Acta Cryst. (2013). E69, m81-m82 [ doi:10.1107/S1600536812051215 ]
![[mu]](/logos/entities/mu_rmgif.gif)
-2,3,5,6-Tetrakis(pyridin-2-yl)pyrazine-bis[(2,2':6',2''-terpyridine)ruthenium(II)] tetrakis(hexafluoridophosphate) acetonitrile tetrasolvateIn the title compound [Ru2(C15H11N3)2(C24H16N6)](PF6)4·4CH3CN, two of the counter-ions and one of the solvent molecules are disordered with occupancies for the major components between 0.57 (2) and 0.64 (1). The structure of the dinuclear tetracation exhibits significant distortion from planarity in the bridging 2,3,5,6-tetrakis(pyridin-2-yl)pyrazine (tppz) ligand, which has a saddle-like geometry with an average dihedral angle of 42.96 (18)° between adjacent pyridine rings. The metal-ligand coordination environment is nearly equivalent for the two RuII atoms, which have a distorted octahedral geometry due to the restricted bite angle [157.57 (13)-159.28 (12)°] of their two mer-arranged tridendate ligands [2,2':6',2''-terpyridine (tpy) and tppz] orthogonal to each other. At the peripheral tpy ligands, the average Ru-N bond distance is 2.072 (4) Å for the outer N atoms trans to each other (Nouter) and 1.984 (1) Å for the central N atoms (Ncentral). At the bridging tppz ligand, the average metal-ligand distances are significantly shorter [2.058 (4) Å for Ru-Nouter and 1.965 (1) Å for Ru-Ncentral] as a result of both the geometric constraints and the stronger ![[pi]](/logos/entities/pi_rmgif.gif)
-acceptor ability of the pyrazine-centered bridge. The dihedral angle between the two tpy planes is 27.11 (6)°. The intramolecular linear distance between the two Ru atoms is 6.6102 (7) Å.
The synthesis of [(tpy)RuII(tppz)RuII(tpy)](PF6)4 was performed by two methods. A) In this route, we took advantage of our previously reported precursor to tppz-bridged dimers, the mixed-valent solvento complex [(EtOH)Cl2RuII(tppz)RuIIICl3] (Chen et al., 2011; Rocha et al., 2008). This precursor was utilized in a reaction with 2 equiv of tpy in EtOH heated at reflux for 8 h, under an Ar atmosphere. Et3N in stoichiometric excess was added as a reductant. Following substitution of the Cl- ligands, the tpy-capped dimer was collected as a solid salt by filtration of the precipitate formed upon addition of a concentrated aqueous solution of NH4PF6 to the reactional mixture. The compound was further purified via alumina column chromatography (MeCN:toluene 1:1 as eluent) and the final product isolated/air-dried by vacuum filtration following precipitation of the salt into Et2O. B) In this method, we followed a literature procedures (Arana & Abruña, 1993; Vogler et al., 1996) by reacting tppz with 2 equiv of the mononuclear RuIIICl3(tpy) complex for 24 h in refluxing EtOH/H2O (2:1 vol. mixture), under Ar and with excess Et3N added. The solid product was isolated and purified as described for method A. The identity of the cation [(tpy)RuII(tppz)RuII(tpy)]4+ (I) in solution was also confirmed by electrochemical and spectroscopic measurements. Single crystals suitable for X-ray analysis were obtained by slow diffusion of Et2O into concentrated MeCN solutions of [(tpy)Ru(tppz)Ru(tpy)](PF6)4.
Two PF6- counterions and one MeCN solvent molecule were disordered, and each refined in two positions. The site-occupancy-factors (sof) of disordered pairs of atoms were refined and tied to sum to 1.0. The sof for the first anion (atoms P2, F7 to F12) was refined to 0.62 (2). The sof for the second anion (atoms P4, F19 to F24) was refined to 0.57 (2). The MeCN sof (atoms N13, C55, C56) was refined to 0.64 (1). For the first anion, only atoms F7, F9, F10, and F12 were disordered. Bond distances of disordered molecule pairs were restrained to have identical values. The disordered atoms P4 and P4' were constrained to have identical temperature factors. For the disordered MeCN molecule, atoms were restrained to have similar Uij components. All H atoms were idealized and refined as riding atoms, with C-H = 0.93 Å (aromatic) or 0.96 Å (methyl) and Uiso(H) = 1.2 (aromatic) or 1.5 (methyl) times Ueq(C). Methyl torsion angles were refined from electron density.
Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).
![[Figure 1]](./zl2523fig1thm.gif)
| Fig. 1. Two views of the single-crystal structure of the cation (I) in [(tpy)Ru(tppz)Ru(tpy)](PF6)4×4MeCN. Displacement ellipsoids are drawn at the 50% probability level. H atoms are omitted for clarity. |
![[Figure 2]](./zl2523fig2thm.gif)
| Fig. 2. Single-crystal structure of [(tpy)Ru(tppz)Ru(tpy)](PF6)4×4MeCN, with all counterions and solvent molecules included. Also shown is the observed disorder in two of the PF6- anions (P2,F7–F12 and P4,F19–F24) and one of the MeCN solvent molecules (N13,C55,C56). Displacement ellipsoids are drawn at th e 50% probability level. H atoms are omitted for clarity. |
| [Ru2(C15H11N3)2(C24H16N6)](PF6)4·4C2H3N | F(000) = 3592 |
| Mr = 1801.20 | Dx = 1.717 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 5749 reflections |
| a = 11.8871 (9) Å | θ = 4.4–44.8° |
| b = 31.824 (2) Å | µ = 0.64 mm−1 |
| c = 18.5168 (14) Å | T = 120 K |
| β = 95.880 (1)° | Block, green |
| V = 6968.0 (9) Å3 | 0.18 × 0.10 × 0.08 mm |
| Z = 4 |
| Bruker D8 with APEXII CCD diffractometer | 12753 independent reflections |
| Radiation source: fine-focus sealed tube | 8864 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.107 |
| ω scans | θmax = 25.4°, θmin = 1.8° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2008) | h = −14→14 |
| Tmin = 0.893, Tmax = 0.950 | k = −38→38 |
