Acta Cryst. (2009). E65, m1184 [ doi:10.1107/S1600536809035302 ]
The title compound, [Ru(C10H8N2)2(C13H7N3S)](PF6)2·CH3CN, was synthesized by the reaction of thiophosgene and bis(2,2'-bipyridine)(1,10-phenanthrolin-5-amine)ruthenium(II) bis(hexafluoridophosphate). The RuII atom adopts a slightly distorted octahedral RuN6 coordinaton formed by four N atoms of two bipyridine ligands and by two N atoms of the 1,10-phenantroline ligand. The isothiocyanate group is almost linear, with an N-C-S angle of 174.4 (6)°. Two of the three hexafluoridophosphate counter-anions are located on inversion centres.
Bis(2,2'-bipyridine)(1,10-phenanthroline-5-amine)ruthenium(II) bis(hexafluoridophosphate) (450 mg, 0.5 mmol) was dissolved in acetone (100 ml). To this dark red solution was added Na2CO3 (212 mg, 2.0 mmol). After addition of CSCl2 (0.5 ml) to the reaction mixture under N2 atmosphere, it was stirred for 7 h. Then the solvent was evaporated under reduced pressure and the residue dissolved in dichloromethane and filtered. The filtrate was dried over anhydrous Na2SO4. After removal of the solvent under reduced pressure, a red crystalline compound was obtained. Yield: 446 mg (95%). Red crystals suitable for X-ray crystallography were grown by slow diffusion of isopropyl ether into a dilute acetonitrile solution of the title compound.
The H atoms were positioned geometrically (aromatic C—H: 0.95 Å, methyl C—H: 0.98 Å) and were included in the riding model approximation; their temperature factors were set to 1.2 times those of the equivalent isotropic temperature factors of the parent site. The highest remaining electron density peaks are close to the Ru atom, with distances of 0.84 and 0.94 Å, respectively.
Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); 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: UdMX (Maris, 2004).
![[Figure 1]](./wm2252fig1thm.gif)
| Fig. 1. View of the cation in the title compound. Thermal ellipsoids are shown at the 50% probability level. H atoms, hexafluoridophosphate anions and the acetonitrile solvent molecule have been omitted for clarity. |
| [Ru(C10H8N2)2(C13H7N3S)](PF6)2·C2H3N | Z = 2 |
| Mr = 981.71 | F(000) = 980 |
| Triclinic, P1 | Dx = 1.765 Mg m−3 |
| Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
| a = 9.129 (3) Å | Cell parameters from 32297 reflections |
| b = 12.397 (4) Å | θ = 2.3–24.9° |
| c = 17.084 (5) Å | µ = 0.67 mm−1 |
| α = 88.618 (4)° | T = 150 K |
| β = 89.704 (5)° | Block, red |
| γ = 72.870 (4)° | 0.24 × 0.13 × 0.10 mm |
| V = 1847.1 (10) Å3 |
| Bruker APEXII CCD diffractometer | 6687 independent reflections |
| Radiation source: X-ray sealed tube | 6155 reflections with I > 2σ(I) |
| Graphite | Rint = 0.061 |
| Detector resolution: 8.3 pixels mm-1 | θmax = 25.3°, θmin = 1.2° |
| ω scans | h = −10→10 |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −14→14 |
| Tmin = 0.83, Tmax = 0.95 | l = −20→20 |
| 178384 measured reflections |
| 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)] = 0.055 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.152 | H-atom parameters constrained |
| S = 1.18 | w = 1/[σ2(Fo2) + (0.0708P)2 + 4.8035P] where P = (Fo2 + 2Fc2)/3 |
| 6687 reflections | (Δ/σ)max = 0.001 |
| 536 parameters | Δρmax = 1.45 e Å−3 |
| 0 restraints | Δρmin = −0.86 e Å−3 |
| [Ru(C10H8N2)2(C13H7N3S)](PF6)2·C2H3N | γ = 72.870 (4)° |
| Mr = 981.71 | V = 1847.1 (10) Å3 |
