxygen displacement parameters were allowed to refine, and isotropic hydrogen displacement parameters were assigned equal to 1.5 Ueq of the corresponding oxygen. The model converged to a 71 (2)/29 (2)% occupation of the two orientations with a large residual electron density peak (approximately 1.33 e Å-3) 0.08 Å from a lattice water hydrogen. The lattice water was remodeled as disordered between the two existing orientations and a third oxygen positioned on the large residual electron density peak. Attempts to refine the isotropic displacement parameter on the third lattice water oxygen and locate its H atoms were unsuccessful. The isotropic displacement parameters for the three lattice water O atoms were refined as a single variable, and the model converged to a 44.7 (12)/38.2 (11)/17.1 (6)% occupation of the three orientations. The final difference map was relatively flat with its residual maximum of 1.88 e Å-3 and minimum -0.75 e Å-3 in the close proximity (0.71 and 0.65 Å, respectively) from Ru1. F2 was refined against ALL reflections. The weighted R-factor wR and goodness of fit S were based on F2, and conventional R-factors R were based on F, with F set to zero for negative F2 values. The threshold expression of F2 > σ(F2) was used only for calculating R-factors(gt) etc. and was not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as 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) top
xyzUiso*/UeqOcc. (<1)
Ru10.68439 (2)0.854477 (17)0.803548 (10)0.01668 (7)
O10.8306 (2)0.74579 (16)0.78384 (10)0.0219 (4)
H1A0.907 (3)0.764 (4)0.806 (2)0.056 (16)*
H1B0.834 (5)0.761 (4)0.7480 (12)0.057 (15)*
O21.0154 (2)0.83963 (19)0.86140 (10)0.0268 (5)
O31.1737 (2)0.86060 (19)0.97088 (10)0.0295 (5)
O40.7930 (2)0.82110 (19)0.67716 (10)0.0283 (5)
O50.6797 (3)0.8431 (2)0.56049 (11)0.0338 (6)
N10.7860 (3)0.98258 (18)0.78912 (11)0.0197 (5)
N20.5489 (3)0.94547 (17)0.82426 (11)0.0170 (4)
N30.5389 (2)0.76007 (17)0.82545 (11)0.0164 (4)
N40.8036 (3)0.85497 (18)0.89526 (11)0.0172 (4)
N50.5823 (3)0.85421 (17)0.70897 (11)0.0167 (4)
C10.9080 (3)0.9967 (2)0.77021 (14)0.0219 (6)
H10.95530.94370.75840.026*
C20.9672 (4)1.0877 (2)0.76742 (15)0.0253 (6)