| 67490 measured reflections | l = −22→22 |
| Refinement on F2 | Primary atom site location: structure-invariant direct methods |
| Least-squares matrix: full | Secondary atom site location: difference Fourier map |
| R[F2 > 2σ(F2)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.102 | H-atom parameters constrained |
| S = 1.10 | w = 1/[σ2(Fo2) + (0.0305P)2] where P = (Fo2 + 2Fc2)/3 |
| 12753 reflections | (Δ/σ)max = 0.001 |
| 1101 parameters | Δρmax = 0.75 e Å−3 |
| 78 restraints | Δρmin = −0.50 e Å−3 |
| [Ru2(C15H11N3)2(C24H16N6)](PF6)4·4C2H3N | V = 6968.0 (9) Å3 |
| Mr = 1801.20 | Z = 4 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 11.8871 (9) Å | µ = 0.64 mm−1 |
| b = 31.824 (2) Å | T = 120 K |
| c = 18.5168 (14) Å | 0.18 × 0.10 × 0.08 mm |
| β = 95.880 (1)° |
| Bruker D8 with APEXII CCD diffractometer | 12753 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2008) | 8864 reflections with I > 2σ(I) |
| Tmin = 0.893, Tmax = 0.950 | Rint = 0.107 |
| 67490 measured reflections | θmax = 25.4° |
| R[F2 > 2σ(F2)] = 0.045 | H-atom parameters constrained |
| wR(F2) = 0.102 | Δρmax = 0.75 e Å−3 |
| S = 1.10 | Δρmin = −0.50 e Å−3 |
| 12753 reflections | Absolute structure: ? |
| 1101 parameters | Flack parameter: ? |
| 78 restraints | Rogers parameter: ? |
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. |
| x | y | z | Uiso*/Ueq | Occ. (<1) | |
| Ru1 | 0.28004 (3) | 0.035873 (10) | 0.746568 (18) | 0.01496 (9) | |
| Ru2 | 0.07869 (3) | 0.229580 (10) | 0.741853 (18) | 0.01721 (10) | |
| P1 | 0.25514 (9) | 0.90082 (4) | 0.56200 (6) | 0.0227 (3) | |
| P2 | 0.28371 (11) | 0.44051 (4) | 0.55316 (7) | 0.0335 (3) | |
| P3 | 0.68786 (11) | 0.30383 (4) | 0.57181 (7) | 0.0338 (3) | |
| F1 | 0.25658 (19) | 0.90561 (7) | 0.64831 (12) | 0.0268 (6) | |
| F2 | 0.24448 (19) | 0.85077 (7) | 0.56958 (14) | 0.0324 (6) | |
| F3 | 0.38934 (19) | 0.89688 (8) | 0.56969 (13) | 0.0331 (6) | |
| F4 | 0.2513 (2) | 0.89662 (8) | 0.47551 (13) | 0.0372 (7) | |
| F5 | 0.26664 (19) | 0.95111 (7) | 0.55527 (12) | 0.0263 (6) | |
| F6 | 0.12030 (19) | 0.90529 (7) | 0.55462 (13) | 0.0279 (6) | |
| F8 | 0.3444 (3) | 0.39580 (9) | 0.55286 (16) | 0.0592 (9) | |
| F11 | 0.2215 (3) | 0.48488 (10) | 0.55481 (17) | 0.0639 (10) | |
| F7 | 0.3737 (7) | 0.4580 (2) | 0.6111 (5) | 0.061 (3) | 0.620 (16) |
| F9 | 0.2061 (7) | 0.42705 (18) | 0.6146 (5) | 0.052 (3) | 0.620 (16) |
| F10 | 0.1800 (9) | 0.4271 (2) | 0.4950 (6) | 0.097 (4) | 0.620 (16) |
| F12 | 0.3450 (10) | 0.4581 (3) | 0.4896 (6) | 0.077 (4) | 0.620 (16) |
| F7' | 0.2920 (19) | 0.4335 (3) | 0.6394 (4) | 0.075 (7) | 0.380 (16) |
| F9' | 0.1765 (9) | 0.4112 (5) | 0.5478 (11) | 0.098 (7) | 0.380 (16) |
| F10' | 0.2855 (15) | 0.4379 (6) | 0.4691 (5) | 0.071 (6) | 0.380 (16) |
| F12' | 0.4061 (9) | 0.4613 (3) | 0.5608 (13) | 0.086 (7) | 0.380 (16) |
| F13 | 0.6356 (2) | 0.31570 (8) | 0.64503 (16) | 0.0503 (8) | |
| F14 | 0.6916 (4) | 0.25661 (10) | 0.5933 (2) | 0.1006 (15) | |
| F15 | 0.8113 (2) | 0.31061 (10) | 0.61355 (15) | 0.0609 (9) | |
| F16 | 0.7432 (3) | 0.29210 (10) | 0.50021 (15) | 0.0635 (9) | |
| F17 | 0.6918 (3) | 0.35241 (9) | 0.55080 (15) | 0.0578 (9) | |
| F18 | 0.5676 (3) | 0.29980 (11) | 0.5294 (2) | 0.0859 (12) | |
| P4 | 0.2383 (7) | 0.1122 (3) | 0.4097 (5) | 0.0257 (6) | 0.57 (2) |
| F19 | 0.3620 (9) | 0.0939 (5) | 0.4252 (8) | 0.058 (4) | 0.57 (2) |
| F20 | 0.1908 (10) | 0.0826 (3) | 0.4676 (3) | 0.048 (3) | 0.57 (2) |
| F21 | 0.2668 (14) | 0.1450 (4) | 0.4736 (7) | 0.054 (3) | 0.57 (2) |
| F22 | 0.1166 (7) | 0.1327 (5) | 0.3952 (5) | 0.051 (3) | 0.57 (2) |
| F23 | 0.2835 (11) | 0.1430 (4) | 0.3528 (6) | 0.068 (3) | 0.57 (2) |
| F24 | 0.2076 (12) | 0.0789 (4) | 0.3475 (7) | 0.069 (4) | 0.57 (2) |
| P4' | 0.2409 (10) | 0.1081 (4) | 0.4068 (7) | 0.0257 (6) | 0.43 (2) |
| F19' | 0.3744 (9) | 0.1053 (5) | 0.4070 (9) | 0.038 (4) | 0.43 (2) |
| F20' | 0.2414 (12) | 0.0637 (5) | 0.4463 (10) | 0.068 (6) | 0.43 (2) |
| F21' | 0.2594 (15) | 0.1316 (8) | 0.4826 (9) | 0.076 (7) | 0.43 (2) |
| F22' | 0.1071 (8) | 0.1098 (5) | 0.4053 (7) | 0.040 (3) | 0.43 (2) |
| F23' | 0.2421 (14) | 0.1526 (3) | 0.3683 (11) | 0.065 (5) | 0.43 (2) |
| F24' | 0.2257 (12) | 0.0861 (5) | 0.3299 (8) | 0.042 (4) | 0.43 (2) |
| N1 | 0.3936 (3) | 0.03905 (10) | 0.66882 (18) | 0.0181 (8) | |
| N2 | 0.3472 (3) | −0.02106 (10) | 0.75424 (17) | 0.0173 (8) | |
| N3 | 0.1865 (3) | 0.00855 (10) | 0.82253 (17) | 0.0193 (8) | |
| N4 | 0.1428 (3) | 0.02977 (10) | 0.66999 (17) | 0.0167 (8) | |
| N5 | 0.2211 (3) | 0.09345 (10) | 0.74346 (17) | 0.0149 (7) | |
| N6 | 0.3934 (3) | 0.06344 (10) | 0.82402 (17) | 0.0163 (8) | |
| N7 | 0.0196 (3) | 0.21001 (10) | 0.63882 (17) | 0.0167 (8) | |
| N8 | 0.1398 (3) | 0.17199 (10) | 0.74223 (17) | 0.0160 (8) | |
| N9 | 0.1634 (3) | 0.22700 (10) | 0.84401 (17) | 0.0175 (8) | |
| N10 | 0.2107 (3) | 0.26278 (10) | 0.70475 (17) | 0.0204 (8) | |
| N11 | 0.0202 (3) | 0.28805 (10) | 0.74401 (17) | 0.0196 (8) | |
| N12 | −0.0772 (3) | 0.21994 (10) | 0.78029 (18) | 0.0209 (8) | |
| N15 | 0.4640 (5) | 0.16296 (15) | 0.6902 (3) | 0.0695 (16) | |
| N16 | 0.8158 (7) | 0.08326 (18) | 0.7468 (3) | 0.110 (3) | |
| C1 | 0.4069 (4) | 0.07013 (14) | 0.6217 (2) | 0.0265 (11) | |
| H1 | 0.3620 | 0.0940 | 0.6231 | 0.032* | |
| C2 | 0.4843 (4) | 0.06829 (16) | 0.5711 (2) | 0.0349 (12) | |
| H2 | 0.4913 | 0.0905 | 0.5393 | 0.042* | |
| C3 | 0.5510 (4) | 0.03303 (16) | 0.5685 (3) | 0.0358 (12) | |
| H3 | 0.6050 | 0.0314 | 0.5357 | 0.043* | |
| C4 | 0.5367 (4) | 0.00044 (15) | 0.6148 (2) | 0.0283 (11) | |
| H4 | 0.5801 | −0.0238 | 0.6129 | 0.034* | |
