Acta Cryst. (2007). E63, m2332 [ doi:10.1107/S1600536807037865 ]
In the crystal structure of the title compound, [RuCl2(C10H8N2)2]·CH2Cl2, the complex consists of two bidentate 2,2'-bipyridyl N-atom donors and two chloride ions coordinated to an RuII centre which lies on a crystallographic twofold rotation axis. Equivalent ligands are cis, each related by the twofold rotation. One dichloromethane solvent molecule per Ru complex is trapped in the crystal structure.
1.0 mmole ruthenium trichloride and 2.0 mmol 2,2'-dipyridyl were refluxed in absolute ethanol for 4 h followed with the addition of 11.8 mmol LiCl and further reflux for additional 1 h. The solvent was then removed by rotary evaporator and the crude product dissolved in dichloromethane, filtered and washed by water and reduced to 20 ml. Chromatography on alumina with 10:1 dichloromethane: methanol as eluent yielded 0.2 g of the neutral complex from the second dark-pink band. Suitable crystals of (I) were obtained upon recrystallization from dichloromethane and slow evapotation of solvent.
All H atoms were positioned geometrically and refined using a riding model, with C—H distances fixed at 0.93 Å (aromatic) and 0.97 Å (methylene) and with Uiso constrained to be 1.2Ueq of the carrier atom.
Data collection: SMART (Bruker, 2006); cell refinement: SAINT-Plus (Bruker, 2006); data reduction: SAINT-Plus; program(s) used to solve structure: XS in SHELXTL (Bruker, 2003); program(s) used to refine structure: XL in SHELXTL; molecular graphics: XP in SHELXTL; software used to prepare material for publication: XCIF in SHELXTL.
![[Figure 1]](./at2362fig1thm.gif)
| Fig. 1. The molecular structure of the title compound (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. |
| [RuCl2(C10H8N2)2]·CH2Cl2 | F000 = 1136 |
| Mr = 569.26 | Dx = 1.638 Mg m−3 |
| Orthorhombic, Aba2 | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: A 2 -2ac | Cell parameters from 7381 reflections |
| a = 12.5658 (9) Å | θ = 2.6–29.6º |
| b = 15.4595 (11) Å | µ = 1.16 mm−1 |
| c = 11.8864 (9) Å | T = 298 (2) K |
| V = 2309.1 (3) Å3 | Plate, red |
| Z = 4 | 0.25 × 0.22 × 0.03 mm |
| Bruker/Siemens SMART APEX diffractometer | 2654 independent reflections |
| Monochromator: graphite | 2310 reflections with I > 2σ(I) |
| Detector resolution: 8.3 pixels mm-1 | Rint = 0.042 |
| T = 298(2) K | θmax = 27.5º |
| ω scans | θmin = 2.6º |
| Absorption correction: multi-scan (SADABS; Bruker, 2004) | h = −16→16 |
| Tmin = 0.761, Tmax = 0.966 | k = −20→20 |
| 16972 measured reflections | l = −15→15 |
| Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
| Least-squares matrix: full | H-atom parameters constrained |