| Triclinic, P1 | Z = 2 |
| a = 9.129 (3) Å | Mo Kα radiation |
| b = 12.397 (4) Å | µ = 0.67 mm−1 |
| c = 17.084 (5) Å | T = 150 K |
| α = 88.618 (4)° | 0.24 × 0.13 × 0.10 mm |
| β = 89.704 (5)° |
| Bruker APEXII CCD diffractometer | 6687 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 6155 reflections with I > 2σ(I) |
| Tmin = 0.83, Tmax = 0.95 | Rint = 0.061 |
| 178384 measured reflections | θmax = 25.3° |
| R[F2 > 2σ(F2)] = 0.055 | H-atom parameters constrained |
| wR(F2) = 0.152 | Δρmax = 1.45 e Å−3 |
| S = 1.18 | Δρmin = −0.86 e Å−3 |
| 6687 reflections | Absolute structure: ? |
| 536 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
Experimental. X-ray crystallographic data for I were collected from a single-crystal sample, which was mounted on a loop fiber. Data were collected using a Bruker smart diffractometer equiped with an APEX II CCD Detector, a graphite monochromator. The crystal-to-detector distance was 5.0 cm, and the data collection was carried out in 512 x 512 pixel mode. The initial unit-cell parameters were determined by a least-squares fit of the angular setting of strong reflections, collected by a 10.0 degree scan in 33 frames over four different parts of the reciprocal space (132 frames total). |
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 | ||
| Ru | 0.38640 (4) | 0.62025 (3) | 0.24834 (2) | 0.03144 (14) | |
| S | −0.09857 (19) | 0.94046 (14) | 0.70014 (10) | 0.0591 (4) | |
| N1 | 0.4231 (4) | 0.7694 (3) | 0.2119 (2) | 0.0367 (8) | |
| N2 | 0.3529 (5) | 0.6162 (4) | 0.1294 (2) | 0.0388 (9) | |
| N3 | 0.6085 (4) | 0.5205 (3) | 0.2332 (2) | 0.0357 (8) | |
| N4 | 0.3658 (5) | 0.4625 (3) | 0.2763 (2) | 0.0341 (8) | |
| N5 | 0.4022 (5) | 0.6486 (3) | 0.3666 (2) | 0.0369 (9) | |
| N6 | 0.1613 (5) | 0.7088 (3) | 0.2710 (2) | 0.0360 (9) | |
| N7 | 0.0887 (6) | 0.8460 (4) | 0.5781 (3) | 0.0602 (13) | |
| C1 | 0.4583 (6) | 0.8450 (4) | 0.2582 (3) | 0.0431 (11) | |
| H1 | 0.4678 | 0.8303 | 0.3130 | 0.052* | |
| C2 | 0.4806 (6) | 0.9433 (4) | 0.2279 (4) | 0.0519 (14) | |
| H2 | 0.5066 | 0.9947 | 0.2615 | 0.062* | |
| C3 | 0.4652 (6) | 0.9660 (5) | 0.1489 (4) | 0.0565 (15) | |
| H3 | 0.4791 | 1.0338 | 0.1275 | 0.068* | |
| C4 | 0.4294 (6) | 0.8901 (5) | 0.1012 (4) | 0.0510 (13) | |
| H4 | 0.4183 | 0.9048 | 0.0464 | 0.061* | |
| C5 | 0.4095 (5) | 0.7919 (4) | 0.1334 (3) | 0.0410 (11) | |
| C6 | 0.3705 (5) | 0.7049 (4) | 0.0877 (3) | 0.0409 (11) | |
| C7 | 0.3534 (6) | 0.7108 (5) | 0.0063 (3) | 0.0536 (14) | |
| H7 | 0.3704 | 0.7722 | −0.0229 | 0.064* | |
| C8 | 0.3122 (7) | 0.6279 (6) | −0.0310 (3) | 0.0581 (15) | |
| H8 | 0.2978 | 0.6322 | −0.0861 | 0.070* | |
| C9 | 0.2917 (7) | 0.5380 (5) | 0.0119 (3) | 0.0524 (13) | |
| H9 | 0.2623 | 0.4800 | −0.0132 | 0.063* | |
| C10 | 0.3144 (6) | 0.5336 (4) | 0.0915 (3) | 0.0430 (11) | |
| H10 | 0.3027 | 0.4706 | 0.1209 | 0.052* | |
| C11 | 0.7259 (6) | 0.5555 (4) | 0.2073 (3) | 0.0433 (11) | |
| H11 | 0.7092 | 0.6338 | 0.1968 | 0.052* | |
| C12 | 0.8704 (6) | 0.4822 (5) | 0.1952 (3) | 0.0463 (12) | |
| H12 | 0.9506 | 0.5099 | 0.1760 | 0.056* | |
| C13 | 0.8972 (6) | 0.3692 (5) | 0.2112 (3) | 0.0459 (12) | |
| H13 | 0.9962 | 0.3177 | 0.2042 | 0.055* | |
| C14 | 0.7764 (6) | 0.3316 (4) | 0.2379 (3) | 0.0410 (11) | |
| H14 | 0.7922 | 0.2537 | 0.2498 | 0.049* | |
| C15 | 0.6340 (6) | 0.4075 (4) | 0.2469 (3) | 0.0371 (10) | |