| C5 | 0.4577 (3) | 0.00342 (13) | 0.6645 (2) | 0.0218 (10) | |
| C6 | 0.4335 (3) | −0.03055 (13) | 0.7148 (2) | 0.0229 (10) | |
| C7 | 0.4878 (4) | −0.06887 (14) | 0.7234 (3) | 0.0324 (12) | |
| H7 | 0.5473 | −0.0756 | 0.6966 | 0.039* | |
| C8 | 0.4517 (4) | −0.09672 (15) | 0.7725 (3) | 0.0380 (13) | |
| H8 | 0.4868 | −0.1228 | 0.7785 | 0.046* | |
| C9 | 0.3652 (4) | −0.08701 (14) | 0.8130 (3) | 0.0360 (13) | |
| H9 | 0.3420 | −0.1060 | 0.8466 | 0.043* | |
| C10 | 0.3126 (4) | −0.04804 (13) | 0.8030 (2) | 0.0239 (10) | |
| C11 | 0.2183 (4) | −0.03205 (13) | 0.8403 (2) | 0.0238 (10) | |
| C12 | 0.1585 (4) | −0.05518 (15) | 0.8870 (3) | 0.0382 (13) | |
| H12 | 0.1801 | −0.0826 | 0.8990 | 0.046* | |
| C13 | 0.0672 (4) | −0.03753 (16) | 0.9158 (3) | 0.0418 (14) | |
| H13 | 0.0270 | −0.0530 | 0.9472 | 0.050* | |
| C14 | 0.0355 (4) | 0.00323 (16) | 0.8978 (2) | 0.0356 (12) | |
| H14 | −0.0265 | 0.0156 | 0.9162 | 0.043* | |
| C15 | 0.0984 (4) | 0.02503 (14) | 0.8517 (2) | 0.0264 (11) | |
| H15 | 0.0785 | 0.0527 | 0.8404 | 0.032* | |
| C16 | 0.0985 (3) | −0.00642 (12) | 0.6426 (2) | 0.0186 (10) | |
| H16 | 0.1383 | −0.0312 | 0.6527 | 0.022* | |
| C17 | −0.0039 (3) | −0.00814 (13) | 0.6002 (2) | 0.0217 (10) | |
| H17 | −0.0318 | −0.0337 | 0.5818 | 0.026* | |
| C18 | −0.0641 (3) | 0.02809 (13) | 0.5853 (2) | 0.0220 (10) | |
| H18 | −0.1333 | 0.0275 | 0.5569 | 0.026* | |
| C19 | −0.0198 (3) | 0.06579 (13) | 0.6135 (2) | 0.0183 (9) | |
| H19 | −0.0606 | 0.0906 | 0.6052 | 0.022* | |
| C20 | 0.0844 (3) | 0.06646 (12) | 0.6537 (2) | 0.0166 (9) | |
| C21 | 0.1359 (3) | 0.10381 (12) | 0.6913 (2) | 0.0158 (9) | |
| C22 | 0.2681 (3) | 0.12141 (12) | 0.7936 (2) | 0.0151 (9) | |
| C23 | 0.3740 (3) | 0.10548 (13) | 0.8336 (2) | 0.0186 (9) | |
| C24 | 0.4533 (3) | 0.13076 (13) | 0.8722 (2) | 0.0197 (10) | |
| H24 | 0.4414 | 0.1595 | 0.8756 | 0.024* | |
| C25 | 0.5505 (3) | 0.11264 (13) | 0.9058 (2) | 0.0244 (10) | |
| H25 | 0.6049 | 0.1292 | 0.9319 | 0.029* | |
| C26 | 0.5665 (4) | 0.07012 (13) | 0.9005 (2) | 0.0242 (10) | |
| H26 | 0.6296 | 0.0573 | 0.9249 | 0.029* | |
| C27 | 0.4869 (3) | 0.04663 (13) | 0.8580 (2) | 0.0211 (10) | |
| H27 | 0.4992 | 0.0180 | 0.8529 | 0.025* | |
| C28 | −0.0338 (3) | 0.23341 (13) | 0.5858 (2) | 0.0207 (10) | |
| H28 | −0.0563 | 0.2605 | 0.5969 | 0.025* | |
| C29 | −0.0568 (3) | 0.21909 (12) | 0.5156 (2) | 0.0191 (10) | |
| H29 | −0.0971 | 0.2357 | 0.4806 | 0.023* | |
| C30 | −0.0194 (3) | 0.17995 (13) | 0.4977 (2) | 0.0203 (10) | |
| H30 | −0.0301 | 0.1704 | 0.4501 | 0.024* | |
| C31 | 0.0343 (3) | 0.15503 (12) | 0.5520 (2) | 0.0172 (9) | |
| H31 | 0.0605 | 0.1285 | 0.5408 | 0.021* | |
| C32 | 0.0491 (3) | 0.16933 (12) | 0.6225 (2) | 0.0166 (9) | |
| C33 | 0.1078 (3) | 0.14650 (12) | 0.6842 (2) | 0.0152 (9) | |
| C34 | 0.2115 (3) | 0.15964 (12) | 0.7997 (2) | 0.0158 (9) | |
| C35 | 0.2151 (3) | 0.18920 (12) | 0.8611 (2) | 0.0174 (9) | |
| C36 | 0.2575 (3) | 0.18020 (13) | 0.9310 (2) | 0.0233 (10) | |
| H36 | 0.2867 | 0.1537 | 0.9426 | 0.028* | |
| C37 | 0.2570 (4) | 0.21042 (14) | 0.9842 (2) | 0.0269 (11) | |
| H37 | 0.2862 | 0.2045 | 1.0316 | 0.032* | |
| C38 | 0.2123 (3) | 0.24982 (14) | 0.9662 (2) | 0.0253 (10) | |
| H38 | 0.2148 | 0.2712 | 1.0006 | 0.030* | |
| C39 | 0.1646 (3) | 0.25648 (13) | 0.8968 (2) | 0.0222 (10) | |
| H39 | 0.1315 | 0.2824 | 0.8853 | 0.027* | |
| C40 | 0.3096 (4) | 0.24702 (13) | 0.6877 (2) | 0.0232 (10) | |
| H40 | 0.3215 | 0.2182 | 0.6911 | 0.028* | |
| C41 | 0.3941 (4) | 0.27222 (13) | 0.6653 (2) | 0.0256 (10) | |
| H41 | 0.4623 | 0.2606 | 0.6547 | 0.031* | |
| C42 | 0.3758 (4) | 0.31444 (14) | 0.6589 (2) | 0.0292 (11) | |
| H42 | 0.4306 | 0.3317 | 0.6421 | 0.035* | |
| C43 | 0.2758 (4) | 0.33143 (14) | 0.6775 (2) | 0.0281 (11) | |
| H43 | 0.2639 | 0.3603 | 0.6746 | 0.034* | |
| C44 | 0.1933 (4) | 0.30535 (13) | 0.7005 (2) | 0.0219 (10) | |
| C45 | 0.0855 (4) | 0.31972 (13) | 0.7234 (2) | 0.0243 (11) | |
| C46 | 0.0477 (4) | 0.36090 (13) | 0.7270 (2) | 0.0314 (12) | |
| H46 | 0.0910 | 0.3830 | 0.7121 | 0.038* | |
| C47 | −0.0548 (4) | 0.36862 (14) | 0.7531 (2) | 0.0352 (12) | |
| H47 | −0.0805 | 0.3961 | 0.7560 | 0.042* | |
| C48 | −0.1195 (4) | 0.33595 (14) | 0.7749 (2) | 0.0319 (12) | |
| H48 | −0.1884 | 0.3412 | 0.7929 | 0.038* | |
| C49 | −0.0805 (4) | 0.29505 (13) | 0.7697 (2) | 0.0227 (10) | |
| C50 | −0.1377 (4) | 0.25614 (14) | 0.7883 (2) | 0.0245 (11) | |
| C51 | −0.2441 (4) | 0.25438 (16) | 0.8121 (2) | 0.0337 (12) | |
| H51 | −0.2842 | 0.2790 | 0.8178 | 0.040* | |
| C52 | −0.2905 (4) | 0.21650 (17) | 0.8274 (3) | 0.0445 (14) | |
| H52 | −0.3622 | 0.2153 | 0.8433 | 0.053* | |
| C53 | −0.2303 (4) | 0.18012 (17) | 0.8190 (3) | 0.0422 (13) | |
| H53 | −0.2603 | 0.1541 | 0.8294 | 0.051* | |
| C54 | −0.1243 (4) | 0.18309 (14) | 0.7947 (2) | 0.0292 (11) | |
| H54 | −0.0842 | 0.1585 | 0.7881 | 0.035* | |
| N13 | 0.0164 (8) | 0.1179 (3) | 0.8910 (5) | 0.068 (3) | 0.639 (11) |
| C55 | 0.0032 (12) | 0.1310 (3) | 0.9445 (7) | 0.056 (3) | 0.639 (11) |
| C56 | 0.006 (2) | 0.1500 (7) | 1.0178 (13) | 0.062 (6) | 0.639 (11) |
| H56A | 0.0421 | 0.1769 | 1.0180 | 0.094* | 0.639 (11) |
| H56B | 0.0467 | 0.1320 | 1.0527 | 0.094* | 0.639 (11) |
| H56C | −0.0703 | 0.1534 | 1.0302 | 0.094* | 0.639 (11) |
| C57 | 0.4656 (4) | 0.26977 (16) | 0.8956 (3) | 0.0340 (12) | |
| N13' | −0.112 (2) | 0.0966 (5) | 0.9245 (9) | 0.112 (10) | 0.361 (11) |
| C55' | −0.070 (3) | 0.1201 (6) | 0.9621 (10) | 0.070 (7) | 0.361 (11) |
| C56' | −0.010 (5) | 0.1545 (15) | 1.003 (3) | 0.089 (15) | 0.361 (11) |