H21.05171.09510.75330.03*
C30.8989 (4)1.1671 (2)0.78585 (15)0.0271 (7)
H30.93881.22810.78580.032*
C40.7706 (3)1.1541 (2)0.80431 (14)0.0238 (6)
H40.72241.20660.81620.029*
C50.7138 (3)1.0614 (2)0.80495 (13)0.0192 (5)
C60.5755 (3)1.0408 (2)0.82248 (13)0.0195 (5)
C70.4762 (3)1.1071 (2)0.83516 (13)0.0220 (6)
H70.49321.17280.83320.026*
C80.3513 (3)1.0738 (2)0.85076 (14)0.0241 (6)
H80.28381.11750.85880.029*
C90.3264 (3)0.9746 (2)0.85441 (14)0.0222 (6)
H90.24380.95180.86550.027*
C100.4287 (3)0.9111 (2)0.84104 (13)0.0179 (5)
C110.4247 (3)0.8048 (2)0.84274 (13)0.0172 (5)
C120.3167 (3)0.7516 (2)0.86093 (14)0.0211 (6)
H120.240.78260.87230.025*
C130.3254 (3)0.6521 (2)0.86178 (14)0.0243 (6)
H130.25480.61570.87420.029*
C140.4393 (4)0.6071 (2)0.84411 (14)0.0246 (6)
H140.44550.54030.84420.029*
C150.5442 (3)0.6626 (2)0.82627 (13)0.0204 (6)
H150.62080.63190.81450.024*
C160.9496 (3)0.8523 (2)0.90556 (13)0.0198 (5)
C171.0293 (3)0.8625 (2)0.96770 (14)0.0239 (6)
C180.9619 (4)0.8716 (3)1.01597 (15)0.0313 (7)
H181.01370.87771.0560.038*
C190.8113 (4)0.8716 (3)1.00338 (15)0.0325 (8)
H190.76210.87691.03530.039*
C200.7385 (4)0.8636 (2)0.94423 (14)0.0246 (6)
H200.63930.86410.93680.03*
C211.2618 (4)0.8666 (3)1.03122 (16)0.0368 (8)
H21A1.24060.92491.05070.055*
H21B1.36040.86651.02820.055*
H21C1.24330.81231.05520.055*
C220.6600 (3)0.8430 (2)0.66391 (13)0.0213 (6)
C230.5886 (4)0.8531 (2)0.60037 (13)0.0237 (6)
C240.4456 (4)0.8693 (2)0.58470 (14)0.0258 (6)
H240.40010.87480.54370.031*
C250.3682 (4)0.8775 (2)0.63204 (15)0.0265 (6)
H250.27010.88780.62280.032*
C260.4396 (3)0.8700 (2)0.69167 (15)0.0221 (6)
H260.38720.87620.72240.026*
C270.6188 (5)0.8566 (3)0.49665 (16)0.0419 (9)
H27A0.54260.81140.48410.063*
H27B0.69080.84660.47290.063*
H27C0.58220.92090.49020.063*
N1S1.1202 (7)0.6086 (5)0.9957 (3)0.100 (2)
C1S1.0325 (6)0.5973 (4)0.9538 (2)0.0565 (12)
C2S0.9285 (7)0.5868 (5)0.9004 (3)0.0691 (16)
H2SA0.91590.64690.87860.104*
H2SB0.83990.56810.9110.104*
H2SC0.95780.53830.87480.104*
O1WA1.0185 (7)0.8383 (7)0.6162 (3)0.0286 (10)*0.447 (12)
H1WA1.036 (13)0.872 (6)0.647 (3)0.043*0.447 (12)
H2WA1.004 (11)0.783 (3)0.625 (4)0.043*0.447 (12)
O1WB1.0160 (9)0.8718 (8)0.6260 (4)0.0286 (10)*0.382 (11)