| R[F2 > 2σ(F2)] = 0.028 | w = 1/[σ2(Fo2) + (0.0344P)2 + 0.0898P] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.064 | (Δ/σ)max = 0.001 |
| S = 1.04 | Δρmax = 0.49 e Å−3 |
| 2654 reflections | Δρmin = −0.28 e Å−3 |
| 137 parameters | Extinction correction: none |
| 1 restraint | Absolute structure: Flack (1983), 1260 Freidel pairs |
| Primary atom site location: structure-invariant direct methods | Flack parameter: −0.01 (5) |
| Secondary atom site location: difference Fourier map |
| [RuCl2(C10H8N2)2]·CH2Cl2 | V = 2309.1 (3) Å3 |
| Mr = 569.26 | Z = 4 |
| Orthorhombic, Aba2 | Mo Kα |
| a = 12.5658 (9) Å | µ = 1.16 mm−1 |
| b = 15.4595 (11) Å | T = 298 (2) K |
| c = 11.8864 (9) Å | 0.25 × 0.22 × 0.03 mm |
| Bruker/Siemens SMART APEX diffractometer | 2654 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 2004) | 2310 reflections with I > 2σ(I) |
| Tmin = 0.761, Tmax = 0.966 | Rint = 0.042 |
| 16972 measured reflections |
| R[F2 > 2σ(F2)] = 0.028 | H-atom parameters constrained |
| wR(F2) = 0.064 | Δρmax = 0.49 e Å−3 |
| S = 1.04 | Δρmin = −0.28 e Å−3 |
| 2654 reflections | Absolute structure: Flack (1983), 1260 Freidel pairs |
| 137 parameters | Flack parameter: −0.01 (5) |
| 1 restraint |
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 > 2sigma(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. |
| x | y | z | Uiso*/Ueq | Occ. (<1) | |
| C2 | 0.2168 (3) | 0.9265 (2) | 0.3118 (3) | 0.0486 (8) | |
| H2 | 0.2240 | 0.9752 | 0.3572 | 0.058* | |
| C3 | 0.2952 (3) | 0.8648 (3) | 0.3151 (4) | 0.0588 (10) | |
| H3 | 0.3537 | 0.8715 | 0.3622 | 0.071* | |
| C4 | 0.2863 (2) | 0.7930 (2) | 0.2481 (4) | 0.0594 (9) | |
| H4 | 0.3387 | 0.7505 | 0.2485 | 0.071* | |
| C5 | 0.1983 (3) | 0.7851 (2) | 0.1802 (3) | 0.0507 (9) | |
| H5 | 0.1906 | 0.7368 | 0.1343 | 0.061* | |
| C6 | 0.1209 (2) | 0.84917 (18) | 0.1803 (3) | 0.0361 (7) | |
| C7 | 0.0243 (3) | 0.84691 (19) | 0.1115 (3) | 0.0369 (7) | |
| C8 | 0.0016 (3) | 0.7830 (2) | 0.0331 (3) | 0.0488 (9) | |
| H8 | 0.0487 | 0.7373 | 0.0225 | 0.059* | |
| C9 | −0.0896 (3) | 0.7873 (2) | −0.0284 (3) | 0.0569 (9) | |
| H9 | −0.1048 | 0.7451 | −0.0818 | 0.068* | |
| C10 | −0.1594 (3) | 0.8549 (2) | −0.0110 (3) | 0.0505 (9) | |
| H10 | −0.2224 | 0.8587 | −0.0519 | 0.061* | |
| C11 | −0.1340 (3) | 0.9165 (2) | 0.0681 (3) | 0.0424 (7) | |
| H11 | −0.1810 | 0.9621 | 0.0798 | 0.051* | |
| C13 | 0.5000 | 1.0000 | 0.1365 (7) | 0.127 (5) | |
| H13A | 0.5485 | 1.0318 | 0.0883 | 0.152* | 0.50 |
| H13B | 0.4515 | 0.9682 | 0.0883 | 0.152* | 0.50 |
| Cl1 | 0.07119 (7) | 1.09792 (5) | 0.38787 (7) | 0.0464 (2) | |
| Cl2 | 0.57183 (12) | 0.92754 (9) | 0.21546 (12) | 0.1012 (5) | |
| N1 | 0.13028 (16) | 0.91993 (13) | 0.2463 (3) | 0.0345 (5) | |
| N12 | −0.0450 (2) | 0.91362 (16) | 0.1286 (2) | 0.0334 (6) | |