| C16 | 0.4958 (6) | 0.3749 (4) | 0.2704 (3) | 0.0359 (10) | |
| C17 | 0.4963 (7) | 0.2647 (4) | 0.2856 (3) | 0.0447 (12) | |
| H17 | 0.5869 | 0.2040 | 0.2786 | 0.054* | |
| C18 | 0.3620 (7) | 0.2441 (4) | 0.3113 (3) | 0.0464 (12) | |
| H18 | 0.3604 | 0.1693 | 0.3234 | 0.056* | |
| C19 | 0.2330 (6) | 0.3325 (4) | 0.3189 (3) | 0.0442 (12) | |
| H19 | 0.1402 | 0.3198 | 0.3361 | 0.053* | |
| C20 | 0.2374 (6) | 0.4408 (4) | 0.3015 (3) | 0.0386 (10) | |
| H20 | 0.1469 | 0.5020 | 0.3075 | 0.046* | |
| C21 | 0.5229 (6) | 0.6167 (4) | 0.4138 (3) | 0.0440 (11) | |
| H21 | 0.6173 | 0.5708 | 0.3936 | 0.053* | |
| C22 | 0.5166 (7) | 0.6483 (5) | 0.4923 (3) | 0.0534 (14) | |
| H22 | 0.6053 | 0.6249 | 0.5246 | 0.064* | |
| C23 | 0.3801 (7) | 0.7136 (5) | 0.5214 (3) | 0.0505 (13) | |
| H23 | 0.3741 | 0.7355 | 0.5746 | 0.061* | |
| C24 | 0.2514 (6) | 0.7481 (4) | 0.4746 (3) | 0.0436 (12) | |
| C25 | 0.1014 (7) | 0.8152 (4) | 0.5000 (3) | 0.0453 (12) | |
| C26 | −0.0220 (7) | 0.8445 (5) | 0.4516 (4) | 0.0527 (14) | |
| H26 | −0.1182 | 0.8893 | 0.4705 | 0.063* | |
| C27 | −0.0085 (6) | 0.8087 (4) | 0.3729 (3) | 0.0450 (12) | |
| C28 | −0.1299 (6) | 0.8342 (5) | 0.3191 (4) | 0.0505 (13) | |
| H28 | −0.2295 | 0.8775 | 0.3348 | 0.061* | |
| C29 | −0.1060 (6) | 0.7975 (5) | 0.2446 (3) | 0.0495 (13) | |
| H29 | −0.1884 | 0.8139 | 0.2082 | 0.059* | |
| C30 | 0.0415 (6) | 0.7351 (4) | 0.2220 (3) | 0.0437 (11) | |
| H30 | 0.0572 | 0.7103 | 0.1696 | 0.052* | |
| C31 | 0.1371 (6) | 0.7452 (4) | 0.3460 (3) | 0.0400 (11) | |
| C32 | 0.2664 (6) | 0.7137 (4) | 0.3967 (3) | 0.0405 (11) | |
| C33 | 0.0016 (7) | 0.8891 (4) | 0.6287 (3) | 0.0510 (13) | |
| P1 | 1.0000 | 0.5000 | 0.5000 | 0.0572 (6) | |
| F11 | 0.9341 (5) | 0.5008 (5) | 0.4141 (3) | 0.0975 (15) | |
| F12 | 0.8596 (5) | 0.4634 (3) | 0.5351 (3) | 0.0808 (13) | |
| F13 | 0.9038 (5) | 0.6276 (3) | 0.5092 (3) | 0.0901 (15) | |
| P2 | 0.5000 | 1.0000 | 0.5000 | 0.0427 (4) | |
| F21 | 0.4009 (6) | 0.9596 (4) | 0.5648 (3) | 0.0951 (15) | |
| F22 | 0.6131 (6) | 0.8810 (4) | 0.5037 (5) | 0.145 (3) | |
| F23 | 0.4083 (11) | 0.9609 (7) | 0.4380 (4) | 0.177 (4) | |
| P3 | 0.17933 (17) | 0.24155 (12) | 0.02025 (9) | 0.0502 (4) | |
| F31 | 0.1520 (7) | 0.1887 (4) | 0.1024 (3) | 0.113 (2) | |
| F32 | 0.0179 (5) | 0.2320 (4) | −0.0039 (5) | 0.129 (2) | |
| F33 | 0.2061 (9) | 0.2892 (4) | −0.0615 (3) | 0.129 (2) | |
| F34 | 0.3376 (6) | 0.2461 (4) | 0.0479 (4) | 0.1127 (19) | |
| F35 | 0.1002 (5) | 0.3654 (3) | 0.0503 (3) | 0.0762 (11) | |
| F36 | 0.2583 (5) | 0.1159 (3) | −0.0085 (2) | 0.0712 (10) | |
| C40 | 0.8638 (9) | 0.0429 (5) | 0.1327 (4) | 0.0609 (16) | |
| C41 | 1.0145 (9) | −0.0209 (6) | 0.1065 (5) | 0.0735 (19) | |
| H41A | 1.0621 | 0.0296 | 0.0780 | 0.110* | |
| H41B | 1.0056 | −0.0805 | 0.0718 | 0.110* | |
| H41C | 1.0779 | −0.0550 | 0.1519 | 0.110* | |
| N8 | 0.7473 (8) | 0.0933 (5) | 0.1538 (4) | 0.0753 (16) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Ru | 0.0366 (2) | 0.0291 (2) | 0.0311 (2) | −0.01360 (15) | 0.00462 (14) | −0.00054 (14) |
| S | 0.0651 (9) | 0.0567 (9) | 0.0595 (9) | −0.0231 (7) | 0.0200 (7) | −0.0170 (7) |
| N1 | 0.038 (2) | 0.0318 (19) | 0.042 (2) | −0.0128 (16) | 0.0057 (17) | −0.0009 (16) |
| N2 | 0.039 (2) | 0.045 (2) | 0.032 (2) | −0.0127 (18) | 0.0064 (16) | −0.0004 (17) |
| N3 | 0.038 (2) | 0.036 (2) | 0.036 (2) | −0.0148 (17) | 0.0040 (16) | −0.0035 (16) |
