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Acta Cryst. (2008). E64, m256    [ doi:10.1107/S1600536807066858 ]

([eta]6-Benzene)(2,2'-bipyridine-[kappa]2N,N')chloridoruthenium(II) chloride methanol sesquisolvate

M. I. J. Polson

Abstract top

In the title compound, [RuCl(C6H6)(C10H8N2)]Cl·1.5CH4O, the RuII atom is in a distorted octahedral environment coordinated by an [eta]6-benzene ring, a chelating 2,2'-bipyridine ligand and a chloride ion. The asymmetric unit is completed by a chloride anion and two methanol molecules, one of which is disordered about a centre of inversion with an occupancy of 0.5. It is an example of a ruthenium complex with a less sterically congested environment than in similar derivatives. In the crystal structure, O-H...Cl hydrogen bonds, together with [pi]-[pi] stacking interactions [centroid-centroid distances of 3.472Å(2) Å], stabilize the structure.

Comment top

The desire for a ruthenium complex which could be used to synthesize facially coordinated complexes led to the preparation of the starting material (1) (Freedman et al. 2001). It is convenient to use, in that the benzene ring can be readily removed in a photolytic reaction leaving ruthenium with three, vacant, facially arranged coordination sites. The RuII atom is in a distorted octahedral environment, Table 1, coordinating to an η6-benzene ring, a chelating 2,2'-bipyridine ligand and a chloride anion. Compared to other similar complexes from the literature, the cation is less bulky both around the benzene ring (Himeda et al., 2007) and in the bipyridine unit (Lalrempuia & Kollipara, 2003). This manifests itself in two angles. The angles between the mean plane of the bipyridine ligand and the mean plane of the benzene ring (60.47 (18)° in 1) become smaller as the ligands become larger due to additional substitution by methyl groups. This forces the two ligands become more parallel to each other. This effect is seen when either the bipyridine (32.24 ° Lalrempuia & Kollipara, 2003) or the benzene ring (36.04° Himeda et al. 2007) is larger due to additional substitution. With the smaller unsubstituted ligands of (1) the ruthenium atom is also more able to sit in the same plane as the bipyridine ligand, lying only 0.075 (1) Å above the plane in the direction of the choride ligand. The methanol solvate molecules form O—H···Cl hydrogen bonds to the chloride anion, Table 2, with D–H A distances of 3.013 (4) Å (O51–Cl2) and 2.986 (6) Å (O61–Cl2). The structure is further stabilized by offset π—π stacking interactions between adjacent N1, C7···C11 rings of the bipyridine ligands, with centroid to centroid distances of 3.472 (2) Å, related by the symmetry operation 1 - x, 1 - y, 1 - z, Fig. 2.

Related literature top

For literature concerning the synthesis of this class of compound, see Freedman et al. (2001). For related structures, see Himeda et al. (2007); Lalrempuia & Kollipara (2003).

Experimental top

The complex was prepared according to literature procedures (Freedman et al. 2001). X-ray quality crystals were grown by slow evaporation of a solution in methanol.