H1WB1.002 (11)0.929 (2)0.633 (5)0.043*0.382 (11)
H2WB0.952 (9)0.843 (7)0.639 (6)0.043*0.382 (11)
O2WC0.9583 (18)0.8538 (11)0.5918 (7)0.0286 (10)*0.171 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ru10.01503 (12)0.01798 (11)0.01807 (11)0.00066 (8)0.00578 (8)0.00032 (8)
O10.0208 (11)0.0243 (11)0.0209 (10)0.0051 (8)0.0048 (9)0.0017 (8)
O20.0184 (11)0.0440 (14)0.0193 (10)0.0036 (9)0.0068 (8)0.0017 (9)
O30.0202 (12)0.0440 (14)0.0221 (10)0.0015 (10)0.0010 (9)0.0014 (10)
O40.0230 (12)0.0401 (13)0.0231 (10)0.0050 (10)0.0074 (9)0.0002 (10)
O50.0373 (14)0.0464 (15)0.0196 (10)0.0059 (12)0.0102 (10)0.0010 (10)
N10.0196 (12)0.0225 (12)0.0163 (10)0.0016 (9)0.0019 (9)0.0010 (9)
N20.0168 (12)0.0180 (11)0.0169 (10)0.0005 (9)0.0052 (9)0.0001 (8)
N30.0134 (11)0.0195 (11)0.0166 (10)0.0031 (8)0.0034 (8)0.0002 (8)
N40.0167 (11)0.0185 (10)0.0172 (10)0.0006 (9)0.0051 (9)0.0000 (9)
N50.0162 (11)0.0159 (10)0.0178 (10)0.0017 (9)0.0030 (9)0.0010 (8)
C10.0192 (14)0.0250 (14)0.0224 (13)0.0019 (11)0.0061 (11)0.0001 (11)
C20.0245 (16)0.0254 (15)0.0269 (14)0.0059 (12)0.0071 (12)0.0038 (12)
C30.0300 (17)0.0238 (15)0.0279 (15)0.0087 (12)0.0073 (13)0.0002 (12)
C40.0254 (16)0.0213 (14)0.0257 (14)0.0013 (12)0.0078 (12)0.0017 (11)
C50.0232 (15)0.0186 (12)0.0164 (12)0.0001 (11)0.0055 (11)0.0015 (10)
C60.0206 (14)0.0220 (13)0.0162 (12)0.0007 (11)0.0043 (10)0.0011 (10)
C70.0275 (16)0.0176 (12)0.0208 (13)0.0015 (11)0.0049 (12)0.0002 (10)
C80.0271 (16)0.0211 (14)0.0253 (14)0.0091 (12)0.0081 (12)0.0005 (11)
C90.0194 (14)0.0243 (14)0.0243 (14)0.0028 (11)0.0077 (11)0.0002 (11)
C100.0150 (13)0.0201 (13)0.0194 (12)0.0001 (10)0.0056 (10)0.0003 (10)
C110.0143 (13)0.0195 (12)0.0174 (12)0.0004 (10)0.0023 (10)0.0005 (10)
C120.0158 (14)0.0254 (14)0.0228 (13)0.0012 (11)0.0057 (11)0.0003 (11)
C130.0236 (15)0.0254 (15)0.0243 (14)0.0085 (12)0.0058 (12)0.0012 (11)
C140.0300 (17)0.0193 (13)0.0228 (14)0.0027 (12)0.0016 (12)0.0004 (11)
C150.0236 (15)0.0182 (13)0.0189 (12)0.0041 (10)0.0032 (11)0.0000 (10)
C160.0188 (14)0.0220 (13)0.0183 (12)0.0004 (11)0.0031 (10)0.0022 (10)
C170.0220 (15)0.0284 (15)0.0196 (13)0.0008 (12)0.0003 (11)0.0013 (11)
C180.0329 (19)0.043 (2)0.0165 (13)0.0030 (15)0.0018 (12)0.0005 (13)