| N4 | 0.044 (2) | 0.0305 (19) | 0.0313 (19) | −0.0155 (17) | 0.0008 (16) | −0.0018 (15) |
| N5 | 0.046 (2) | 0.0314 (19) | 0.039 (2) | −0.0206 (17) | 0.0010 (18) | 0.0002 (16) |
| N6 | 0.041 (2) | 0.0303 (19) | 0.039 (2) | −0.0144 (16) | 0.0103 (17) | 0.0019 (16) |
| N7 | 0.076 (3) | 0.056 (3) | 0.053 (3) | −0.025 (3) | 0.022 (3) | −0.016 (2) |
| C1 | 0.044 (3) | 0.033 (2) | 0.053 (3) | −0.012 (2) | 0.009 (2) | −0.002 (2) |
| C2 | 0.044 (3) | 0.032 (3) | 0.081 (4) | −0.013 (2) | 0.013 (3) | −0.004 (3) |
| C3 | 0.048 (3) | 0.039 (3) | 0.083 (4) | −0.015 (2) | 0.011 (3) | 0.018 (3) |
| C4 | 0.047 (3) | 0.048 (3) | 0.061 (3) | −0.020 (2) | 0.007 (3) | 0.016 (3) |
| C5 | 0.035 (2) | 0.040 (3) | 0.047 (3) | −0.011 (2) | 0.008 (2) | 0.007 (2) |
| C6 | 0.034 (2) | 0.049 (3) | 0.041 (3) | −0.015 (2) | 0.002 (2) | 0.005 (2) |
| C7 | 0.050 (3) | 0.073 (4) | 0.041 (3) | −0.026 (3) | 0.002 (2) | 0.017 (3) |
| C8 | 0.055 (3) | 0.092 (5) | 0.035 (3) | −0.034 (3) | −0.004 (2) | 0.003 (3) |
| C9 | 0.052 (3) | 0.071 (4) | 0.041 (3) | −0.028 (3) | 0.002 (2) | −0.009 (3) |
| C10 | 0.046 (3) | 0.046 (3) | 0.041 (3) | −0.020 (2) | 0.002 (2) | −0.005 (2) |
| C11 | 0.045 (3) | 0.039 (3) | 0.049 (3) | −0.016 (2) | 0.004 (2) | −0.006 (2) |
| C12 | 0.038 (3) | 0.055 (3) | 0.050 (3) | −0.018 (2) | 0.004 (2) | −0.010 (2) |
| C13 | 0.042 (3) | 0.048 (3) | 0.044 (3) | −0.007 (2) | 0.000 (2) | −0.013 (2) |
| C14 | 0.046 (3) | 0.037 (3) | 0.039 (3) | −0.010 (2) | −0.001 (2) | −0.005 (2) |
| C15 | 0.045 (3) | 0.038 (2) | 0.030 (2) | −0.014 (2) | 0.0004 (19) | −0.0069 (18) |
| C16 | 0.046 (3) | 0.034 (2) | 0.031 (2) | −0.017 (2) | 0.0028 (19) | −0.0040 (18) |
| C17 | 0.057 (3) | 0.032 (2) | 0.046 (3) | −0.013 (2) | 0.002 (2) | −0.004 (2) |
| C18 | 0.064 (3) | 0.034 (3) | 0.049 (3) | −0.026 (2) | 0.003 (2) | 0.001 (2) |
| C19 | 0.053 (3) | 0.045 (3) | 0.043 (3) | −0.027 (2) | 0.004 (2) | 0.002 (2) |
| C20 | 0.042 (3) | 0.041 (3) | 0.037 (2) | −0.018 (2) | 0.003 (2) | −0.002 (2) |
| C21 | 0.049 (3) | 0.041 (3) | 0.047 (3) | −0.019 (2) | −0.002 (2) | −0.003 (2) |
| C22 | 0.065 (4) | 0.051 (3) | 0.047 (3) | −0.021 (3) | −0.009 (3) | 0.002 (2) |
| C23 | 0.065 (4) | 0.047 (3) | 0.044 (3) | −0.023 (3) | 0.005 (3) | −0.003 (2) |
| C24 | 0.057 (3) | 0.037 (3) | 0.043 (3) | −0.024 (2) | 0.010 (2) | −0.003 (2) |
| C25 | 0.058 (3) | 0.041 (3) | 0.042 (3) | −0.023 (2) | 0.014 (2) | −0.004 (2) |
| C26 | 0.056 (3) | 0.042 (3) | 0.061 (3) | −0.017 (3) | 0.019 (3) | −0.003 (2) |
| C27 | 0.054 (3) | 0.035 (3) | 0.050 (3) | −0.020 (2) | 0.012 (2) | −0.002 (2) |
| C28 | 0.041 (3) | 0.047 (3) | 0.064 (4) | −0.014 (2) | 0.005 (2) | 0.003 (3) |
| C29 | 0.043 (3) | 0.047 (3) | 0.059 (3) | −0.014 (2) | 0.003 (2) | 0.005 (2) |
| C30 | 0.044 (3) | 0.042 (3) | 0.048 (3) | −0.018 (2) | 0.001 (2) | 0.004 (2) |
| C31 | 0.047 (3) | 0.030 (2) | 0.048 (3) | −0.018 (2) | 0.009 (2) | 0.003 (2) |
| C32 | 0.056 (3) | 0.029 (2) | 0.042 (3) | −0.021 (2) | 0.014 (2) | −0.0019 (19) |
| C33 | 0.063 (3) | 0.039 (3) | 0.056 (3) | −0.022 (3) | 0.014 (3) | −0.004 (2) |
| P1 | 0.0660 (14) | 0.0391 (10) | 0.0700 (14) | −0.0214 (10) | 0.0305 (11) | −0.0011 (9) |
| F11 | 0.081 (3) | 0.127 (4) | 0.083 (3) | −0.028 (3) | 0.022 (2) | −0.014 (3) |
| F12 | 0.088 (3) | 0.057 (2) | 0.107 (3) | −0.037 (2) | 0.051 (2) | −0.008 (2) |
| F13 | 0.103 (3) | 0.045 (2) | 0.123 (4) | −0.022 (2) | 0.060 (3) | −0.005 (2) |