Refinement top

The C and O atoms of both methanol solvate molecules were refined isotropically. One of these molecules (C60, O60) is disordered about an inversion centre and was refined with the occupancy of all atoms fixed at 0.5. A l l H-atoms were positioned geometrically and refined using a riding model with d(C—H) = 0.93 Å, Uiso=1.2Ueq (C) for aromatic, 0.96 Å, Uiso = 1.5Ueq (C) for CH3 atoms and 0.82 Å, Uiso = 1.5Ueq (O) for the OH groups.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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) and Mercury (Bruno et al., 2002); software used to prepare material for publication: publCIF (Westrip, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of (1), showing displacement ellipsoids at the 50% probability level.
[Figure 2] Fig. 2. A packing diagram showing the π stacking. The close centroid-centroid approach is shown as a dashed line.
(η6-Benzene)(2,2'-bipyridine-κ2N,N')chloridoruthenium(II) chloride methanol sesquisolvate top
Crystal data top
[RuCl(C6H6)(C10H8N2)]Cl·1.5CH4OZ = 2
Mr = 454.33F000 = 458
Triclinic, P1Dx = 1.718 Mg m−3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71073 Å
a = 6.9027 (11) ÅCell parameters from 3474 reflections
b = 10.2346 (16) Åθ = 2.5–26.4º
c = 12.895 (2) ŵ = 1.21 mm−1
α = 85.597 (2)ºT = 93 (2) K
β = 84.531 (2)ºBlock, yellow
γ = 75.875 (2)º0.36 × 0.34 × 0.13 mm
V = 878.1 (2) Å3
Data collection top
Bruker APEXII CCD area-detector
diffractometer		3082 independent reflections
Radiation source: sealed tube2867 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.014
T = 93(2) Kθmax = 25.1º
φ and ω scansθmin = 2.5º
Absorption correction: multi-scan
(SADABS; Bruker, 2007)		h = −8→8
Tmin = 0.660, Tmax = 0.854k = −12→12
4385 measured reflectionsl = −15→10
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.033H-atom parameters constrained
wR(F2) = 0.086  w = 1/[σ2(Fo2) + (0.0562P)2 + 0.5007P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max < 0.001
3082 reflectionsΔρmax = 1.13 e Å−3
220 parametersΔρmin = −0.69 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[RuCl(C6H6)(C10H8N2)]Cl·1.5CH4Oγ = 75.875 (2)º
Mr = 454.33V = 878.1 (2) Å3
Triclinic, P1Z = 2
a = 6.9027 (11) ÅMo Kα
b = 10.2346 (16) ŵ = 1.21 mm−1
c = 12.895 (2) ÅT = 93 (2) K
α = 85.597 (2)º0.36 × 0.34 × 0.13 mm
β = 84.531 (2)º
Data collection top
Bruker APEXII CCD area-detector
diffractometer		3082 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2007)		2867 reflections with I > 2σ(I)
Tmin = 0.660, Tmax = 0.854Rint = 0.014
4385 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.033220 parameters
wR(F2) = 0.086H-atom parameters constrained
S = 1.06Δρmax = 1.13 e Å−3
3082 reflectionsΔρmin = −0.69 e Å−3
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 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, conventional 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 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)
Ru10.60854 (4)0.67682 (3)0.77268 (2)0.02474 (11)
Cl10.89451 (12)0.76724 (9)0.71514 (7)0.0277 (2)
Cl20.12633 (18)0.29047 (14)0.82005 (9)0.0536 (3)
N10.6736 (4)0.5821 (3)0.6319 (2)0.0217 (6)
N20.4510 (4)0.8207 (3)0.6686 (2)0.0244 (6)
C70.6008 (5)0.6559 (3)0.5465 (2)0.0201 (7)
C120.4677 (5)0.7878 (3)0.5677 (3)0.0217 (7)
C20.4713 (8)0.7559 (5)0.9230 (3)0.0530 (13)
H20.42720.85590.92890.064*
