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Acta Cryst. (2007). E63, m3088    [ doi:10.1107/S1600536807058680 ]

trans-Bis(2,2'-bipyridine)dichloridoruthenium(II)

P. Klüfers and A. Zangl

Abstract top

In the title compound, [RuCl2(C10H8N2)2], the Ru atom is located on a crystallographic inversion center. The bipyridine (bpy) ligands are thus coordinated trans, leading to steric interactions between pairs of opposite ortho-H atoms. The result is a marked deviation from the expected planarity of some units; the two pyridine rings of an individual bpy ligand enclose a 23.8 (1)° angle. With the RuN4 plane, the same pyridine rings enclose angles of 22.3 (1) and 21.0 (1)°. The octahedral environment of the Ru atom, however, is not markedly distorted, with the Ru-Cl axis enclosing a 87.32 (6)° angle with the RuN4 plane. In the crystal structure, the most significant intermolecular interaction, besides the expected [pi] stacking [3.424 (3) Å perpendicular distance of parallel-stacked rings, and 3.389 (3) Å closest ring-atom distance for an inclined contact], is a weak C-H...Cl hydrogen bond.

Comment top

The title compound, C20H16Cl2N4Ru, was obtained accidentally on the attempted preparation of [Ru(cis-CptdH-2)(bipy)2] (cis-CptdH-2 = twofold deprotonated cis-1,2-cyclopentanediol, bipy = 2,2'-bipyridine).

The molecular structure is shown in Fig. 1. The five-membered chelate ring Ru—N1—C5—C6—N2 adopts an envelope conformation on Ru (Q2 = 0.2785 (17) Å, φ2 = 184.3 (5)°). Ring-puckering parameters (Cremer & Pople, 1975) were calculated with PLATON (Spek, 2003).

Bond lengths and angles are comparable to similar compounds (Weathers et al., 1997).

The molecular packing is shown in Fig. 2 which shows a layer of molecules of (I) in the bc plane. Hydrogen bonds of the C–H···Cl type connect these layers along [100]. [100]-stacking is supported by π stacking of aromatic rings that enclose a 23.8 (1)° angle, the closest ring···atom contact being 3.389 (3) Å.

π stacking is also observed for adjacent molecules along [001] between aromatic rings that are connected by an inversion center. The perpendicular ring distance is 3.424 (3) Å for this interaction.

Related literature top

Sullivan et al. (1978) describe the respective cis-coordinated complex which was used as the starting material for the synthesis of the title compound. Weathers et al. (1997) describe a related complex cation with the chlorido ligands of the title compound substituted by aqua ligands. For ring puckering analysis, see: Cremer & Pople (1975).

Experimental top

The title compound was obtained accidentally on the attempted preparation of [Ru(cis-CptdH-2)(bipy)2] by refluxing 58 mg (0.12 mmol) cis-[RuCl2(bipy)2] (Sullivan et al., 1978), 27 mg (0.26 mmol) cis-1,2-cyclopentanediol and 15 mg (0.27 mmol) KOH for 4 h in a solution of 1.4 ml H2O and 4 ml 2-propanol under an inert gas atmosphere (N2). When the closed reaction flask was left standing at room temperature in bright daylight, violet-black crystals were obtained after several months.

Refinement top

All H atoms were included in calculated positions and refined as riding on their parent atoms with one common isotropic displacement parameter.

Computing details top

Data collection: COLLECT (Hooft, 2004); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: HKL 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, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with atom labels and anisotropic displacement ellipsoids (drawn at 50% probability level) for non-H atoms.
[Figure 2] Fig. 2. A layer of molecules of (I) in the bc plane.
i>trans-Bis(2,2'-bipyridine)dichloridoruthenium(II) top
Crystal data top
[RuCl2(C10H8N2)2]F000 = 484
Mr = 484.34Dx = 1.785 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 6762 reflections
a = 7.0047 (3) Åθ = 3.1–27.5º
b = 14.9489 (6) ŵ = 1.18 mm−1
c = 8.7301 (3) ÅT = 200 (2) K
β = 99.692 (2)ºPlatelet, black-violet
V = 901.10 (6) Å30.15 × 0.10 × 0.06 mm
Z = 2
Data collection top
Nonius KappaCCD
diffractometer		2067 independent reflections
Radiation source: rotating anode1719 reflections with I > 2σ(I)
Monochromator: MONTEL, graded multilayered X-ray opticsRint = 0.041
T = 200(2) Kθmax = 27.5º
φ and ω scansθmin = 3.3º
Absorption correction: multi-scan
(SADABS; Sheldrick, 2001)		h = −9→8
Tmin = 0.763, Tmax = 0.932k = −19→19
10312 measured reflectionsl = −11→11
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)] = 0.026H-atom parameters constrained
wR(F2) = 0.058  w = 1/[σ2(Fo2) + (0.015P)2 + 0.9494P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max < 0.001
2067 reflectionsΔρmax = 0.53 e Å−3
125 parametersΔρmin = −0.56 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[RuCl2(C10H8N2)2]V = 901.10 (6) Å3
Mr = 484.34Z = 2
Monoclinic, P21/cMo Kα
a = 7.0047 (3) ŵ = 1.18 mm−1
b = 14.9489 (6) ÅT = 200 (2) K
c = 8.7301 (3) Å0.15 × 0.10 × 0.06 mm
β = 99.692 (2)º
Data collection top
Nonius KappaCCD
diffractometer		2067 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2001)		1719 reflections with I > 2σ(I)
Tmin = 0.763, Tmax = 0.932Rint = 0.041
10312 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.026125 parameters
wR(F2) = 0.058H-atom parameters constrained
S = 1.06Δρmax = 0.53 e Å−3
2067 reflectionsΔρmin = −0.56 e Å−3
Special details top