C190.0323 (19)0.048 (2)0.0192 (14)0.0048 (15)0.0102 (13)0.0016 (13)
C200.0239 (15)0.0320 (16)0.0204 (13)0.0022 (12)0.0103 (12)0.0024 (12)
C210.0303 (19)0.048 (2)0.0262 (16)0.0020 (16)0.0074 (14)0.0008 (15)
C220.0231 (15)0.0220 (14)0.0191 (12)0.0015 (11)0.0053 (11)0.0007 (10)
C230.0299 (16)0.0225 (14)0.0188 (12)0.0011 (12)0.0050 (11)0.0021 (11)
C240.0295 (17)0.0239 (15)0.0208 (13)0.0016 (12)0.0024 (12)0.0001 (11)
C250.0207 (16)0.0267 (15)0.0302 (16)0.0007 (12)0.0004 (12)0.0000 (12)
C260.0193 (15)0.0196 (13)0.0275 (14)0.0007 (10)0.0054 (12)0.0010 (11)
C270.060 (3)0.046 (2)0.0200 (15)0.013 (2)0.0080 (16)0.0018 (15)
N1S0.092 (4)0.124 (6)0.072 (4)0.029 (4)0.011 (3)0.010 (4)
C1S0.052 (3)0.069 (3)0.048 (3)0.016 (2)0.006 (2)0.001 (2)
C2S0.079 (4)0.067 (4)0.055 (3)0.002 (3)0.000 (3)0.012 (3)
Geometric parameters (Å, º) top
Ru1—O12.163 (2)C9—H90.93
Ru1—N12.084 (3)C10—C111.479 (4)
Ru1—N21.933 (2)C11—C121.395 (4)
Ru1—N32.043 (2)C12—C131.385 (4)
Ru1—N42.124 (2)C12—H120.93
Ru1—N52.131 (2)C13—C141.381 (5)
O1—H1A0.837 (19)C13—H130.93
O1—H1B0.831 (19)C14—C151.386 (4)
O2—C161.281 (3)C14—H140.93
O3—C171.370 (4)C15—H150.93
O3—C211.434 (4)C16—C171.443 (4)
O4—C221.283 (4)C17—C181.366 (4)
O5—C231.371 (4)C18—C191.411 (5)
O5—C271.433 (4)C18—H180.93
N1—C11.333 (4)C19—C201.362 (5)
N1—C51.378 (4)C19—H190.93
N2—C61.350 (4)C20—H200.93
N2—C101.365 (3)C21—H21A0.96
N3—C151.356 (4)C21—H21B0.96
N3—C111.377 (3)C21—H21C0.96
N4—C161.370 (4)C22—C231.445 (4)
N4—C201.365 (3)C23—C241.360 (5)
N5—C221.372 (4)C24—C251.410 (5)
N5—C261.360 (4)C24—H240.93
C1—C21.392 (4)C25—C261.366 (4)
C1—H10.93C25—H250.93
C2—C31.386 (5)C26—H260.93
C2—H20.93C27—H27A0.96
C3—C41.383 (4)C27—H27B0.96
C3—H30.93C27—H27C0.96
C4—C51.399 (4)N1S—C1S1.132 (7)
C4—H40.93C1S—C2S1.392 (7)
C5—C61.482 (4)C2S—H2SA0.96
C6—C71.393 (4)C2S—H2SB0.96
C7—C81.389 (4)C2S—H2SC0.96
C7—H70.93O1WA—H1WA0.83 (2)
C8—C91.404 (4)O1WA—H2WA0.81 (2)
C8—H80.93O1WB—H1WB0.82 (2)
C9—C101.394 (4)O1WB—H2WB0.84 (2)
N1—Ru1—N280.47 (10)N3—C11—C10114.7 (2)
N2—Ru1—N380.81 (10)C12—C11—C10124.1 (3)
N1—Ru1—N3161.28 (10)C13—C12—C11119.1 (3)
N2—Ru1—N491.42 (10)C13—C12—H12120.4
N3—Ru1—N491.86 (9)C11—C12—H12120.4
N1—Ru1—N488.20 (9)C14—C13—C12119.8 (3)