C10.3440 (7)0.6888 (5)0.8796 (3)0.0463 (11)
H10.21010.74070.85790.056*
C60.4177 (8)0.5533 (5)0.8541 (3)0.0499 (13)
H60.33750.50850.81400.060*
C30.6688 (8)0.6925 (6)0.9351 (3)0.0557 (14)
H30.76340.74780.94960.067*
C40.7456 (8)0.5604 (6)0.9086 (3)0.0515 (12)
H40.89390.52240.90470.062*
C50.6250 (8)0.4896 (5)0.8699 (3)0.0489 (12)
H50.68800.40120.83850.059*
C110.7918 (5)0.4575 (3)0.6204 (3)0.0234 (7)
H110.84300.40540.68030.028*
C80.6504 (5)0.6079 (3)0.4470 (2)0.0220 (7)
H80.60230.66280.38760.026*
C90.7708 (5)0.4794 (4)0.4354 (3)0.0232 (7)
H90.80480.44420.36820.028*
C100.8406 (5)0.4030 (4)0.5234 (3)0.0236 (7)
H100.92150.31400.51740.028*
C140.2393 (5)0.9964 (4)0.5210 (3)0.0307 (8)
H140.16551.05620.47080.037*
C130.3616 (5)0.8737 (4)0.4923 (3)0.0255 (7)
H130.37290.84850.42220.031*
C160.3322 (5)0.9412 (4)0.6948 (3)0.0307 (8)
H160.32160.96500.76520.037*
C150.2259 (5)1.0307 (4)0.6237 (3)0.0337 (9)
H150.14441.11500.64470.040*
O510.5683 (5)0.2257 (4)0.7539 (3)0.0553 (8)
H510.44590.23340.77160.083*
C500.6807 (7)0.1122 (5)0.8067 (4)0.0484 (11)
H50A0.59760.08370.86580.073*
H50B0.79730.13470.83220.073*
H50C0.72610.03880.75900.073*
O610.1958 (9)0.0351 (6)0.9544 (5)0.0413 (13)*0.50
H610.18720.10920.92010.062*0.50
C60−0.002 (4)0.035 (3)1.016 (2)0.135 (8)*0.50
H60A0.01490.03641.09090.202*0.50
H60B−0.0448−0.04591.00320.202*0.50
H60C−0.10280.11560.99500.202*0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ru10.02860 (18)0.03351 (18)0.01564 (16)−0.01396 (12)−0.00330 (11)−0.00015 (11)
Cl10.0235 (4)0.0287 (4)0.0335 (5)−0.0100 (3)−0.0057 (3)−0.0006 (3)
Cl20.0509 (7)0.0718 (8)0.0416 (6)−0.0182 (6)−0.0168 (5)0.0028 (5)
N10.0215 (14)0.0283 (15)0.0187 (13)−0.0131 (12)−0.0036 (11)0.0024 (11)
N20.0206 (14)0.0305 (16)0.0246 (15)−0.0109 (12)−0.0005 (11)−0.0024 (12)
C70.0175 (16)0.0258 (17)0.0203 (16)−0.0120 (13)−0.0044 (12)0.0032 (13)
C120.0176 (16)0.0281 (17)0.0231 (16)−0.0140 (14)−0.0012 (13)0.0022 (13)
C20.072 (3)0.064 (3)0.028 (2)−0.031 (3)0.017 (2)−0.015 (2)
C10.041 (2)0.076 (3)0.0229 (19)−0.021 (2)0.0037 (17)0.008 (2)
C60.073 (3)0.081 (3)0.0145 (18)−0.058 (3)−0.0018 (19)0.0070 (19)
C30.065 (3)0.099 (4)0.0178 (19)−0.046 (3)−0.0041 (19)−0.006 (2)
C40.054 (3)0.085 (4)0.0195 (19)−0.027 (3)−0.0085 (19)0.016 (2)
C50.074 (3)0.048 (3)0.022 (2)−0.020 (2)0.007 (2)0.0148 (18)
C110.0226 (17)0.0259 (17)0.0242 (17)−0.0112 (14)−0.0059 (13)0.0049 (13)
C80.0191 (16)0.0318 (18)0.0176 (16)−0.0122 (14)−0.0039 (12)0.0046 (13)
C90.0179 (16)0.0344 (19)0.0217 (16)−0.0140 (14)−0.0014 (13)−0.0033 (14)
C100.0167 (16)0.0267 (17)0.0298 (18)−0.0096 (14)−0.0039 (13)0.0007 (14)
C140.0183 (17)0.0299 (19)0.046 (2)−0.0122 (15)−0.0043 (15)0.0085 (16)
C130.0214 (17)0.0291 (18)0.0296 (18)−0.0138 (14)−0.0050 (14)0.0045 (14)
C160.0263 (19)0.036 (2)0.0326 (19)−0.0139 (16)0.0049 (15)−0.0091 (16)
C150.0213 (18)0.0283 (19)0.051 (2)−0.0086 (15)0.0045 (16)−0.0028 (17)
O510.063 (2)0.058 (2)0.0437 (18)−0.0138 (17)−0.0090 (16)0.0107 (15)
C500.048 (3)0.042 (2)0.054 (3)−0.010 (2)−0.012 (2)0.005 (2)
Geometric parameters (Å, °) top
Ru1—N12.083 (3)C4—H41.0000
Ru1—N22.084 (3)C5—H51.0000
Ru1—C12.165 (4)C11—C101.387 (5)
Ru1—C62.186 (4)C11—H110.9500
Ru1—C52.193 (4)C8—C91.385 (5)
Ru1—C22.198 (4)C8—H80.9500
Ru1—C42.198 (4)C9—C101.384 (5)
Ru1—C32.199 (4)C9—H90.9500
Ru1—Cl12.4105 (9)C10—H100.9500
N1—C111.346 (4)C14—C151.385 (6)
N1—C71.352 (4)C14—C131.386 (5)
N2—C161.351 (5)C14—H140.9500