| Ru1 | 0.0000 | 1.0000 | 0.24825 (6) | 0.02831 (8) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C2 | 0.0427 (18) | 0.0461 (19) | 0.057 (2) | 0.0029 (15) | −0.0107 (17) | −0.0032 (16) |
| C3 | 0.0386 (18) | 0.065 (2) | 0.072 (3) | 0.0103 (17) | −0.0118 (18) | 0.010 (2) |
| C4 | 0.0447 (17) | 0.0552 (19) | 0.078 (2) | 0.0240 (15) | 0.004 (3) | 0.008 (3) |
| C5 | 0.050 (2) | 0.0377 (17) | 0.064 (2) | 0.0135 (15) | 0.0081 (18) | −0.0020 (16) |
| C6 | 0.0382 (16) | 0.0276 (14) | 0.0424 (17) | 0.0005 (12) | 0.0058 (13) | 0.0014 (13) |
| C7 | 0.0469 (18) | 0.0267 (15) | 0.0372 (16) | 0.0018 (12) | 0.0049 (13) | −0.0023 (13) |
| C8 | 0.061 (2) | 0.0390 (19) | 0.0468 (19) | 0.0030 (16) | 0.0043 (17) | −0.0140 (16) |
| C9 | 0.069 (2) | 0.054 (2) | 0.048 (2) | −0.0087 (18) | −0.0080 (19) | −0.0144 (17) |
| C10 | 0.052 (2) | 0.056 (2) | 0.0440 (19) | −0.0116 (17) | −0.0157 (17) | 0.0007 (17) |
| C11 | 0.0425 (17) | 0.0387 (17) | 0.0460 (18) | 0.0010 (14) | −0.0048 (14) | 0.0035 (14) |
| C13 | 0.190 (11) | 0.130 (8) | 0.061 (5) | 0.101 (7) | 0.000 | 0.000 |
| Cl1 | 0.0544 (5) | 0.0369 (4) | 0.0479 (4) | −0.0043 (4) | −0.0010 (4) | −0.0102 (4) |
| Cl2 | 0.1190 (12) | 0.0895 (8) | 0.0952 (11) | 0.0280 (8) | −0.0265 (8) | 0.0055 (8) |
| N1 | 0.0339 (11) | 0.0295 (10) | 0.0403 (12) | 0.0028 (8) | −0.0011 (15) | 0.0003 (14) |
| N12 | 0.0352 (13) | 0.0269 (14) | 0.0380 (14) | 0.0006 (11) | 0.0017 (12) | 0.0019 (11) |
| Ru1 | 0.03049 (13) | 0.02159 (12) | 0.03284 (14) | 0.00206 (12) | 0.000 | 0.000 |
| C2—N1 | 1.342 (4) | C9—H9 | 0.9300 |
| C2—C3 | 1.372 (5) | C10—C11 | 1.376 (5) |
| C2—H2 | 0.9300 | C10—H10 | 0.9300 |
| C3—C4 | 1.370 (6) | C11—N12 | 1.330 (4) |
| C3—H3 | 0.9300 | C11—H11 | 0.9300 |
| C4—C5 | 1.374 (5) | C13—Cl2i | 1.718 (5) |
| C4—H4 | 0.9300 | C13—Cl2 | 1.718 (5) |
| C5—C6 | 1.388 (4) | C13—H13A | 0.9700 |
| C5—H5 | 0.9300 | C13—H13B | 0.9700 |
| C6—N1 | 1.351 (4) | Cl1—Ru1 | 2.4179 (9) |
| C6—C7 | 1.464 (4) | N1—Ru1 | 2.052 (2) |
| C7—N12 | 1.365 (4) | N12—Ru1 | 2.031 (3) |
| C7—C8 | 1.388 (5) | Ru1—N12ii | 2.031 (3) |
| C8—C9 | 1.362 (5) | Ru1—N1ii | 2.052 (2) |
| C8—H8 | 0.9300 | Ru1—Cl1ii | 2.4179 (9) |
| C9—C10 | 1.379 (5) | ||
| N1—C2—C3 | 123.0 (3) | C10—C11—H11 | 118.6 |
| N1—C2—H2 | 118.5 | Cl2i—C13—Cl2 | 113.7 (5) |
| C3—C2—H2 | 118.5 | Cl2i—C13—H13A | 108.8 |
| C4—C3—C2 | 119.3 (3) | Cl2—C13—H13A | 108.8 |
| C4—C3—H3 | 120.4 | Cl2i—C13—H13B | 108.8 |
| C2—C3—H3 | 120.4 | Cl2—C13—H13B | 108.8 |
| C3—C4—C5 | 118.6 (3) | H13A—C13—H13B | 107.7 |
| C3—C4—H4 | 120.7 | C2—N1—C6 | 117.9 (3) |
| C5—C4—H4 | 120.7 | C2—N1—Ru1 | 126.4 (2) |
| C4—C5—C6 | 120.0 (3) | C6—N1—Ru1 | 115.21 (19) |
| C4—C5—H5 | 120.0 | C11—N12—C7 | 118.8 (3) |
| C6—C5—H5 | 120.0 | C11—N12—Ru1 | 126.2 (2) |
| N1—C6—C5 | 121.2 (3) | C7—N12—Ru1 | 115.0 (2) |