Experimental. µ × r = 0.116, Tmin/Tmax = 0.899

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ru0.00000.00000.00000.01748 (9)
Cl1−0.18499 (9)0.12549 (4)−0.11057 (7)0.02946 (15)
N1−0.1977 (3)−0.09044 (12)−0.1129 (2)0.0204 (4)
N20.1001 (3)−0.02145 (12)−0.2052 (2)0.0206 (4)
C1−0.3740 (3)−0.11069 (15)−0.0811 (3)0.0243 (5)
H1−0.4268−0.0741−0.00970.033 (3)*
C2−0.4811 (3)−0.18208 (16)−0.1476 (3)0.0290 (6)
H2−0.6049−0.1944−0.12180.033 (3)*
C3−0.4071 (4)−0.23546 (17)−0.2521 (3)0.0339 (6)
H3−0.4755−0.2869−0.29540.033 (3)*
C4−0.2302 (4)−0.21242 (16)−0.2925 (3)0.0319 (6)
H4−0.1772−0.2473−0.36610.033 (3)*
C5−0.1312 (3)−0.13828 (15)−0.2249 (3)0.0223 (5)
C60.0355 (3)−0.09807 (15)−0.2809 (3)0.0231 (5)
C70.1040 (4)−0.12659 (18)−0.4124 (3)0.0307 (6)
H70.0631−0.1823−0.45890.033 (3)*
C80.2319 (4)−0.07363 (19)−0.4754 (3)0.0344 (6)
H80.2803−0.0920−0.56580.033 (3)*
C90.2882 (4)0.00714 (18)−0.4039 (3)0.0333 (6)
H90.37300.0460−0.44650.033 (3)*
C100.2200 (4)0.03048 (17)−0.2706 (3)0.0273 (5)
H100.25980.0860−0.22260.033 (3)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ru0.02017 (14)0.01732 (13)0.01542 (13)0.00075 (10)0.00439 (9)−0.00161 (10)
Cl10.0339 (3)0.0278 (3)0.0268 (3)0.0094 (3)0.0055 (3)0.0018 (3)
N10.0196 (10)0.0255 (10)0.0163 (9)0.0011 (8)0.0032 (8)−0.0005 (8)
N20.0226 (10)0.0228 (10)0.0167 (9)0.0017 (8)0.0045 (8)−0.0008 (7)
C10.0246 (12)0.0245 (12)0.0242 (13)0.0042 (10)0.0053 (10)0.0006 (9)
C20.0206 (12)0.0333 (13)0.0328 (14)−0.0006 (10)0.0036 (11)0.0009 (11)
C30.0306 (14)0.0311 (13)0.0395 (16)−0.0061 (11)0.0038 (12)−0.0120 (12)
C40.0314 (14)0.0300 (13)0.0348 (15)−0.0028 (11)0.0074 (12)−0.0133 (11)
C50.0233 (12)0.0233 (11)0.0203 (12)0.0022 (9)0.0036 (9)−0.0036 (9)
C60.0244 (12)0.0253 (12)0.0191 (12)0.0043 (9)0.0022 (10)−0.0030 (9)
C70.0288 (13)0.0358 (14)0.0275 (13)0.0033 (11)0.0048 (11)−0.0110 (11)
C80.0322 (14)0.0505 (16)0.0224 (13)0.0041 (13)0.0097 (11)−0.0054 (12)
C90.0319 (14)0.0431 (15)0.0279 (13)0.0002 (12)0.0136 (11)0.0069 (12)
C100.0308 (13)0.0275 (12)0.0247 (13)−0.0014 (10)0.0084 (11)0.0015 (10)
Geometric parameters (Å, °) top
Ru—N22.0560 (19)C3—C41.388 (4)
Ru—N2i2.0560 (19)C3—H30.9500
Ru—N12.0632 (18)C4—C51.385 (3)
Ru—N1i2.0632 (18)C4—H40.9500
Ru—Cl1i2.3893 (6)C5—C61.468 (3)
Ru—Cl12.3893 (6)C6—C71.384 (3)
N1—C11.345 (3)C7—C81.378 (4)
N1—C51.356 (3)C7—H70.9500
N2—C101.340 (3)C8—C91.386 (4)
N2—C61.361 (3)C8—H80.9500
C1—C21.376 (3)C9—C101.375 (4)
C1—H10.9500C9—H90.9500
C2—C31.377 (4)C10—H100.9500
C2—H20.9500
N2—Ru—N2i180.00 (9)C3—C2—H2120.3
N2—Ru—N177.38 (7)C2—C3—C4118.5 (2)
N2i—Ru—N1102.62 (7)C2—C3—H3120.8
N2—Ru—N1i102.62 (7)C4—C3—H3120.8