| H56D | 0.0695 | 0.1494 | 1.0074 | 0.133* | 0.361 (11) |
| H56E | −0.0357 | 0.1561 | 1.0507 | 0.133* | 0.361 (11) |
| H56F | −0.0265 | 0.1806 | 0.9781 | 0.133* | 0.361 (11) |
| N14 | 0.4391 (3) | 0.24561 (14) | 0.8530 (2) | 0.0425 (11) | |
| C58 | 0.5019 (4) | 0.30040 (16) | 0.9534 (3) | 0.0525 (15) | |
| H58A | 0.5589 | 0.2879 | 0.9872 | 0.079* | |
| H58B | 0.4382 | 0.3083 | 0.9783 | 0.079* | |
| H58C | 0.5323 | 0.3249 | 0.9321 | 0.079* | |
| C59 | 0.5485 (6) | 0.16313 (16) | 0.6670 (3) | 0.0489 (16) | |
| C60 | 0.6584 (5) | 0.16184 (17) | 0.6398 (3) | 0.0640 (18) | |
| H60A | 0.6938 | 0.1889 | 0.6459 | 0.096* | |
| H60B | 0.6495 | 0.1546 | 0.5892 | 0.096* | |
| H60C | 0.7048 | 0.1412 | 0.6663 | 0.096* | |
| C61 | 0.7993 (5) | 0.0490 (2) | 0.7523 (3) | 0.0512 (15) | |
| C62 | 0.7804 (5) | 0.00479 (17) | 0.7588 (3) | 0.0589 (17) | |
| H62A | 0.7081 | 0.0001 | 0.7762 | 0.088* | |
| H62B | 0.8387 | −0.0072 | 0.7923 | 0.088* | |
| H62C | 0.7817 | −0.0083 | 0.7121 | 0.088* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Ru1 | 0.01606 (19) | 0.01215 (18) | 0.01674 (19) | 0.00127 (14) | 0.00196 (14) | −0.00011 (14) |
| Ru2 | 0.0201 (2) | 0.01344 (19) | 0.01807 (19) | 0.00433 (15) | 0.00167 (15) | −0.00166 (15) |
| P1 | 0.0194 (6) | 0.0221 (7) | 0.0266 (7) | 0.0011 (5) | 0.0021 (5) | −0.0013 (5) |
| P2 | 0.0376 (8) | 0.0355 (8) | 0.0278 (7) | −0.0062 (6) | 0.0048 (6) | 0.0005 (6) |
| P3 | 0.0380 (8) | 0.0253 (7) | 0.0379 (8) | 0.0073 (6) | 0.0027 (6) | −0.0078 (6) |
| F1 | 0.0291 (15) | 0.0270 (14) | 0.0245 (14) | −0.0054 (11) | 0.0043 (11) | 0.0011 (11) |
| F2 | 0.0264 (15) | 0.0183 (14) | 0.0521 (18) | 0.0015 (11) | 0.0018 (13) | −0.0053 (12) |
| F3 | 0.0191 (14) | 0.0351 (16) | 0.0455 (17) | 0.0015 (12) | 0.0057 (12) | −0.0005 (13) |
| F4 | 0.0368 (17) | 0.0472 (18) | 0.0269 (15) | 0.0078 (13) | 0.0008 (12) | −0.0110 (13) |
| F5 | 0.0304 (15) | 0.0200 (13) | 0.0294 (15) | −0.0019 (11) | 0.0066 (12) | 0.0039 (11) |
| F6 | 0.0183 (13) | 0.0254 (14) | 0.0398 (16) | −0.0003 (11) | 0.0014 (11) | −0.0067 (12) |
| F8 | 0.094 (3) | 0.0336 (18) | 0.053 (2) | 0.0041 (17) | 0.0224 (18) | −0.0046 (15) |
| F11 | 0.068 (2) | 0.062 (2) | 0.066 (2) | 0.0283 (18) | 0.0262 (18) | 0.0213 (18) |
| F7 | 0.046 (5) | 0.038 (4) | 0.094 (7) | −0.010 (3) | −0.025 (4) | −0.018 (4) |
| F9 | 0.056 (5) | 0.038 (3) | 0.068 (6) | 0.007 (3) | 0.030 (4) | 0.025 (3) |
| F10 | 0.115 (7) | 0.081 (5) | 0.080 (7) | −0.034 (5) | −0.055 (6) | 0.024 (4) |
| F12 | 0.121 (9) | 0.053 (5) | 0.070 (7) | 0.012 (5) | 0.071 (6) | 0.015 (4) |
| F7' | 0.16 (2) | 0.046 (7) | 0.019 (5) | 0.048 (10) | 0.006 (7) | −0.006 (4) |
| F9' | 0.033 (6) | 0.127 (12) | 0.138 (18) | −0.025 (7) | 0.028 (8) | −0.018 (11) |
| F10' | 0.112 (14) | 0.074 (11) | 0.025 (5) | 0.055 (9) | −0.003 (7) | 0.002 (6) |
| F12' | 0.046 (7) | 0.043 (6) | 0.17 (2) | −0.023 (5) | 0.021 (9) | −0.016 (10) |
| F13 | 0.0499 (19) | 0.0447 (18) | 0.061 (2) | −0.0099 (15) | 0.0293 (16) | −0.0184 (15) |
| F14 | 0.204 (5) | 0.0232 (19) | 0.080 (3) | 0.005 (2) | 0.039 (3) | 0.0015 (18) |
| F15 | 0.0428 (19) | 0.095 (3) | 0.0421 (19) | 0.0274 (18) | −0.0063 (15) | −0.0161 (18) |
| F16 | 0.085 (3) | 0.069 (2) | 0.0383 (19) | 0.0147 (19) | 0.0131 (17) | −0.0218 (17) |
| F17 | 0.096 (3) | 0.0345 (18) | 0.0394 (18) | 0.0012 (17) | −0.0082 (17) | −0.0002 (14) |
| F18 | 0.048 (2) | 0.100 (3) | 0.105 (3) | −0.004 (2) | −0.017 (2) | −0.047 (2) |
| P4 | 0.0226 (7) | 0.0271 (16) | 0.0282 (9) | 0.0022 (9) | 0.0056 (6) | −0.0040 (10) |
| F19 | 0.033 (5) | 0.098 (9) | 0.042 (6) | 0.047 (5) | 0.001 (4) | 0.001 (5) |
| F20 | 0.062 (6) | 0.030 (5) | 0.053 (4) | −0.010 (4) | 0.007 (3) | 0.009 (3) |
| F21 | 0.056 (6) | 0.044 (5) | 0.062 (6) | −0.016 (4) | 0.014 (4) | −0.029 (4) |
| F22 | 0.028 (4) | 0.081 (8) | 0.044 (4) | 0.024 (5) | 0.002 (3) | −0.011 (5) |
| F23 | 0.065 (7) | 0.086 (8) | 0.054 (5) | −0.004 (5) | 0.018 (5) | 0.029 (5) |
| F24 | 0.093 (8) | 0.071 (7) | 0.046 (6) | −0.024 (5) | 0.013 (5) | −0.041 (5) |
| P4' | 0.0226 (7) | 0.0271 (16) | 0.0282 (9) | 0.0022 (9) | 0.0056 (6) | −0.0040 (10) |
| F19' | 0.024 (5) | 0.043 (6) | 0.046 (9) | −0.006 (4) | 0.000 (4) | −0.015 (6) |
| F20' | 0.046 (7) | 0.039 (8) | 0.114 (10) | −0.012 (6) | −0.022 (6) | 0.045 (7) |
| F21' | 0.031 (8) | 0.143 (18) | 0.052 (8) | 0.022 (9) | −0.001 (6) | −0.057 (10) |
| F22' | 0.022 (4) | 0.038 (7) | 0.062 (6) | −0.003 (4) | 0.005 (4) | −0.010 (5) |
| F23' | 0.060 (10) | 0.020 (5) | 0.107 (12) | −0.002 (5) | −0.029 (7) | 0.022 (6) |
| F24' | 0.030 (6) | 0.056 (7) | 0.038 (7) | 0.025 (6) | −0.009 (5) | −0.019 (5) |
| N1 | 0.0149 (19) | 0.0183 (19) | 0.021 (2) | −0.0022 (15) | 0.0005 (15) | −0.0010 (16) |
| N2 | 0.019 (2) | 0.0140 (18) | 0.0180 (19) | 0.0019 (15) | −0.0035 (15) | −0.0024 (15) |
| N3 | 0.021 (2) | 0.019 (2) | 0.0173 (19) | −0.0043 (16) | −0.0003 (16) | −0.0003 (16) |
| N4 | 0.0180 (19) | 0.0160 (19) | 0.0169 (19) | 0.0018 (15) | 0.0056 (15) | 0.0002 (15) |
| N5 | 0.0135 (18) | 0.0169 (19) | 0.0142 (18) | −0.0005 (15) | 0.0012 (15) | 0.0003 (15) |
| N6 | 0.0180 (19) | 0.0124 (18) | 0.0190 (19) | −0.0018 (15) | 0.0050 (15) | −0.0016 (15) |
| N7 | 0.0164 (19) | 0.0172 (19) | 0.0165 (19) | 0.0029 (15) | 0.0022 (15) | 0.0014 (15) |
| N8 | 0.0193 (19) | 0.0136 (18) | 0.0152 (19) | 0.0009 (15) | 0.0030 (15) | −0.0003 (15) |
| N9 | 0.020 (2) | 0.0138 (19) | 0.0193 (19) | −0.0008 (15) | 0.0035 (15) | −0.0021 (15) |
| N10 | 0.024 (2) | 0.019 (2) | 0.018 (2) | 0.0008 (16) | −0.0003 (16) | −0.0025 (15) |
| N11 | 0.026 (2) | 0.0165 (19) | 0.0148 (19) | 0.0041 (16) | −0.0021 (16) | −0.0067 (15) |