| P2 | 0.0473 (10) | 0.0392 (9) | 0.0432 (10) | −0.0152 (8) | 0.0076 (8) | −0.0015 (8) |
| F21 | 0.112 (4) | 0.068 (3) | 0.104 (3) | −0.028 (2) | 0.058 (3) | 0.008 (2) |
| F22 | 0.096 (4) | 0.054 (3) | 0.268 (8) | −0.002 (2) | 0.091 (5) | 0.028 (4) |
| F23 | 0.297 (10) | 0.212 (8) | 0.097 (4) | −0.193 (8) | −0.071 (5) | 0.027 (4) |
| P3 | 0.0517 (8) | 0.0431 (7) | 0.0573 (9) | −0.0161 (6) | 0.0128 (7) | −0.0050 (6) |
| F31 | 0.170 (5) | 0.068 (3) | 0.100 (3) | −0.032 (3) | 0.080 (4) | −0.011 (2) |
| F32 | 0.066 (3) | 0.074 (3) | 0.248 (8) | −0.018 (2) | −0.009 (4) | −0.045 (4) |
| F33 | 0.223 (7) | 0.065 (3) | 0.073 (3) | −0.002 (3) | 0.052 (4) | 0.006 (2) |
| F34 | 0.073 (3) | 0.094 (3) | 0.176 (6) | −0.031 (3) | −0.002 (3) | −0.034 (4) |
| F35 | 0.079 (3) | 0.050 (2) | 0.102 (3) | −0.0215 (18) | 0.034 (2) | −0.0191 (19) |
| F36 | 0.078 (2) | 0.0481 (19) | 0.083 (3) | −0.0129 (17) | 0.027 (2) | −0.0085 (18) |
| C40 | 0.076 (5) | 0.045 (3) | 0.071 (4) | −0.032 (3) | 0.005 (3) | −0.004 (3) |
| C41 | 0.086 (5) | 0.063 (4) | 0.079 (5) | −0.033 (4) | 0.021 (4) | −0.006 (3) |
| N8 | 0.077 (4) | 0.059 (3) | 0.094 (5) | −0.027 (3) | 0.002 (3) | −0.015 (3) |
| Ru—N1 | 2.056 (4) | C17—H17 | 0.95 |
| Ru—N3 | 2.059 (4) | C18—C19 | 1.360 (8) |
| Ru—N2 | 2.059 (4) | C18—H18 | 0.95 |
| Ru—N4 | 2.064 (4) | C19—C20 | 1.381 (7) |
| Ru—N6 | 2.065 (4) | C19—H19 | 0.95 |
| Ru—N5 | 2.072 (4) | C20—H20 | 0.95 |
| S—C33 | 1.554 (6) | C21—C22 | 1.403 (8) |
| N1—C1 | 1.350 (6) | C21—H21 | 0.95 |
| N1—C5 | 1.363 (6) | C22—C23 | 1.369 (8) |
| N2—C6 | 1.345 (6) | C22—H22 | 0.95 |
| N2—C10 | 1.357 (6) | C23—C24 | 1.379 (8) |
| N3—C11 | 1.339 (6) | C23—H23 | 0.95 |
| N3—C15 | 1.365 (6) | C24—C32 | 1.401 (7) |
| N4—C20 | 1.344 (6) | C24—C25 | 1.448 (8) |
| N4—C16 | 1.358 (6) | C25—C26 | 1.356 (8) |
| N5—C21 | 1.326 (7) | C26—C27 | 1.419 (8) |
| N5—C32 | 1.370 (6) | C26—H26 | 0.95 |
| N6—C30 | 1.337 (7) | C27—C28 | 1.402 (8) |
| N6—C31 | 1.365 (6) | C27—C31 | 1.412 (7) |
| N7—C33 | 1.197 (7) | C28—C29 | 1.356 (8) |
| N7—C25 | 1.391 (7) | C28—H28 | 0.95 |
| C1—C2 | 1.382 (7) | C29—C30 | 1.398 (8) |
| C1—H1 | 0.95 | C29—H29 | 0.95 |
| C2—C3 | 1.371 (9) | C30—H30 | 0.95 |
| C2—H2 | 0.95 | C31—C32 | 1.420 (8) |
| C3—C4 | 1.370 (9) | P1—F13i | 1.578 (4) |
| C3—H3 | 0.95 | P1—F13 | 1.578 (4) |
| C4—C5 | 1.383 (7) | P1—F11 | 1.588 (5) |
| C4—H4 | 0.95 | P1—F11i | 1.588 (5) |
| C5—C6 | 1.472 (7) | P1—F12 | 1.591 (3) |
| C6—C7 | 1.396 (7) | P1—F12i | 1.591 (3) |
| C7—C8 | 1.366 (9) | P2—F23ii | 1.526 (5) |
| C7—H7 | 0.95 | P2—F23 | 1.526 (5) |
| C8—C9 | 1.376 (9) | P2—F22ii | 1.531 (4) |
| C8—H8 | 0.95 | P2—F22 | 1.531 (4) |
| C9—C10 | 1.374 (7) | P2—F21 | 1.589 (4) |
| C9—H9 | 0.95 | P2—F21ii | 1.589 (4) |
| C10—H10 | 0.95 | P3—F34 | 1.540 (5) |
| C11—C12 | 1.381 (7) | P3—F33 | 1.549 (5) |
| C11—H11 | 0.95 | P3—F32 | 1.571 (5) |
| C12—C13 | 1.370 (8) | P3—F31 | 1.585 (5) |
| C12—H12 | 0.95 | P3—F35 | 1.589 (4) |
| C13—C14 | 1.388 (8) | P3—F36 | 1.600 (4) |
| C13—H13 | 0.95 | C40—N8 | 1.125 (9) |
| C14—C15 | 1.372 (7) | C40—C41 | 1.445 (10) |
| C14—H14 | 0.95 | C41—H41a | 0.98 |
| C15—C16 | 1.484 (7) | C41—H41b | 0.98 |
| C16—C17 | 1.383 (7) | C41—H41c | 0.98 |
| C17—C18 | 1.390 (8) | ||
| N1—Ru—N3 | 96.28 (15) | N4—C20—H20 | 118.9 |
| N1—Ru—N2 | 79.03 (16) | C19—C20—H20 | 118.9 |
| N3—Ru—N2 | 88.79 (16) | N5—C21—C22 | 122.5 (5) |
| N1—Ru—N4 | 174.09 (15) | N5—C21—H21 | 118.7 |