N2—Ru1—N592.34 (10)C14—C13—H13120.1
N3—Ru1—N592.06 (9)C12—C13—H13120.1
N1—Ru1—N589.11 (9)C13—C14—C15119.3 (3)
N4—Ru1—N5174.95 (9)C13—C14—H14120.3
N2—Ru1—O1176.31 (9)C15—C14—H14120.3
N3—Ru1—O195.76 (9)N3—C15—C14122.1 (3)
N1—Ru1—O1102.94 (10)N3—C15—H15118.9
N4—Ru1—O187.32 (9)C14—C15—H15118.9
N5—Ru1—O189.13 (9)O2—C16—N4121.2 (3)
Ru1—O1—H1A101 (4)O2—C16—C17120.1 (3)
Ru1—O1—H1B100 (4)N4—C16—C17118.7 (3)
H1A—O1—H1B107 (5)C18—C17—O3126.4 (3)
C17—O3—C21116.3 (3)C18—C17—C16121.3 (3)
C23—O5—C27116.3 (3)O3—C17—C16112.3 (3)
C1—N1—C5118.7 (3)C17—C18—C19118.1 (3)
C1—N1—Ru1129.8 (2)C17—C18—H18121
C5—N1—Ru1111.48 (19)C19—C18—H18121
C6—N2—C10121.7 (2)C20—C19—C18119.5 (3)
C6—N2—Ru1119.66 (19)C20—C19—H19120.2
C10—N2—Ru1118.65 (19)C18—C19—H19120.2
C15—N3—C11118.5 (2)C19—C20—N4123.4 (3)
C15—N3—Ru1128.3 (2)C19—C20—H20118.3
C11—N3—Ru1113.25 (19)N4—C20—H20118.3
C20—N4—C16119.0 (3)O3—C21—H21A109.5
C20—N4—Ru1121.5 (2)O3—C21—H21B109.5
C16—N4—Ru1119.41 (18)H21A—C21—H21B109.5
C26—N5—C22118.3 (3)O3—C21—H21C109.5
C26—N5—Ru1120.78 (19)H21A—C21—H21C109.5
C22—N5—Ru1120.8 (2)H21B—C21—H21C109.5
N1—C1—C2122.6 (3)O4—C22—N5121.2 (3)
N1—C1—H1118.7O4—C22—C23119.8 (3)
C2—C1—H1118.7N5—C22—C23118.9 (3)
C3—C2—C1119.3 (3)C24—C23—O5126.1 (3)
C3—C2—H2120.4C24—C23—C22121.2 (3)
C1—C2—H2120.4O5—C23—C22112.7 (3)
C4—C3—C2118.9 (3)C23—C24—C25118.4 (3)
C4—C3—H3120.5C23—C24—H24120.8
C2—C3—H3120.5C25—C24—H24120.8
C3—C4—C5119.5 (3)C26—C25—C24118.9 (3)
C3—C4—H4120.2C26—C25—H25120.6
C5—C4—H4120.2C24—C25—H25120.6
N1—C5—C4120.9 (3)N5—C26—C25124.2 (3)
N1—C5—C6115.7 (3)N5—C26—H26117.9
C4—C5—C6123.4 (3)C25—C26—H26117.9
N2—C6—C7120.1 (3)O5—C27—H27A109.5
N2—C6—C5112.4 (3)O5—C27—H27B109.5
C7—C6—C5127.4 (3)H27A—C27—H27B109.5
C8—C7—C6119.2 (3)O5—C27—H27C109.5
C8—C7—H7120.4H27A—C27—H27C109.5
C6—C7—H7120.4H27B—C27—H27C109.5
C7—C8—C9120.4 (3)N1S—C1S—C2S176.9 (7)
C7—C8—H8119.8C1S—C2S—H2SA109.5
C9—C8—H8119.8C1S—C2S—H2SB109.5
C10—C9—C8118.3 (3)H2SA—C2S—H2SB109.5
C10—C9—H9120.8C1S—C2S—H2SC109.5
C8—C9—H9120.8H2SA—C2S—H2SC109.5
N2—C10—C9120.2 (3)H2SB—C2S—H2SC109.5
N2—C10—C11112.6 (2)H1WA—O1WA—H2WA111 (5)
C9—C10—C11127.2 (3)H1WB—O1WB—H2WB104 (5)
N3—C11—C12121.2 (3)
N2—Ru1—N1—C1179.1 (3)C4—C5—C6—N2175.1 (3)
N3—Ru1—N1—C1179.6 (3)N1—C5—C6—C7174.0 (3)