| N12 | 0.023 (2) | 0.022 (2) | 0.019 (2) | 0.0052 (16) | 0.0040 (16) | −0.0026 (16) |
| N15 | 0.086 (4) | 0.046 (3) | 0.078 (4) | 0.018 (3) | 0.016 (3) | −0.013 (3) |
| N16 | 0.216 (8) | 0.040 (4) | 0.078 (5) | 0.014 (4) | 0.030 (5) | −0.010 (3) |
| C1 | 0.029 (3) | 0.024 (3) | 0.026 (3) | −0.003 (2) | 0.001 (2) | 0.004 (2) |
| C2 | 0.042 (3) | 0.043 (3) | 0.022 (3) | −0.015 (3) | 0.010 (2) | 0.002 (2) |
| C3 | 0.027 (3) | 0.048 (3) | 0.035 (3) | −0.014 (3) | 0.013 (2) | −0.010 (3) |
| C4 | 0.023 (3) | 0.034 (3) | 0.029 (3) | −0.003 (2) | 0.005 (2) | −0.011 (2) |
| C5 | 0.016 (2) | 0.024 (3) | 0.025 (3) | 0.0004 (19) | 0.0007 (19) | −0.007 (2) |
| C6 | 0.021 (2) | 0.021 (2) | 0.025 (3) | 0.003 (2) | −0.005 (2) | −0.007 (2) |
| C7 | 0.030 (3) | 0.031 (3) | 0.034 (3) | 0.015 (2) | −0.013 (2) | −0.006 (2) |
| C8 | 0.046 (3) | 0.021 (3) | 0.043 (3) | 0.017 (2) | −0.015 (3) | −0.001 (2) |
| C9 | 0.052 (3) | 0.018 (3) | 0.036 (3) | 0.002 (2) | −0.006 (3) | 0.009 (2) |
| C10 | 0.036 (3) | 0.013 (2) | 0.021 (3) | −0.003 (2) | −0.002 (2) | 0.0008 (19) |
| C11 | 0.032 (3) | 0.020 (2) | 0.019 (2) | −0.005 (2) | 0.000 (2) | 0.001 (2) |
| C12 | 0.053 (4) | 0.029 (3) | 0.032 (3) | −0.016 (3) | 0.005 (3) | 0.006 (2) |
| C13 | 0.057 (4) | 0.040 (3) | 0.030 (3) | −0.025 (3) | 0.016 (3) | 0.000 (3) |
| C14 | 0.034 (3) | 0.046 (3) | 0.029 (3) | −0.009 (3) | 0.013 (2) | −0.006 (2) |
| C15 | 0.030 (3) | 0.026 (3) | 0.024 (3) | −0.007 (2) | 0.004 (2) | −0.007 (2) |
| C16 | 0.022 (2) | 0.010 (2) | 0.023 (2) | 0.0006 (18) | 0.0027 (19) | −0.0040 (18) |
| C17 | 0.027 (3) | 0.015 (2) | 0.023 (2) | −0.0052 (19) | 0.004 (2) | −0.0007 (19) |
| C18 | 0.020 (2) | 0.024 (3) | 0.022 (2) | −0.005 (2) | −0.0007 (19) | 0.000 (2) |
| C19 | 0.017 (2) | 0.018 (2) | 0.020 (2) | 0.0017 (18) | 0.0021 (19) | 0.0007 (18) |
| C20 | 0.018 (2) | 0.015 (2) | 0.016 (2) | 0.0019 (18) | 0.0028 (18) | 0.0000 (18) |
| C21 | 0.019 (2) | 0.016 (2) | 0.014 (2) | −0.0002 (18) | 0.0062 (18) | 0.0001 (18) |
| C22 | 0.020 (2) | 0.013 (2) | 0.014 (2) | −0.0004 (17) | 0.0060 (18) | 0.0008 (17) |
| C23 | 0.019 (2) | 0.020 (2) | 0.018 (2) | −0.0009 (19) | 0.0044 (18) | 0.0010 (19) |
| C24 | 0.023 (2) | 0.016 (2) | 0.019 (2) | 0.0019 (19) | −0.0014 (19) | −0.0029 (18) |
| C25 | 0.020 (2) | 0.029 (3) | 0.024 (3) | −0.004 (2) | −0.002 (2) | −0.004 (2) |
| C26 | 0.023 (3) | 0.026 (3) | 0.021 (2) | 0.004 (2) | −0.005 (2) | −0.005 (2) |
| C27 | 0.025 (3) | 0.018 (2) | 0.020 (2) | 0.0075 (19) | 0.003 (2) | 0.0008 (19) |
| C28 | 0.021 (2) | 0.017 (2) | 0.024 (3) | 0.0027 (19) | 0.0024 (19) | 0.0024 (19) |
| C29 | 0.019 (2) | 0.019 (2) | 0.018 (2) | 0.0007 (18) | −0.0043 (18) | 0.0033 (18) |
| C30 | 0.022 (2) | 0.023 (2) | 0.016 (2) | −0.0064 (19) | 0.0024 (19) | −0.0014 (19) |
| C31 | 0.018 (2) | 0.012 (2) | 0.022 (2) | 0.0019 (17) | 0.0026 (18) | −0.0024 (18) |
| C32 | 0.016 (2) | 0.017 (2) | 0.017 (2) | 0.0008 (18) | 0.0026 (18) | −0.0034 (18) |
| C33 | 0.017 (2) | 0.015 (2) | 0.014 (2) | −0.0019 (17) | 0.0043 (18) | 0.0000 (18) |
| C34 | 0.017 (2) | 0.014 (2) | 0.017 (2) | −0.0034 (18) | 0.0050 (18) | 0.0020 (18) |
| C35 | 0.018 (2) | 0.016 (2) | 0.019 (2) | 0.0001 (18) | 0.0052 (18) | 0.0004 (18) |
| C36 | 0.029 (3) | 0.020 (2) | 0.020 (2) | 0.004 (2) | −0.001 (2) | 0.000 (2) |
| C37 | 0.033 (3) | 0.030 (3) | 0.016 (2) | 0.004 (2) | −0.001 (2) | 0.002 (2) |
| C38 | 0.029 (3) | 0.025 (3) | 0.022 (3) | 0.000 (2) | 0.002 (2) | −0.006 (2) |
| C39 | 0.025 (3) | 0.016 (2) | 0.025 (3) | 0.0071 (19) | 0.002 (2) | −0.004 (2) |
| C40 | 0.026 (3) | 0.020 (2) | 0.023 (2) | 0.000 (2) | −0.003 (2) | 0.0002 (19) |
| C41 | 0.023 (3) | 0.029 (3) | 0.024 (3) | −0.004 (2) | 0.000 (2) | 0.001 (2) |
| C42 | 0.032 (3) | 0.032 (3) | 0.023 (3) | −0.014 (2) | −0.001 (2) | −0.005 (2) |
| C43 | 0.046 (3) | 0.018 (2) | 0.019 (3) | −0.009 (2) | −0.001 (2) | −0.003 (2) |
| C44 | 0.033 (3) | 0.017 (2) | 0.014 (2) | 0.002 (2) | −0.0072 (19) | −0.0017 (19) |
| C45 | 0.034 (3) | 0.014 (2) | 0.022 (3) | 0.006 (2) | −0.008 (2) | −0.0020 (19) |
| C46 | 0.047 (3) | 0.014 (2) | 0.031 (3) | 0.003 (2) | −0.009 (2) | 0.000 (2) |
| C47 | 0.048 (3) | 0.015 (3) | 0.040 (3) | 0.012 (2) | −0.007 (3) | −0.004 (2) |
| C48 | 0.035 (3) | 0.032 (3) | 0.028 (3) | 0.018 (2) | −0.005 (2) | −0.011 (2) |
| C49 | 0.030 (3) | 0.023 (3) | 0.016 (2) | 0.012 (2) | 0.001 (2) | −0.0050 (19) |
| C50 | 0.025 (3) | 0.035 (3) | 0.013 (2) | 0.010 (2) | −0.0009 (19) | −0.007 (2) |
| C51 | 0.027 (3) | 0.043 (3) | 0.031 (3) | 0.015 (2) | 0.003 (2) | −0.006 (2) |
| C52 | 0.032 (3) | 0.050 (4) | 0.055 (4) | 0.005 (3) | 0.022 (3) | −0.003 (3) |
| C53 | 0.032 (3) | 0.045 (3) | 0.052 (4) | −0.002 (3) | 0.018 (3) | 0.002 (3) |
| C54 | 0.030 (3) | 0.027 (3) | 0.033 (3) | 0.005 (2) | 0.010 (2) | 0.000 (2) |
| N13 | 0.080 (7) | 0.039 (5) | 0.082 (7) | 0.021 (5) | 0.000 (6) | −0.004 (5) |
| C55 | 0.066 (9) | 0.032 (6) | 0.069 (9) | 0.016 (6) | 0.012 (6) | −0.001 (6) |
| C56 | 0.092 (17) | 0.027 (7) | 0.077 (11) | −0.002 (8) | 0.051 (10) | −0.009 (7) |
| C57 | 0.020 (3) | 0.036 (3) | 0.046 (3) | 0.007 (2) | 0.004 (2) | 0.006 (3) |
| N13' | 0.23 (3) | 0.056 (12) | 0.038 (10) | 0.041 (13) | −0.055 (13) | −0.011 (8) |
| C55' | 0.118 (19) | 0.050 (13) | 0.046 (12) | 0.039 (13) | 0.025 (14) | 0.018 (10) |
| C56' | 0.054 (18) | 0.10 (3) | 0.11 (3) | 0.00 (2) | 0.011 (17) | 0.02 (2) |
| N14 | 0.033 (3) | 0.048 (3) | 0.047 (3) | 0.004 (2) | 0.005 (2) | −0.003 (2) |
| C58 | 0.042 (3) | 0.034 (3) | 0.079 (4) | −0.001 (3) | −0.006 (3) | −0.010 (3) |