| N3—Ru—N4 | 78.91 (15) | C22—C21—H21 | 118.7 |
| N2—Ru—N4 | 97.32 (15) | C23—C22—C21 | 118.6 (5) |
| N1—Ru—N6 | 88.69 (15) | C23—C22—H22 | 120.7 |
| N3—Ru—N6 | 174.60 (15) | C21—C22—H22 | 120.7 |
| N2—Ru—N6 | 94.23 (16) | C22—C23—C24 | 120.8 (5) |
| N4—Ru—N6 | 96.25 (15) | C22—C23—H23 | 119.6 |
| N1—Ru—N5 | 94.83 (15) | C24—C23—H23 | 119.6 |
| N3—Ru—N5 | 97.41 (16) | C23—C24—C32 | 117.4 (5) |
| N2—Ru—N5 | 171.75 (16) | C23—C24—C25 | 125.1 (5) |
| N4—Ru—N5 | 89.23 (14) | C32—C24—C25 | 117.5 (5) |
| N6—Ru—N5 | 80.03 (16) | C26—C25—N7 | 121.2 (5) |
| C1—N1—C5 | 118.4 (4) | C26—C25—C24 | 122.4 (5) |
| C1—N1—RU | 126.2 (3) | N7—C25—C24 | 116.4 (5) |
| C5—N1—RU | 115.4 (3) | C25—C26—C27 | 120.5 (5) |
| C6—N2—C10 | 118.9 (4) | C25—C26—H26 | 119.7 |
| C6—N2—RU | 115.5 (3) | C27—C26—H26 | 119.7 |
| C10—N2—RU | 125.6 (3) | C28—C27—C31 | 117.4 (5) |
| C11—N3—C15 | 117.9 (4) | C28—C27—C26 | 124.4 (5) |
| C11—N3—RU | 126.1 (3) | C31—C27—C26 | 118.3 (5) |
| C15—N3—RU | 115.9 (3) | C29—C28—C27 | 120.3 (5) |
| C20—N4—C16 | 118.5 (4) | C29—C28—H28 | 119.9 |
| C20—N4—RU | 125.6 (3) | C27—C28—H28 | 119.9 |
| C16—N4—RU | 115.9 (3) | C28—C29—C30 | 119.2 (5) |
| C21—N5—C32 | 118.1 (4) | C28—C29—H29 | 120.4 |
| C21—N5—RU | 129.4 (4) | C30—C29—H29 | 120.4 |
| C32—N5—RU | 112.4 (3) | N6—C30—C29 | 122.9 (5) |
| C30—N6—C31 | 118.0 (4) | N6—C30—H30 | 118.6 |
| C30—N6—RU | 128.5 (3) | C29—C30—H30 | 118.6 |
| C31—N6—RU | 113.5 (3) | N6—C31—C27 | 122.3 (5) |
| C33—N7—C25 | 144.9 (6) | N6—C31—C32 | 116.4 (4) |
| N1—C1—C2 | 121.7 (5) | C27—C31—C32 | 121.3 (5) |
| N1—C1—H1 | 119.1 | N5—C32—C24 | 122.5 (5) |
| C2—C1—H1 | 119.1 | N5—C32—C31 | 117.5 (4) |
| C3—C2—C1 | 119.6 (6) | C24—C32—C31 | 119.9 (5) |
| C3—C2—H2 | 120.2 | N7—C33—S | 174.4 (6) |
| C1—C2—H2 | 120.2 | F13i—P1—F13 | 180.0 (4) |
| C4—C3—C2 | 119.3 (5) | F13i—P1—F11 | 89.6 (3) |
| C4—C3—H3 | 120.4 | F13—P1—F11 | 90.4 (3) |
| C2—C3—H3 | 120.4 | F13i—P1—F11i | 90.4 (3) |
| C3—C4—C5 | 119.7 (5) | F13—P1—F11i | 89.6 (3) |
| C3—C4—H4 | 120.2 | F11—P1—F11i | 180.000 (2) |
| C5—C4—H4 | 120.2 | F13i—P1—F12 | 90.9 (2) |
| N1—C5—C4 | 121.3 (5) | F13—P1—F12 | 89.1 (2) |
| N1—C5—C6 | 114.6 (4) | F11—P1—F12 | 90.3 (3) |
| C4—C5—C6 | 124.1 (5) | F11i—P1—F12 | 89.7 (3) |
| N2—C6—C7 | 120.8 (5) | F13i—P1—F12i | 89.1 (2) |
| N2—C6—C5 | 115.5 (4) | F13—P1—F12i | 90.9 (2) |
| C7—C6—C5 | 123.7 (5) | F11—P1—F12i | 89.7 (3) |
| C8—C7—C6 | 119.7 (5) | F11i—P1—F12i | 90.3 (3) |
| C8—C7—H7 | 120.2 | F12—P1—F12i | 180.000 (1) |
| C6—C7—H7 | 120.2 | F23ii—P2—F23 | 180.0 (6) |
| C7—C8—C9 | 119.6 (5) | F23ii—P2—F22ii | 89.3 (5) |
| C7—C8—H8 | 120.2 | F23—P2—F22ii | 90.7 (5) |
| C9—C8—H8 | 120.2 | F23ii—P2—F22 | 90.7 (5) |
| C10—C9—C8 | 119.0 (5) | F23—P2—F22 | 89.3 (5) |
| C10—C9—H9 | 120.5 | F22ii—P2—F22 | 180.0 (6) |
| C8—C9—H9 | 120.5 | F23ii—P2—F21 | 91.9 (4) |
| N2—C10—C9 | 122.1 (5) | F23—P2—F21 | 88.1 (4) |
| N2—C10—H10 | 118.9 | F22ii—P2—F21 | 91.9 (3) |
| C9—C10—H10 | 118.9 | F22—P2—F21 | 88.1 (3) |
| N3—C11—C12 | 122.6 (5) | F23ii—P2—F21ii | 88.1 (4) |
| N3—C11—H11 | 118.7 | F23—P2—F21ii | 91.9 (4) |
| C12—C11—H11 | 118.7 | F22ii—P2—F21ii | 88.1 (3) |
| C13—C12—C11 | 119.5 (5) | F22—P2—F21ii | 91.9 (3) |
| C13—C12—H12 | 120.2 | F21—P2—F21ii | 180.000 (2) |
| C11—C12—H12 | 120.2 | F34—P3—F33 | 90.6 (4) |
| C12—C13—C14 | 118.6 (5) | F34—P3—F32 | 176.7 (4) |
| C12—C13—H13 | 120.7 | F33—P3—F32 | 92.6 (4) |