N2—C121.356 (4)C13—H130.9500
C7—C81.392 (5)C16—C151.374 (6)
C7—C121.464 (5)C16—H160.9500
C12—C131.394 (5)C15—H150.9500
C2—C31.378 (8)O51—C501.398 (6)
C2—C11.417 (7)O51—H510.8400
C2—H21.0000C50—H50A0.9800
C1—C61.408 (7)C50—H50B0.9800
C1—H11.0000C50—H50C0.9800
C6—C51.447 (7)O61—C601.51 (3)
C6—H61.0000O61—H610.8400
C3—C41.383 (8)C60—H60A0.9800
C3—H31.0000C60—H60B0.9800
C4—C51.378 (7)C60—H60C0.9800
N1—Ru1—N277.18 (11)C1—C6—Ru170.3 (2)
N1—Ru1—C1127.42 (15)C5—C6—Ru170.9 (2)
N2—Ru1—C191.75 (15)C1—C6—H6120.4
N1—Ru1—C699.21 (14)C5—C6—H6120.4
N2—Ru1—C6111.47 (16)Ru1—C6—H6120.4
C1—Ru1—C637.76 (19)C2—C3—C4120.9 (5)
N1—Ru1—C594.95 (14)C2—C3—Ru171.7 (2)
N2—Ru1—C5148.17 (16)C4—C3—Ru171.6 (2)
C1—Ru1—C568.40 (19)C2—C3—H3119.0
C6—Ru1—C538.58 (19)C4—C3—H3119.0
N1—Ru1—C2165.29 (15)Ru1—C3—H3119.0
N2—Ru1—C2101.06 (17)C5—C4—C3120.4 (5)
C1—Ru1—C237.89 (18)C5—C4—Ru171.5 (2)
C6—Ru1—C267.59 (18)C3—C4—Ru171.7 (3)
C5—Ru1—C278.80 (19)C5—C4—H4119.3
N1—Ru1—C4116.02 (17)C3—C4—H4119.3
N2—Ru1—C4166.80 (17)Ru1—C4—H4119.3
C1—Ru1—C480.20 (18)C4—C5—C6120.4 (5)
C6—Ru1—C468.00 (18)C4—C5—Ru171.9 (3)
C5—Ru1—C436.57 (19)C6—C5—Ru170.5 (2)
C2—Ru1—C466.2 (2)C4—C5—H5119.1
N1—Ru1—C3151.14 (18)C6—C5—H5119.1
N2—Ru1—C3130.37 (18)Ru1—C5—H5119.1
C1—Ru1—C367.60 (18)N1—C11—C10121.8 (3)
C6—Ru1—C379.73 (17)N1—C11—H11119.1
C5—Ru1—C366.1 (2)C10—C11—H11119.1
C2—Ru1—C336.5 (2)C9—C8—C7119.3 (3)
C4—Ru1—C336.7 (2)C9—C8—H8120.4
N1—Ru1—Cl184.01 (8)C7—C8—H8120.4
N2—Ru1—Cl186.34 (8)C10—C9—C8118.8 (3)
C1—Ru1—Cl1147.23 (14)C10—C9—H9120.6
C6—Ru1—Cl1162.19 (14)C8—C9—H9120.6
C5—Ru1—Cl1123.93 (14)C9—C10—C11119.6 (3)
C2—Ru1—Cl1110.55 (13)C9—C10—H10120.2
C4—Ru1—Cl194.76 (13)C11—C10—H10120.2
C3—Ru1—Cl189.00 (13)C15—C14—C13119.2 (3)
C11—N1—C7119.0 (3)C15—C14—H14120.4
C11—N1—Ru1124.3 (2)C13—C14—H14120.4
C7—N1—Ru1116.5 (2)C14—C13—C12119.1 (3)
C16—N2—C12118.5 (3)C14—C13—H13120.4
C16—N2—Ru1125.0 (2)C12—C13—H13120.4
C12—N2—Ru1116.5 (2)N2—C16—C15122.7 (3)
N1—C7—C8121.6 (3)N2—C16—H16118.6
N1—C7—C12114.8 (3)C15—C16—H16118.6
C8—C7—C12123.6 (3)C16—C15—C14119.0 (3)
N2—C12—C13121.4 (3)C16—C15—H15120.5
N2—C12—C7114.6 (3)C14—C15—H15120.5
C13—C12—C7124.0 (3)C50—O51—H51109.5
C3—C2—C1120.7 (5)O51—C50—H50A109.5
C3—C2—Ru171.8 (3)O51—C50—H50B109.5
C1—C2—Ru169.8 (2)H50A—C50—H50B109.5
C3—C2—H2118.9O51—C50—H50C109.5
C1—C2—H2118.9H50A—C50—H50C109.5
Ru1—C2—H2118.9H50B—C50—H50C109.5
C6—C1—C2119.4 (5)C60—O61—H61109.5
C6—C1—Ru171.9 (2)O61—C60—H60A109.5
C2—C1—Ru172.3 (2)O61—C60—H60B109.5
C6—C1—H1120.0H60A—C60—H60B109.5
C2—C1—H1120.0O61—C60—H60C109.5
Ru1—C1—H1120.0H60A—C60—H60C109.5
C1—C6—C5118.2 (4)H60B—C60—H60C109.5
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O51—H51···Cl20.842.183.013 (4)170
O61—H61···Cl20.842.152.986 (6)171
Table 1
Selected geometric parameters (Å, °) top
Ru1—N12.083 (3)Ru1—C22.198 (4)
Ru1—N22.084 (3)Ru1—C42.198 (4)
Ru1—C12.165 (4)Ru1—C32.199 (4)
Ru1—C62.186 (4)Ru1—Cl12.4105 (9)
Ru1—C52.193 (4)
N1—Ru1—N277.18 (11)N2—Ru1—Cl186.34 (8)
N1—Ru1—Cl184.01 (8)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O51—H51···Cl20.842.183.013 (4)170
O61—H61···Cl20.842.152.986 (6)171
Acknowledgements top

The author acknowledges the extensive advice of Professor Peter Steel and funding from the New Zealand Foundation of Research, Science and Technology.

references
References top

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Westrip, S. P. (2008). publCIF. In preparation.