N4—Ru1—N1—C189.1 (3)C4—C5—C6—C76.3 (5)
N5—Ru1—N1—C186.6 (3)N2—C6—C7—C81.3 (4)
O1—Ru1—N1—C12.3 (3)C5—C6—C7—C8179.8 (3)
N2—Ru1—N1—C54.01 (19)C6—C7—C8—C90.7 (5)
N3—Ru1—N1—C52.8 (4)C7—C8—C9—C101.0 (5)
N4—Ru1—N1—C587.7 (2)C6—N2—C10—C92.7 (4)
N5—Ru1—N1—C596.5 (2)Ru1—N2—C10—C9178.0 (2)
O1—Ru1—N1—C5174.57 (19)C6—N2—C10—C11177.2 (3)
N3—Ru1—N2—C6178.0 (2)Ru1—N2—C10—C112.1 (3)
N1—Ru1—N2—C61.6 (2)C8—C9—C10—N20.7 (4)
N4—Ru1—N2—C686.4 (2)C8—C9—C10—C11179.2 (3)
N5—Ru1—N2—C690.3 (2)C15—N3—C11—C120.2 (4)
N3—Ru1—N2—C101.3 (2)Ru1—N3—C11—C12178.2 (2)
N1—Ru1—N2—C10179.1 (2)C15—N3—C11—C10179.4 (3)
N4—Ru1—N2—C1092.9 (2)Ru1—N3—C11—C101.0 (3)
N5—Ru1—N2—C1090.4 (2)N2—C10—C11—N32.0 (4)
N2—Ru1—N3—C15178.1 (3)C9—C10—C11—N3178.1 (3)
N1—Ru1—N3—C15176.9 (3)N2—C10—C11—C12177.2 (3)
N4—Ru1—N3—C1587.0 (3)C9—C10—C11—C122.7 (5)
N5—Ru1—N3—C1589.8 (3)N3—C11—C12—C130.3 (4)
O1—Ru1—N3—C150.5 (3)C10—C11—C12—C13178.8 (3)
N2—Ru1—N3—C110.09 (19)C11—C12—C13—C140.7 (5)
N1—Ru1—N3—C111.3 (4)C12—C13—C14—C150.6 (5)
N4—Ru1—N3—C1191.23 (19)C11—N3—C15—C140.3 (4)
N5—Ru1—N3—C1191.95 (19)Ru1—N3—C15—C14177.9 (2)
O1—Ru1—N3—C11178.72 (19)C13—C14—C15—N30.1 (5)
N2—Ru1—N4—C2035.1 (2)C20—N4—C16—O2176.6 (3)
N3—Ru1—N4—C2045.8 (2)Ru1—N4—C16—O27.2 (4)
N1—Ru1—N4—C20115.5 (2)C20—N4—C16—C172.4 (4)
O1—Ru1—N4—C20141.5 (2)Ru1—N4—C16—C17173.8 (2)
N2—Ru1—N4—C16141.0 (2)C21—O3—C17—C181.6 (5)
N3—Ru1—N4—C16138.1 (2)C21—O3—C17—C16177.7 (3)
N1—Ru1—N4—C1660.6 (2)O2—C16—C17—C18176.9 (3)
O1—Ru1—N4—C1642.5 (2)N4—C16—C17—C182.0 (5)
N2—Ru1—N5—C2630.0 (2)O2—C16—C17—O32.4 (4)
N3—Ru1—N5—C2650.9 (2)N4—C16—C17—O3178.6 (3)
N1—Ru1—N5—C26110.4 (2)O3—C17—C18—C19179.7 (3)
O1—Ru1—N5—C26146.6 (2)C16—C17—C18—C190.5 (5)
N2—Ru1—N5—C22146.6 (2)C17—C18—C19—C200.7 (6)
N3—Ru1—N5—C22132.5 (2)C18—C19—C20—N40.4 (6)
N1—Ru1—N5—C2266.2 (2)C16—N4—C20—C191.2 (5)
O1—Ru1—N5—C2236.8 (2)Ru1—N4—C20—C19174.9 (3)
C5—N1—C1—C21.8 (4)C26—N5—C22—O4174.9 (3)
Ru1—N1—C1—C2174.9 (2)Ru1—N5—C22—O48.4 (4)
N1—C1—C2—C31.1 (5)C26—N5—C22—C232.9 (4)
C1—C2—C3—C42.5 (5)Ru1—N5—C22—C23173.8 (2)
C2—C3—C4—C51.0 (5)C27—O5—C23—C243.8 (5)
C1—N1—C5—C43.3 (4)C27—O5—C23—C22177.1 (3)
Ru1—N1—C5—C4174.0 (2)O4—C22—C23—C24175.1 (3)
C1—N1—C5—C6177.0 (3)N5—C22—C23—C242.8 (5)