| C59 | 0.077 (5) | 0.030 (3) | 0.041 (4) | 0.014 (3) | 0.012 (3) | −0.009 (3) |
| C60 | 0.107 (6) | 0.044 (4) | 0.043 (4) | 0.014 (4) | 0.018 (4) | −0.001 (3) |
| C61 | 0.073 (4) | 0.047 (4) | 0.036 (3) | 0.009 (3) | 0.015 (3) | −0.003 (3) |
| C62 | 0.066 (4) | 0.048 (4) | 0.059 (4) | −0.015 (3) | −0.012 (3) | 0.019 (3) |
| Ru1—N5 | 1.960 (3) | C13—C14 | 1.382 (6) |
| Ru1—N2 | 1.979 (3) | C13—H13 | 0.9300 |
| Ru1—N4 | 2.058 (3) | C14—C15 | 1.378 (6) |
| Ru1—N6 | 2.060 (3) | C14—H14 | 0.9300 |
| Ru1—N3 | 2.071 (3) | C15—H15 | 0.9300 |
| Ru1—N1 | 2.074 (3) | C16—C17 | 1.381 (5) |
| Ru2—N8 | 1.971 (3) | C16—H16 | 0.9300 |
| Ru2—N11 | 1.989 (3) | C17—C18 | 1.370 (5) |
| Ru2—N9 | 2.051 (3) | C17—H17 | 0.9300 |
| Ru2—N7 | 2.061 (3) | C18—C19 | 1.390 (5) |
| Ru2—N10 | 2.067 (3) | C18—H18 | 0.9300 |
| Ru2—N12 | 2.074 (3) | C19—C20 | 1.379 (5) |
| P1—F3 | 1.592 (2) | C19—H19 | 0.9300 |
| P1—F6 | 1.601 (2) | C20—C21 | 1.478 (5) |
| P1—F4 | 1.603 (3) | C21—C33 | 1.402 (5) |
| P1—F1 | 1.604 (2) | C22—C34 | 1.401 (5) |
| P1—F2 | 1.605 (2) | C22—C23 | 1.483 (5) |
| P1—F5 | 1.612 (2) | C23—C24 | 1.382 (5) |
| P2—F7 | 1.539 (6) | C24—C25 | 1.381 (5) |
| P2—F12 | 1.550 (6) | C24—H24 | 0.9300 |
| P2—F10' | 1.560 (10) | C25—C26 | 1.371 (6) |
| P2—F9' | 1.574 (10) | C25—H25 | 0.9300 |
| P2—F12' | 1.590 (10) | C26—C27 | 1.387 (6) |
| P2—F9 | 1.595 (5) | C26—H26 | 0.9300 |
| P2—F11 | 1.595 (3) | C27—H27 | 0.9300 |
| P2—F8 | 1.596 (3) | C28—C29 | 1.379 (5) |
| P2—F7' | 1.605 (8) | C28—H28 | 0.9300 |
| P2—F10 | 1.608 (6) | C29—C30 | 1.374 (5) |
| P3—F14 | 1.554 (3) | C29—H29 | 0.9300 |
| P3—F18 | 1.564 (3) | C30—C31 | 1.384 (5) |
| P3—F16 | 1.584 (3) | C30—H30 | 0.9300 |
| P3—F13 | 1.594 (3) | C31—C32 | 1.376 (5) |
| P3—F17 | 1.596 (3) | C31—H31 | 0.9300 |
| P3—F15 | 1.602 (3) | C32—C33 | 1.468 (5) |
| P4—F23 | 1.573 (9) | C34—C35 | 1.473 (5) |
| P4—F20 | 1.576 (8) | C35—C36 | 1.370 (5) |
| P4—F19 | 1.580 (8) | C36—C37 | 1.377 (6) |
| P4—F24 | 1.581 (9) | C36—H36 | 0.9300 |
| P4—F22 | 1.584 (8) | C37—C38 | 1.389 (6) |
| P4—F21 | 1.587 (9) | C37—H37 | 0.9300 |
| P4'—F24' | 1.582 (11) | C38—C39 | 1.367 (5) |
| P4'—F21' | 1.585 (11) | C38—H38 | 0.9300 |
| P4'—F23' | 1.587 (11) | C39—H39 | 0.9300 |
| P4'—F19' | 1.589 (11) | C40—C41 | 1.382 (6) |
| P4'—F22' | 1.589 (11) | C40—H40 | 0.9300 |
| P4'—F20' | 1.590 (11) | C41—C42 | 1.364 (6) |
| N1—C1 | 1.339 (5) | C41—H41 | 0.9300 |
| N1—C5 | 1.373 (5) | C42—C43 | 1.382 (6) |
| N2—C10 | 1.341 (5) | C42—H42 | 0.9300 |
| N2—C6 | 1.352 (5) | C43—C44 | 1.384 (6) |
| N3—C15 | 1.334 (5) | C43—H43 | 0.9300 |
| N3—C11 | 1.376 (5) | C44—C45 | 1.464 (6) |
| N4—C16 | 1.343 (5) | C45—C46 | 1.390 (5) |
| N4—C20 | 1.376 (5) | C46—C47 | 1.377 (6) |
| N5—C22 | 1.364 (5) | C46—H46 | 0.9300 |
| N5—C21 | 1.366 (5) | C47—C48 | 1.378 (6) |
| N6—C27 | 1.332 (5) | C47—H47 | 0.9300 |
| N6—C23 | 1.372 (5) | C48—C49 | 1.388 (5) |
| N7—C28 | 1.339 (5) | C48—H48 | 0.9300 |
| N7—C32 | 1.383 (5) | C49—C50 | 1.470 (6) |
| N8—C34 | 1.352 (5) | C50—C51 | 1.382 (6) |
| N8—C33 | 1.369 (5) | C51—C52 | 1.367 (6) |
| N9—C39 | 1.354 (5) | C51—H51 | 0.9300 |
| N9—C35 | 1.373 (5) | C52—C53 | 1.378 (6) |
| N10—C40 | 1.345 (5) | C52—H52 | 0.9300 |
| N10—C44 | 1.371 (5) | C53—C54 | 1.384 (6) |
| N11—C49 | 1.351 (5) | C53—H53 | 0.9300 |
| N11—C45 | 1.351 (5) | C54—H54 | 0.9300 |
| N12—C54 | 1.338 (5) | N13—C55 | 1.100 (10) |
| N12—C50 | 1.374 (5) | C55—C56 | 1.484 (18) |
| N15—C59 | 1.132 (7) | C56—H56A | 0.9600 |
| N16—C61 | 1.114 (7) | C56—H56B | 0.9600 |
| C1—C2 | 1.379 (6) | C56—H56C | 0.9600 |
| C1—H1 | 0.9300 | C57—N14 | 1.124 (6) |
| C2—C3 | 1.378 (6) | C57—C58 | 1.478 (7) |
| C2—H2 | 0.9300 | N13'—C55' | 1.105 (16) |
| C3—C4 | 1.367 (6) | C55'—C56' | 1.47 (2) |
| C3—H3 | 0.9300 | C56'—H56D | 0.9600 |
| C4—C5 | 1.384 (5) | C56'—H56E | 0.9600 |
| C4—H4 | 0.9300 | C56'—H56F | 0.9600 |
| C5—C6 | 1.474 (6) | C58—H58A | 0.9600 |
| C6—C7 | 1.382 (6) | C58—H58B | 0.9600 |
| C7—C8 | 1.370 (6) | C58—H58C | 0.9600 |
| C7—H7 | 0.9300 | C59—C60 | 1.449 (8) |
| C8—C9 | 1.369 (6) | C60—H60A | 0.9600 |
| C8—H8 | 0.9300 | C60—H60B | 0.9600 |
| C9—C10 | 1.393 (6) | C60—H60C | 0.9600 |
| C9—H9 | 0.9300 | C61—C62 | 1.432 (8) |
| C10—C11 | 1.467 (6) | C62—H62A | 0.9600 |
| C11—C12 | 1.386 (6) | C62—H62B | 0.9600 |
| C12—C13 | 1.377 (7) | C62—H62C | 0.9600 |
| C12—H12 | 0.9300 | ||
| N5—Ru1—N2 | 176.41 (13) | C4—C5—C6 | 124.0 (4) |
| N5—Ru1—N4 | 79.19 (13) | N2—C6—C7 | 120.4 (4) |
| N2—Ru1—N4 | 104.39 (13) | N2—C6—C5 | 112.7 (3) |
| N5—Ru1—N6 | 80.12 (13) | C7—C6—C5 | 126.9 (4) |
| N2—Ru1—N6 | 96.29 (13) | C8—C7—C6 | 118.3 (5) |
| N4—Ru1—N6 | 159.28 (12) | C8—C7—H7 | 120.9 |
| N5—Ru1—N3 | 101.38 (13) | C6—C7—H7 | 120.9 |
| N2—Ru1—N3 | 78.91 (13) | C9—C8—C7 | 121.4 (4) |
| N4—Ru1—N3 | 89.18 (12) | C9—C8—H8 | 119.3 |
| N6—Ru1—N3 | 93.68 (12) | C7—C8—H8 | 119.3 |
| N5—Ru1—N1 | 100.95 (13) | C8—C9—C10 | 118.7 (4) |
| N2—Ru1—N1 | 78.93 (13) | C8—C9—H9 | 120.7 |
| N4—Ru1—N1 | 93.01 (12) | C10—C9—H9 | 120.7 |
| N6—Ru1—N1 | 92.11 (12) | N2—C10—C9 | 119.7 (4) |
| N3—Ru1—N1 | 157.57 (13) | N2—C10—C11 | 113.4 (4) |
| N8—Ru2—N11 | 178.32 (14) | C9—C10—C11 | 126.9 (4) |
| N8—Ru2—N9 | 79.26 (13) | N3—C11—C12 | 120.1 (4) |
| N11—Ru2—N9 | 99.13 (13) | N3—C11—C10 | 114.7 (4) |
| N8—Ru2—N7 | 79.21 (13) | C12—C11—C10 | 125.1 (4) |
| N11—Ru2—N7 | 102.40 (13) | C13—C12—C11 | 120.0 (5) |
| N9—Ru2—N7 | 158.45 (13) | C13—C12—H12 | 120.0 |
| N8—Ru2—N10 | 100.63 (13) | C11—C12—H12 | 120.0 |
| N11—Ru2—N10 | 78.89 (14) | C12—C13—C14 | 119.7 (4) |
| N9—Ru2—N10 | 90.55 (13) | C12—C13—H13 | 120.1 |