N2i—Ru—N1i77.38 (7)C5—C4—C3119.6 (2)
N1—Ru—N1i180.00 (12)C5—C4—H4120.2
N2—Ru—Cl1i89.32 (5)C3—C4—H4120.2
N2i—Ru—Cl1i90.68 (5)N1—C5—C4121.4 (2)
N1—Ru—Cl1i87.32 (5)N1—C5—C6114.42 (19)
N1i—Ru—Cl1i92.68 (5)C4—C5—C6123.7 (2)
N2—Ru—Cl190.68 (5)N2—C6—C7121.9 (2)
N2i—Ru—Cl189.32 (5)N2—C6—C5113.6 (2)
N1—Ru—Cl192.68 (5)C7—C6—C5123.8 (2)
N1i—Ru—Cl187.31 (5)C8—C7—C6119.6 (2)
Cl1i—Ru—Cl1180.00 (3)C8—C7—H7120.2
C1—N1—C5117.97 (19)C6—C7—H7120.2
C1—N1—Ru127.93 (16)C7—C8—C9118.4 (2)
C5—N1—Ru113.93 (15)C7—C8—H8120.8
C10—N2—C6117.5 (2)C9—C8—H8120.8
C10—N2—Ru127.67 (16)C10—C9—C8119.3 (2)
C6—N2—Ru114.84 (16)C10—C9—H9120.4
N1—C1—C2122.8 (2)C8—C9—H9120.4
N1—C1—H1118.6N2—C10—C9123.0 (2)
C2—C1—H1118.6N2—C10—H10118.5
C1—C2—C3119.3 (2)C9—C10—H10118.5
C1—C2—H2120.3
N2—Ru—N1—C1−163.6 (2)C1—N1—C5—C4−7.4 (3)
N2i—Ru—N1—C116.4 (2)Ru—N1—C5—C4168.23 (18)
Cl1i—Ru—N1—C1106.46 (19)C1—N1—C5—C6164.8 (2)
Cl1—Ru—N1—C1−73.54 (19)Ru—N1—C5—C6−19.6 (2)
N2—Ru—N1—C521.26 (15)C3—C4—C5—N13.9 (4)
N2i—Ru—N1—C5−158.74 (15)C3—C4—C5—C6−167.5 (2)
Cl1i—Ru—N1—C5−68.65 (15)C10—N2—C6—C76.1 (3)
Cl1—Ru—N1—C5111.35 (15)Ru—N2—C6—C7−173.60 (18)
N1—Ru—N2—C10160.5 (2)C10—N2—C6—C5−164.9 (2)
N1i—Ru—N2—C10−19.5 (2)Ru—N2—C6—C515.4 (2)
Cl1i—Ru—N2—C10−112.12 (19)N1—C5—C6—N22.9 (3)
Cl1—Ru—N2—C1067.88 (19)C4—C5—C6—N2174.9 (2)
N1—Ru—N2—C6−19.82 (15)N1—C5—C6—C7−168.0 (2)
N1i—Ru—N2—C6160.18 (15)C4—C5—C6—C74.0 (4)
Cl1i—Ru—N2—C667.58 (15)N2—C6—C7—C8−4.3 (4)
Cl1—Ru—N2—C6−112.42 (15)C5—C6—C7—C8165.8 (2)
C5—N1—C1—C25.6 (3)C6—C7—C8—C90.1 (4)
Ru—N1—C1—C2−169.29 (17)C7—C8—C9—C102.0 (4)
N1—C1—C2—C3−0.4 (4)C6—N2—C10—C9−4.0 (3)
C1—C2—C3—C4−3.2 (4)Ru—N2—C10—C9175.73 (18)
C2—C3—C4—C51.5 (4)C8—C9—C10—N20.0 (4)
Symmetry codes: (i) −x, −y, −z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C3—H3···Cl1ii0.952.723.573 (3)150
Symmetry codes: (ii) −x−1, y−1/2, −z−1/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C3—H3···Cl1i0.952.723.573 (3)150
Symmetry codes: (i) −x−1, y−1/2, −z−1/2.
Acknowledgements top

The authors thank Dr Matthias Hinrichs for professional support.

references
References top

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Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358.

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Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press.

Sheldrick, G. M. (1997). SHELXL97. University of Göttingen, Germany.

Sheldrick, G. M. (2001). SADABS. Version 2. University of Göttingen, Germany.

Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13.

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Weathers, N. R., Sadoski, R. C., Durham, B. & Cordes, A. W. (1997). Acta Cryst. C53, 1047–1049.