| C14—C13—H13 | 120.7 | F34—P3—F31 | 90.3 (4) |
| C15—C14—C13 | 119.6 (5) | F33—P3—F31 | 178.0 (3) |
| C15—C14—H14 | 120.2 | F32—P3—F31 | 86.6 (4) |
| C13—C14—H14 | 120.2 | F34—P3—F35 | 91.2 (3) |
| N3—C15—C14 | 121.7 (5) | F33—P3—F35 | 90.9 (2) |
| N3—C15—C16 | 114.5 (4) | F32—P3—F35 | 89.8 (2) |
| C14—C15—C16 | 123.7 (4) | F31—P3—F35 | 90.9 (2) |
| N4—C16—C17 | 121.5 (5) | F34—P3—F36 | 88.8 (3) |
| N4—C16—C15 | 114.7 (4) | F33—P3—F36 | 90.2 (2) |
| C17—C16—C15 | 123.8 (5) | F32—P3—F36 | 90.1 (2) |
| C16—C17—C18 | 119.0 (5) | F31—P3—F36 | 88.0 (2) |
| C16—C17—H17 | 120.5 | F35—P3—F36 | 178.9 (2) |
| C18—C17—H17 | 120.5 | N8—C40—C41 | 179.0 (8) |
| C19—C18—C17 | 119.2 (5) | C40—C41—H41A | 109.5 |
| C19—C18—H18 | 120.4 | C40—C41—H41B | 109.5 |
| C17—C18—H18 | 120.4 | H41A—C41—H41B | 109.5 |
| C18—C19—C20 | 119.7 (5) | C40—C41—H41C | 109.5 |
| C18—C19—H19 | 120.2 | H41A—C41—H41C | 109.5 |
| C20—C19—H19 | 120.2 | H41B—C41—H41C | 109.5 |
| N4—C20—C19 | 122.1 (5) | ||
| N3—RU—N1—C1 | −92.9 (4) | C6—N2—C10—C9 | −0.5 (8) |
| N2—RU—N1—C1 | 179.6 (4) | RU—N2—C10—C9 | 178.9 (4) |
| N6—RU—N1—C1 | 85.0 (4) | C8—C9—C10—N2 | 1.6 (9) |
| N5—RU—N1—C1 | 5.1 (4) | C15—N3—C11—C12 | −0.8 (7) |
| N3—RU—N1—C5 | 87.3 (3) | RU—N3—C11—C12 | −176.9 (4) |
| N2—RU—N1—C5 | −0.2 (3) | N3—C11—C12—C13 | −1.0 (8) |
| N6—RU—N1—C5 | −94.8 (3) | C11—C12—C13—C14 | 1.2 (8) |
| N5—RU—N1—C5 | −174.7 (3) | C12—C13—C14—C15 | 0.5 (7) |
| N1—RU—N2—C6 | 0.4 (3) | C11—N3—C15—C14 | 2.6 (7) |
| N3—RU—N2—C6 | −96.2 (4) | RU—N3—C15—C14 | 179.0 (3) |
| N4—RU—N2—C6 | −174.9 (3) | C11—N3—C15—C16 | −176.1 (4) |
| N6—RU—N2—C6 | 88.3 (4) | RU—N3—C15—C16 | 0.3 (5) |
| N1—RU—N2—C10 | −179.0 (4) | C13—C14—C15—N3 | −2.5 (7) |
| N3—RU—N2—C10 | 84.4 (4) | C13—C14—C15—C16 | 176.1 (4) |
| N4—RU—N2—C10 | 5.7 (4) | C20—N4—C16—C17 | 3.4 (7) |
| N6—RU—N2—C10 | −91.2 (4) | RU—N4—C16—C17 | −178.3 (4) |
| N1—RU—N3—C11 | 0.1 (4) | C20—N4—C16—C15 | −176.4 (4) |
| N2—RU—N3—C11 | 78.9 (4) | RU—N4—C16—C15 | 1.9 (5) |
| N4—RU—N3—C11 | 176.6 (4) | N3—C15—C16—N4 | −1.4 (6) |
| N5—RU—N3—C11 | −95.6 (4) | C14—C15—C16—N4 | 179.9 (4) |
| N1—RU—N3—C15 | −176.0 (3) | N3—C15—C16—C17 | 178.8 (4) |
| N2—RU—N3—C15 | −97.2 (3) | C14—C15—C16—C17 | 0.1 (7) |
| N4—RU—N3—C15 | 0.5 (3) | N4—C16—C17—C18 | −3.2 (7) |
| N5—RU—N3—C15 | 88.3 (3) | C15—C16—C17—C18 | 176.5 (5) |
| N3—RU—N4—C20 | 176.8 (4) | C16—C17—C18—C19 | 1.6 (8) |
| N2—RU—N4—C20 | −95.9 (4) | C17—C18—C19—C20 | −0.3 (8) |
| N6—RU—N4—C20 | −0.8 (4) | C16—N4—C20—C19 | −2.1 (7) |
| N5—RU—N4—C20 | 79.1 (4) | RU—N4—C20—C19 | 179.9 (4) |
| N3—RU—N4—C16 | −1.3 (3) | C18—C19—C20—N4 | 0.6 (8) |
| N2—RU—N4—C16 | 86.0 (3) | C32—N5—C21—C22 | −0.8 (7) |
| N6—RU—N4—C16 | −178.9 (3) | RU—N5—C21—C22 | 176.3 (4) |
| N5—RU—N4—C16 | −99.0 (3) | N5—C21—C22—C23 | 0.6 (8) |
| N1—RU—N5—C21 | −93.1 (4) | C21—C22—C23—C24 | −0.2 (8) |
| N3—RU—N5—C21 | 3.9 (4) | C22—C23—C24—C32 | −0.1 (8) |
| N4—RU—N5—C21 | 82.6 (4) | C22—C23—C24—C25 | 178.8 (5) |
| N6—RU—N5—C21 | 179.1 (4) | C33—N7—C25—C26 | 5.7 (12) |
| N1—RU—N5—C32 | 84.1 (3) | C33—N7—C25—C24 | −172.5 (8) |
| N3—RU—N5—C32 | −178.9 (3) | C23—C24—C25—C26 | −178.5 (5) |
| N4—RU—N5—C32 | −100.2 (3) | C32—C24—C25—C26 | 0.3 (7) |
| N6—RU—N5—C32 | −3.7 (3) | C23—C24—C25—N7 | −0.4 (8) |
| N1—RU—N6—C30 | 87.0 (4) | C32—C24—C25—N7 | 178.5 (4) |
| N2—RU—N6—C30 | 8.1 (4) | N7—C25—C26—C27 | −177.5 (5) |
| N4—RU—N6—C30 | −89.8 (4) | C24—C25—C26—C27 | 0.6 (8) |