| N7—Ru2—N10 | 92.59 (12) | C14—C13—H13 | 120.1 |
| N8—Ru2—N12 | 101.72 (13) | C15—C14—C13 | 118.0 (5) |
| N11—Ru2—N12 | 78.74 (14) | C15—C14—H14 | 121.0 |
| N9—Ru2—N12 | 92.80 (13) | C13—C14—H14 | 121.0 |
| N7—Ru2—N12 | 92.36 (13) | N3—C15—C14 | 123.5 (4) |
| N10—Ru2—N12 | 157.63 (13) | N3—C15—H15 | 118.3 |
| F3—P1—F6 | 179.39 (15) | C14—C15—H15 | 118.3 |
| F3—P1—F4 | 90.49 (14) | N4—C16—C17 | 122.5 (4) |
| F6—P1—F4 | 89.79 (14) | N4—C16—H16 | 118.8 |
| F3—P1—F1 | 90.57 (13) | C17—C16—H16 | 118.8 |
| F6—P1—F1 | 89.14 (13) | C18—C17—C16 | 119.5 (4) |
| F4—P1—F1 | 178.79 (15) | C18—C17—H17 | 120.2 |
| F3—P1—F2 | 90.07 (13) | C16—C17—H17 | 120.2 |
| F6—P1—F2 | 90.47 (13) | C17—C18—C19 | 118.8 (4) |
| F4—P1—F2 | 90.58 (14) | C17—C18—H18 | 120.6 |
| F1—P1—F2 | 90.00 (13) | C19—C18—H18 | 120.6 |
| F3—P1—F5 | 89.60 (13) | C20—C19—C18 | 120.1 (4) |
| F6—P1—F5 | 89.85 (13) | C20—C19—H19 | 120.0 |
| F4—P1—F5 | 89.98 (14) | C18—C19—H19 | 120.0 |
| F1—P1—F5 | 89.45 (13) | N4—C20—C19 | 120.7 (4) |
| F2—P1—F5 | 179.36 (16) | N4—C20—C21 | 113.8 (3) |
| F7—P2—F12 | 93.0 (5) | C19—C20—C21 | 125.0 (4) |
| F7—P2—F10' | 129.4 (7) | N5—C21—C33 | 116.9 (3) |
| F7—P2—F9' | 139.3 (7) | N5—C21—C20 | 112.4 (3) |
| F12—P2—F9' | 127.3 (7) | C33—C21—C20 | 130.6 (4) |
| F10'—P2—F9' | 90.0 (7) | N5—C22—C34 | 117.1 (4) |
| F10'—P2—F12' | 90.3 (8) | N5—C22—C23 | 112.6 (3) |
| F9'—P2—F12' | 168.2 (8) | C34—C22—C23 | 130.3 (4) |
| F7—P2—F9 | 90.7 (4) | N6—C23—C24 | 121.3 (4) |
| F12—P2—F9 | 171.6 (4) | N6—C23—C22 | 114.4 (3) |
| F10'—P2—F9 | 139.9 (7) | C24—C23—C22 | 124.0 (4) |
| F12'—P2—F9 | 129.7 (8) | C25—C24—C23 | 119.0 (4) |
| F7—P2—F11 | 87.6 (3) | C25—C24—H24 | 120.5 |
| F12—P2—F11 | 87.2 (3) | C23—C24—H24 | 120.5 |
| F10'—P2—F11 | 96.9 (5) | C26—C25—C24 | 119.7 (4) |
| F9'—P2—F11 | 98.7 (6) | C26—C25—H25 | 120.2 |
| F12'—P2—F11 | 93.0 (4) | C24—C25—H25 | 120.2 |
| F9—P2—F11 | 85.5 (2) | C25—C26—C27 | 118.8 (4) |
| F7—P2—F8 | 92.4 (3) | C25—C26—H26 | 120.6 |
| F12—P2—F8 | 94.0 (3) | C27—C26—H26 | 120.6 |
| F10'—P2—F8 | 84.1 (5) | N6—C27—C26 | 122.7 (4) |
| F9'—P2—F8 | 80.5 (6) | N6—C27—H27 | 118.7 |
| F12'—P2—F8 | 87.8 (4) | C26—C27—H27 | 118.7 |
| F9—P2—F8 | 93.3 (2) | N7—C28—C29 | 122.7 (4) |
| F11—P2—F8 | 178.79 (18) | N7—C28—H28 | 118.6 |
| F12—P2—F7' | 145.0 (7) | C29—C28—H28 | 118.6 |
| F10'—P2—F7' | 168.2 (6) | C30—C29—C28 | 119.2 (4) |
| F9'—P2—F7' | 87.0 (7) | C30—C29—H29 | 120.4 |
| F12'—P2—F7' | 90.4 (8) | C28—C29—H29 | 120.4 |
| F11—P2—F7' | 94.9 (4) | C29—C30—C31 | 118.8 (4) |
| F8—P2—F7' | 84.2 (4) | C29—C30—H30 | 120.6 |
| F7—P2—F10 | 172.8 (4) | C31—C30—H30 | 120.6 |
| F12—P2—F10 | 88.6 (5) | C32—C31—C30 | 120.2 (4) |
| F12'—P2—F10 | 143.2 (8) | C32—C31—H31 | 119.9 |
| F9—P2—F10 | 86.9 (4) | C30—C31—H31 | 119.9 |
| F11—P2—F10 | 85.6 (3) | C31—C32—N7 | 120.4 (4) |
| F8—P2—F10 | 94.4 (3) | C31—C32—C33 | 125.3 (4) |
| F7'—P2—F10 | 126.4 (7) | N7—C32—C33 | 113.8 (3) |
| F14—P3—F18 | 92.9 (2) | N8—C33—C21 | 117.1 (3) |
| F14—P3—F16 | 89.06 (19) | N8—C33—C32 | 112.9 (3) |
| F18—P3—F16 | 89.84 (19) | C21—C33—C32 | 130.0 (4) |
| F14—P3—F13 | 90.81 (18) | N8—C34—C22 | 117.3 (4) |
| F18—P3—F13 | 91.75 (18) | N8—C34—C35 | 112.8 (3) |
| F16—P3—F13 | 178.40 (19) | C22—C34—C35 | 129.8 (4) |
| F14—P3—F17 | 176.7 (2) | C36—C35—N9 | 120.9 (4) |
| F18—P3—F17 | 90.30 (19) | C36—C35—C34 | 125.1 (4) |
| F16—P3—F17 | 89.95 (17) | N9—C35—C34 | 113.8 (3) |
| F13—P3—F17 | 90.09 (16) | C35—C36—C37 | 120.1 (4) |
| F14—P3—F15 | 90.3 (2) | C35—C36—H36 | 120.0 |
| F18—P3—F15 | 176.8 (2) | C37—C36—H36 | 120.0 |
| F16—P3—F15 | 89.83 (17) | C36—C37—C38 | 119.3 (4) |
| F13—P3—F15 | 88.58 (16) | C36—C37—H37 | 120.4 |
| F17—P3—F15 | 86.48 (18) | C38—C37—H37 | 120.4 |
| F23—P4—F20 | 178.1 (8) | C39—C38—C37 | 118.5 (4) |
| F23—P4—F19 | 88.6 (7) | C39—C38—H38 | 120.8 |
| F20—P4—F19 | 92.7 (6) | C37—C38—H38 | 120.8 |
| F23—P4—F24 | 90.0 (7) | N9—C39—C38 | 122.9 (4) |
| F20—P4—F24 | 91.3 (7) | N9—C39—H39 | 118.5 |
| F19—P4—F24 | 91.5 (7) | C38—C39—H39 | 118.5 |
| F23—P4—F22 | 90.0 (6) | N10—C40—C41 | 122.3 (4) |
| F20—P4—F22 | 88.6 (6) | N10—C40—H40 | 118.9 |
| F19—P4—F22 | 177.3 (8) | C41—C40—H40 | 118.9 |
| F24—P4—F22 | 90.8 (7) | C42—C41—C40 | 118.9 (4) |
| F23—P4—F21 | 91.6 (8) | C42—C41—H41 | 120.6 |
| F20—P4—F21 | 87.1 (6) | C40—C41—H41 | 120.6 |
| F19—P4—F21 | 89.0 (8) | C41—C42—C43 | 119.8 (4) |
| F24—P4—F21 | 178.3 (9) | C41—C42—H42 | 120.1 |
| F22—P4—F21 | 88.7 (8) | C43—C42—H42 | 120.1 |
| F24'—P4'—F21' | 177.5 (11) | C42—C43—C44 | 119.8 (4) |
| F24'—P4'—F23' | 89.7 (9) | C42—C43—H43 | 120.1 |
| F21'—P4'—F23' | 88.2 (10) | C44—C43—H43 | 120.1 |
| F24'—P4'—F19' | 89.9 (9) | N10—C44—C43 | 120.2 (4) |
| F21'—P4'—F19' | 88.7 (9) | N10—C44—C45 | 115.0 (4) |
| F23'—P4'—F19' | 89.8 (8) | C43—C44—C45 | 124.8 (4) |
| F24'—P4'—F22' | 88.7 (8) | N11—C45—C46 | 119.4 (4) |
| F21'—P4'—F22' | 92.7 (9) | N11—C45—C44 | 113.3 (4) |
| F23'—P4'—F22' | 91.0 (8) | C46—C45—C44 | 127.3 (4) |
| F19'—P4'—F22' | 178.4 (11) | C47—C46—C45 | 119.2 (4) |
| F24'—P4'—F20' | 90.9 (9) | C47—C46—H46 | 120.4 |
| F21'—P4'—F20' | 91.1 (9) | C45—C46—H46 | 120.4 |
| F23'—P4'—F20' | 179.1 (11) | C46—C47—C48 | 120.6 (4) |
| F19'—P4'—F20' | 89.6 (8) | C46—C47—H47 | 119.7 |
| F22'—P4'—F20' | 89.7 (7) | C48—C47—H47 | 119.7 |
| C1—N1—C5 | 117.9 (4) | C47—C48—C49 | 119.1 (4) |
| C1—N1—Ru1 | 128.1 (3) | C47—C48—H48 | 120.4 |
| C5—N1—Ru1 | 113.9 (3) | C49—C48—H48 | 120.4 |
| C10—N2—C6 | 121.5 (4) | N11—C49—C48 | 119.5 (4) |
| C10—N2—Ru1 | 119.0 (3) | N11—C49—C50 | 113.0 (3) |
| C6—N2—Ru1 | 119.2 (3) | C48—C49—C50 | 127.4 (4) |