Ru1—N1—C5—C65.7 (3)O4—C22—C23—O54.0 (4)
C3—C4—C5—N11.9 (5)N5—C22—C23—O5178.1 (3)
C3—C4—C5—C6178.4 (3)O5—C23—C24—C25179.9 (3)
C10—N2—C6—C73.0 (4)C22—C23—C24—C250.9 (5)
Ru1—N2—C6—C7177.7 (2)C23—C24—C25—C260.7 (5)
C10—N2—C6—C5178.2 (2)C22—N5—C26—C251.3 (4)
Ru1—N2—C6—C51.1 (3)Ru1—N5—C26—C25175.3 (2)
N1—C5—C6—N24.7 (4)C24—C25—C26—N50.6 (5)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···O20.84 (2)1.78 (3)2.561 (3)155 (5)
O1—H1B···O40.83 (2)1.76 (3)2.550 (3)159 (5)

Experimental details

Crystal data
Chemical formula[Ru(C6H6NO2)2(C15H11N3)(H2O)]·C2H3N·H2O
Mr659.66
Crystal system, space groupMonoclinic, P21/c
Temperature (K)100
a, b, c (Å)9.5695 (10), 13.8950 (16), 22.229 (3)
β (°) 101.720 (9)
V3)2894.1 (6)
Z4
Radiation typeMo Kα
µ (mm1)0.60
Crystal size (mm)0.4 × 0.2 × 0.1
Data collection
DiffractometerOxford Diffraction Sapphire 3CCD
diffractometer
Absorption correctionMulti-scan
(CrysAlis RED; Oxford Diffraction, 2006)
Tmin, Tmax0.863, 0.944
No. of measured, independent and
observed [I > 2σ(I)] reflections
55112, 8112, 7939
Rint0.036
(sin θ/λ)max1)0.703
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.057, 0.115, 1.09
No. of reflections8112
No. of parameters406
No. of restraints9
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
w = 1/[σ2(Fo2) + (0.0261P)2 + 10.7726P]
where P = (Fo2 + 2Fc2)/3
Δρmax, Δρmin (e Å3)1.88, 0.75

Computer programs: CrysAlis CCD (Oxford Diffraction, 2006), CrysAlis CCD, CrysAlis RED (Oxford Diffraction, 2006), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), SHELXL97 and WinGX (Farrugia, 1999).

Selected geometric parameters (Å, º) top
Ru1—O12.163 (2)N4—C201.365 (3)
Ru1—N12.084 (3)N5—C221.372 (4)
Ru1—N21.933 (2)N5—C261.360 (4)
Ru1—N32.043 (2)C16—C171.443 (4)
Ru1—N42.124 (2)C17—C181.366 (4)
Ru1—N52.131 (2)C18—C191.411 (5)
O2—C161.281 (3)C19—C201.362 (5)
O3—C171.370 (4)C22—C231.445 (4)
O4—C221.283 (4)C23—C241.360 (5)
O5—C231.371 (4)C24—C251.410 (5)
N4—C161.370 (4)C25—C261.366 (4)
N1—Ru1—N280.47 (10)N2—Ru1—N380.81 (10)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···O20.837 (19)1.78 (3)2.561 (3)155 (5)
O1—H1B···O40.831 (19)1.76 (3)2.550 (3)159 (5)
 

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