| N5—RU—N6—C30 | −177.9 (4) | C25—C26—C27—C28 | 179.5 (5) |
| N1—RU—N6—C31 | −91.9 (3) | C25—C26—C27—C31 | −2.0 (8) |
| N2—RU—N6—C31 | −170.8 (3) | C31—C27—C28—C29 | 0.7 (8) |
| N4—RU—N6—C31 | 91.4 (3) | C26—C27—C28—C29 | 179.2 (5) |
| N5—RU—N6—C31 | 3.2 (3) | C27—C28—C29—C30 | −0.8 (8) |
| C5—N1—C1—C2 | −0.1 (7) | C31—N6—C30—C29 | −0.2 (7) |
| RU—N1—C1—C2 | −179.9 (4) | RU—N6—C30—C29 | −179.0 (4) |
| N1—C1—C2—C3 | 0.8 (8) | C28—C29—C30—N6 | 0.5 (8) |
| C1—C2—C3—C4 | −0.7 (8) | C30—N6—C31—C27 | 0.1 (6) |
| C2—C3—C4—C5 | 0.0 (8) | RU—N6—C31—C27 | 179.1 (3) |
| C1—N1—C5—C4 | −0.7 (7) | C30—N6—C31—C32 | 178.8 (4) |
| RU—N1—C5—C4 | 179.2 (4) | RU—N6—C31—C32 | −2.2 (5) |
| C1—N1—C5—C6 | −179.8 (4) | C28—C27—C31—N6 | −0.3 (7) |
| RU—N1—C5—C6 | 0.0 (5) | C26—C27—C31—N6 | −178.9 (4) |
| C3—C4—C5—N1 | 0.7 (8) | C28—C27—C31—C32 | −178.9 (4) |
| C3—C4—C5—C6 | 179.8 (5) | C26—C27—C31—C32 | 2.4 (7) |
| C10—N2—C6—C7 | −1.6 (7) | C21—N5—C32—C24 | 0.5 (7) |
| RU—N2—C6—C7 | 178.9 (4) | RU—N5—C32—C24 | −177.1 (3) |
| C10—N2—C6—C5 | 178.9 (4) | C21—N5—C32—C31 | −178.7 (4) |
| RU—N2—C6—C5 | −0.6 (5) | RU—N5—C32—C31 | 3.8 (5) |
| N1—C5—C6—N2 | 0.4 (6) | C23—C24—C32—N5 | −0.1 (7) |
| C4—C5—C6—N2 | −178.7 (5) | C25—C24—C32—N5 | −179.0 (4) |
| N1—C5—C6—C7 | −179.1 (5) | C23—C24—C32—C31 | 179.1 (4) |
| C4—C5—C6—C7 | 1.8 (8) | C25—C24—C32—C31 | 0.1 (7) |
| N2—C6—C7—C8 | 2.7 (8) | N6—C31—C32—N5 | −1.1 (6) |
| C5—C6—C7—C8 | −177.9 (5) | C27—C31—C32—N5 | 177.6 (4) |
| C6—C7—C8—C9 | −1.6 (9) | N6—C31—C32—C24 | 179.8 (4) |
| C7—C8—C9—C10 | −0.5 (9) | C27—C31—C32—C24 | −1.5 (7) |
| Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+1, −y+2, −z+1. |
| Ru—N1 | 2.056 (4) | Ru—N4 | 2.064 (4) |
| Ru—N3 | 2.059 (4) | Ru—N6 | 2.065 (4) |
| Ru—N2 | 2.059 (4) | Ru—N5 | 2.072 (4) |
The authors are greatful to the Natural Sciences and Engineering Research Council of Canada and the Université de Montréal for financial support.
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Ye, B.-H., Ji, L.-N., Xue, F. & Mak, T. C. W. (1999). Transition Met. Chem. 24, 8–12.
RuII polypyridyl complexes, mainly [Ru(bpy)3]2+ (bpy = 2,2'-bipyridine) and its derivatives have been studied extensively during the past three decades for their excellent photophysical properties characterized by long excited state lifetimes which makes them suitable choice for chromophores in light-harvesting devices (Medlycott & Hanan, 2005, 2006). Such good emissive properties of this class of compounds also make them useful in labelling biomolecules (Bertini et al., 1994). The title compound can be used to label biomolecules through a thiourea linkage by reaction of the isothiocyanate group on it with an amino group of the protein (Ryan et al., 1992; Khimich et al., 2007).
The crystal structure of the title compound reveals that the ruthenium atom has a slightly distorted octahedral coordinaton sphere and the isothiocyanate group is almost linear with a N—C—S angle of 174.4 (6)°. The six Ru—N bond distances falls in a short range of 2.056 (4) to 2.072 (4) Å, with the two longer ones being that with the phenanthroline moiety. The bite angles for the 2,2'-bipyridine lingands are 79.03 (16)° and 78.91 (15)°, while that for the phenanthroline is 78.91 (15)°.
For crystal structures of related RuII complexes with bidentate polypyridyl ligands, see: Ye et al. (1999); Huang & Ogawa (2006); Batey et al. (2007).