| C15—N3—C11 | 118.7 (4) | N12—C50—C51 | 120.4 (4) |
| C15—N3—Ru1 | 127.5 (3) | N12—C50—C49 | 114.9 (4) |
| C11—N3—Ru1 | 113.8 (3) | C51—C50—C49 | 124.7 (4) |
| C16—N4—C20 | 118.4 (3) | C52—C51—C50 | 120.2 (4) |
| C16—N4—Ru1 | 126.4 (3) | C52—C51—H51 | 119.9 |
| C20—N4—Ru1 | 114.7 (2) | C50—C51—H51 | 119.9 |
| C22—N5—C21 | 123.1 (3) | C51—C52—C53 | 119.5 (5) |
| C22—N5—Ru1 | 118.0 (3) | C51—C52—H52 | 120.3 |
| C21—N5—Ru1 | 118.9 (3) | C53—C52—H52 | 120.3 |
| C27—N6—C23 | 118.3 (3) | C52—C53—C54 | 118.7 (5) |
| C27—N6—Ru1 | 127.7 (3) | C52—C53—H53 | 120.7 |
| C23—N6—Ru1 | 113.5 (3) | C54—C53—H53 | 120.7 |
| C28—N7—C32 | 118.2 (3) | N12—C54—C53 | 122.5 (4) |
| C28—N7—Ru2 | 127.0 (3) | N12—C54—H54 | 118.7 |
| C32—N7—Ru2 | 114.6 (2) | C53—C54—H54 | 118.7 |
| C34—N8—C33 | 123.2 (3) | N13—C55—C56 | 170.6 (17) |
| C34—N8—Ru2 | 118.4 (3) | N14—C57—C58 | 178.1 (6) |
| C33—N8—Ru2 | 118.4 (3) | N13'—C55'—C56' | 172 (4) |
| C39—N9—C35 | 118.0 (3) | C55'—C56'—H56D | 109.5 |
| C39—N9—Ru2 | 127.3 (3) | C55'—C56'—H56E | 109.5 |
| C35—N9—Ru2 | 114.4 (3) | H56D—C56'—H56E | 109.5 |
| C40—N10—C44 | 119.0 (4) | C55'—C56'—H56F | 109.5 |
| C40—N10—Ru2 | 126.8 (3) | H56D—C56'—H56F | 109.5 |
| C44—N10—Ru2 | 114.2 (3) | H56E—C56'—H56F | 109.5 |
| C49—N11—C45 | 122.2 (4) | C57—C58—H58A | 109.5 |
| C49—N11—Ru2 | 119.1 (3) | C57—C58—H58B | 109.5 |
| C45—N11—Ru2 | 118.7 (3) | H58A—C58—H58B | 109.5 |
| C54—N12—C50 | 118.6 (4) | C57—C58—H58C | 109.5 |
| C54—N12—Ru2 | 127.2 (3) | H58A—C58—H58C | 109.5 |
| C50—N12—Ru2 | 114.1 (3) | H58B—C58—H58C | 109.5 |
| N1—C1—C2 | 122.9 (4) | N15—C59—C60 | 177.3 (7) |
| N1—C1—H1 | 118.6 | C59—C60—H60A | 109.5 |
| C2—C1—H1 | 118.6 | C59—C60—H60B | 109.5 |
| C3—C2—C1 | 119.0 (4) | H60A—C60—H60B | 109.5 |
| C3—C2—H2 | 120.5 | C59—C60—H60C | 109.5 |
| C1—C2—H2 | 120.5 | H60A—C60—H60C | 109.5 |
| C4—C3—C2 | 119.1 (4) | H60B—C60—H60C | 109.5 |
| C4—C3—H3 | 120.4 | N16—C61—C62 | 178.7 (7) |
| C2—C3—H3 | 120.4 | C61—C62—H62A | 109.5 |
| C3—C4—C5 | 120.1 (4) | C61—C62—H62B | 109.5 |
| C3—C4—H4 | 119.9 | H62A—C62—H62B | 109.5 |
| C5—C4—H4 | 119.9 | C61—C62—H62C | 109.5 |
| N1—C5—C4 | 120.9 (4) | H62A—C62—H62C | 109.5 |
| N1—C5—C6 | 115.0 (4) | H62B—C62—H62C | 109.5 |
Support by the US Department of Energy through the Laboratory Directed Research and Development (LDRD) program at LANL is gratefully acknowledged.
Arana, C. R. & Abruña, H. D. (1993). Inorg. Chem. 32, 194–203.
Bruker (2007). APEX and SAINT-Plus. Bruker AXS, Inc., Madison, Wisconsin, USA.
Chen, W., Rein, F. N., Scott, B. L. & Rocha, R. C. (2011). Chem. Eur. J. 17, 5595–5604.
Dattelbaum, D. M., Hartshorn, C. M. & Meyer, T. J. (2002). J. Am. Chem. Soc. 124, 4938–4939.
Flores-Torres, S., Hutchison, G. R., Stoltzberg, L. J. & Abruña, H. D. (2006). J. Am. Chem. Soc. 128, 1513–1522.
Gourdon, A. & Launay, J.-P. (1998). Inorg. Chem. 37, 5336–5341.
Jones, S. W., Vrana, L. M. & Brewer, K. J. (1998). J. Organomet. Chem. 554, 29–40.
Rocha, R. C., Rein, F. N., Jude, H., Shreve, A. P., Concepcion, J. J. & Meyer, T. J. (2008). Angew. Chem. Int. Ed. 47, 503–506.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Thummel, R. P. & Chirayil, S. (1988). Inorg. Chim. Acta, 154, 77–81.
Vogler, L. M., Jones, S. W., Jensen, G. E., Brewer, R. G. & Brewer, K. J. (1996). Inorg. Chim. Acta, 250, 155–162.
Wadman, S. H., Havenith, R. W. A., Hartl, F., Lutz, M., Spek, A. L., van Klink, G. P. M. & van Koten, G. (2009). Inorg. Chem. 48, 5685–5696.
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.
Yoshikawa, N., Yamabe, S., Kanehisa, N., Inoue, T., Takashima, H. & Tsukahara, K. (2011). J. Phys. Org. Chem. 24, 1110–1118.
The PF6- salt of the symmetric dinuclear complex [(tpy)RuII(µ-tppz)RuII(tpy)]4+ (I) in acetonitrile crystallized in the monoclinic space group (P21/c). Its crystal structure is shown in Figs. 1 and 2, and discussed below.
A structure of the compound [(tpy)Ru(tppz)Ru(tpy)](PF6)4 was recently reported (Yoshikawa et al., 2011). In this case, the compound crystallized in the triclinic (P1) space group, without containing solvent molecules in the unit. However, the relatively poor quality of that structure (R-factor = 15.61%) and relatively large deviations in metal-ligand bond distances (0.02 Å) and angles (0.6–0.8°) precludes an accurate comparison with the data reported here. A better comparative analysis involves the only other crystallographically characterized compound featuring the {(tpy)Ru(tppz)Ru} fragment, the PF6- salt of the photocatalyst [(tpy)RuII(tppz)RuII(bpy)(Cl)]3+ (II; Chen et al., 2011).
In the {(tpy)Ru(tppz)} moiety of II, the average Ru—N distances (tpy: Ru—Nouter = 2.071 (4) Å and Ru—Ncentral = 1.984 (4) Å; tppz: Ru—Nouter = 2.056 (4) Å and Ru—Ncentral = 1.963 (4) Å) and bite angles of the mer-coordinated tpy and tppz (157.59 (17)°–159.43 (16)°) are nearly identical to those observed for I. Also similar but even more pronounced in II is the highly distorted saddle-like conformation adopted by the bridging tppz ligand, with an average torsion angle of 52.2 (3)° between adjacent pyridyl rings.
In [(tpy)Ru(tppz)Ru(tpy)](PF6)4×4MeCN, the cation (I) packs in alternating layers with the PF6- anions and solvent molecules packed between the cations. No significant interactions are present between different layers. Two of the PF6- counterions and one of the MeCN solvent molecules are disordered (Fig. 2). The percentage of the major disordered component is 62 (2)% for the first anion (atoms P2, F7 to F12), 57 (2)% for the second anion (P4, F19 to F24), and 64 (1)% for the solvent molecule (N13, C55, C56).