| N1—C6—C7 | 114.5 (2) | N12—Ru1—N12ii | 91.08 (15) |
| C5—C6—C7 | 124.3 (3) | N12—Ru1—N1 | 79.47 (11) |
| N12—C7—C8 | 120.4 (3) | N12ii—Ru1—N1 | 99.59 (11) |
| N12—C7—C6 | 115.3 (3) | N12—Ru1—N1ii | 99.59 (11) |
| C8—C7—C6 | 124.2 (3) | N12ii—Ru1—N1ii | 79.47 (11) |
| C9—C8—C7 | 119.9 (3) | N1—Ru1—N1ii | 178.68 (19) |
| C9—C8—H8 | 120.0 | N12—Ru1—Cl1 | 174.38 (8) |
| C7—C8—H8 | 120.0 | N12ii—Ru1—Cl1 | 88.07 (7) |
| C8—C9—C10 | 119.5 (3) | N1—Ru1—Cl1 | 95.19 (8) |
| C8—C9—H9 | 120.3 | N1ii—Ru1—Cl1 | 85.72 (8) |
| C10—C9—H9 | 120.3 | N12—Ru1—Cl1ii | 88.07 (7) |
| C11—C10—C9 | 118.6 (3) | N12ii—Ru1—Cl1ii | 174.38 (8) |
| C11—C10—H10 | 120.7 | N1—Ru1—Cl1ii | 85.72 (8) |
| C9—C10—H10 | 120.7 | N1ii—Ru1—Cl1ii | 95.19 (8) |
| N12—C11—C10 | 122.8 (3) | Cl1—Ru1—Cl1ii | 93.31 (5) |
| N12—C11—H11 | 118.6 |
| Symmetry codes: (i) −x+1, −y+2, z; (ii) −x, −y+2, z. |
This work was supported in part by the Deanship of Academic Research, University of Jordan. Thanks are also due to Brendan Twamley, University Research Office, University of Idaho, Moscow, ID.
Bruker (2003). XS, XL, XP and XCIF in SHELXTL. Version 6.14. Bruker AXS Inc., Madison, Wisconsin, USA.
Bruker (2004). SADABS. Version 2004/1. Bruker AXS Inc., Madison, Wisconsin, USA.
Bruker (2006). SMART (Version 5.632) and SAINT-Plus (Version 7.23a). Bruker AXS Inc., Madison, Wisconsin, USA.
Eggleston, D. S., Goldsby, K. A., Hodgson, D. J. & Meyer, T. J. (1985). Inorg. Chem. 24, 4573–?.
Flack, H. D. (1983). Acta Cryst. A39, 876–881.
Lackner, W., Schmid, R., Kirchner, K. & Merieter, K. (2004). Private communication to the Cambridge Structural Database (deposition number CCDC 231460). CCDC, Union Road, Cambridge, England.
Nag, S., Drew, M. G. B. & Datta, D. (2006). Inorg. Chem. Commun. 9, 310–312.
The structure of the title compound, (I), is shown in Fig. 1. A l l bond lengths and angles are normal. The complex has been reported earlier in lower symmetry space groups as the hydrate in C2/c (Eggleston et al., 1985), as an acetone solvate in P21/n (Lackner et al., 2004), and as an I2 adduct in C2/c (Nag et al., 2006).
The structure of (I) displays distorted octahedral coordination to the metal cation, without any significant hydrogen bonding. The solvent molecule is free in the lattice and displays larger thermal displacements than seen in the Ru complex.
The 2,2'-bipyridyl ligand is planar. The five membered chelate ring is folded about the N1···N12 line with a dihedral angle between the plane of the ligand, and the N1/Ru1/N12 plane of 5.0 (2)°. The dihedral angle between the least square planes of the two fold rotation related 2,2'-bipyridyl ligands is 87.78°. The Cl1—Ru1—Cl1i [symmetry code: (i) −x, −y + 2, z] angle is 93.31 (5)°.