Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801008765/na6081sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801008765/na6081Isup2.hkl |
CCDC reference: 170734
Key indicators
- Single-crystal X-ray study
- T = 150 K
- Mean (C-C) = 0.005 Å
- Disorder in main residue
- R factor = 0.043
- wR factor = 0.110
- Data-to-parameter ratio = 14.5
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Alert Level C:
PLAT_301 Alert C Main Residue Disorder ........................ 10.00 Perc.
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check
0.31 g (0.43 mmol) dichloro-cis-bis[2(2-pyridyl)-4-methylcarboxyquinoline]ruthenium(II) was dissolved in 20 ml of methanol and 0.183 g (1.10 mmol) AgNO3 was added to the dissolved substrate and the solution was left stirring for 2 h. The resulting white precipitate was then filtered off and 72 mg (0.45 mmol) of 2,2'-bipyridine in 10 ml of methanol was added to the filtrate which was then left to reflux for 24 h. The solvent was removed by rotary evaporation and the resulting dark-red product was purified by column chromatography (alumina) using methylene chloride/methanol (1:1, v/v) as the eluant. After concentrating the volume of the eluant to 30 ml, the product was precipitated with saturated aqueous potassium hexafluorophosphate. The resulting shiny dark-red product was then washed with ether and vacuum dried (yield: 0.35 g, 76%).
During the structure refinement, the atoms of the ester group (C15, O1, O2 and C16) all had very large anisotropic displacement parameters. There was an improvement in the refinement when these atoms were treated as disordered atoms. The final disorder model consists of two positions for the ester group rotationally disordered about the C8—C15 bond which each have 50% occupancy.
Data collection: COLLECT (Nonius BV, 2001); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXTL (Sheldrick 1999); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Fig. 1. ORTEP drawing with atomic numbering of the title compound. Displacement ellipsoids are plotted at the 50% probability level. H atoms have been omitted for clarity. |
[Ru(C16H12N2O2)2(C10H8N2)](PF6)2 | F(000) = 2160 |
Mr = 1075.75 | Dx = 1.672 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 23.6702 (5) Å | Cell parameters from 20509 reflections |
b = 13.5602 (3) Å | θ = 2.6–27.5° |
c = 16.6057 (4) Å | µ = 0.55 mm−1 |
β = 126.7172 (11)° | T = 150 K |
V = 4272.49 (17) Å3 | Prism, dark-red |
Z = 4 | 0.35 × 0.13 × 0.08 mm |
Nonius KappaCCD diffractometer | 4797 independent reflections |
Radiation source: fine-focus sealed tube | 4271 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.024 |
Detector resolution: 9 pixels mm-1 | θmax = 27.5°, θmin = 2.8° |
ϕ scans, and ω scans with κ offsets | h = −30→30 |
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) | k = −17→17 |
Tmin = 0.832, Tmax = 0.958 | l = −21→17 |
15700 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)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.110 | H-atom parameters constrained |
S = 1.12 | w = 1/[σ2(Fo2) + (0.0477P)2 + 12.6286P] where P = (Fo2 + 2Fc2)/3 |
4797 reflections | (Δ/σ)max = 0.002 |
330 parameters | Δρmax = 1.18 e Å−3 |
34 restraints | Δρmin = −1.04 e Å−3 |
[Ru(C16H12N2O2)2(C10H8N2)](PF6)2 | V = 4272.49 (17) Å3 |
Mr = 1075.75 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 23.6702 (5) Å | µ = 0.55 mm−1 |
b = 13.5602 (3) Å | T = 150 K |
c = 16.6057 (4) Å | 0.35 × 0.13 × 0.08 mm |
β = 126.7172 (11)° |
Nonius KappaCCD diffractometer | 4797 independent reflections |
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) | 4271 reflections with I > 2σ(I) |
Tmin = 0.832, Tmax = 0.958 | Rint = 0.024 |
15700 measured reflections |
R[F2 > 2σ(F2)] = 0.043 | 34 restraints |
wR(F2) = 0.110 | H-atom parameters constrained |
S = 1.12 | w = 1/[σ2(Fo2) + (0.0477P)2 + 12.6286P] where P = (Fo2 + 2Fc2)/3 |
4797 reflections | Δρmax = 1.18 e Å−3 |
330 parameters | Δρmin = −1.04 e Å−3 |
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 | 0.0000 | 0.30705 (2) | 0.2500 | 0.01905 (11) | |
N1 | 0.10768 (13) | 0.31286 (17) | 0.32561 (18) | 0.0223 (5) | |
N2 | 0.02990 (12) | 0.42548 (17) | 0.35136 (17) | 0.0205 (5) | |
N5 | 0.01848 (12) | 0.19061 (17) | 0.34096 (18) | 0.0223 (5) | |
C1 | 0.14691 (17) | 0.2463 (2) | 0.3182 (2) | 0.0295 (6) | |
H1A | 0.1251 | 0.1874 | 0.2811 | 0.035* | |
C2 | 0.21737 (18) | 0.2607 (3) | 0.3625 (3) | 0.0387 (8) | |
H2A | 0.2432 | 0.2132 | 0.3545 | 0.046* | |
C3 | 0.25027 (17) | 0.3447 (3) | 0.4185 (3) | 0.0398 (8) | |
H3A | 0.2987 | 0.3562 | 0.4490 | 0.048* | |
C4 | 0.21142 (16) | 0.4122 (3) | 0.4297 (2) | 0.0319 (7) | |
H4A | 0.2332 | 0.4698 | 0.4692 | 0.038* | |
C5 | 0.14042 (15) | 0.3946 (2) | 0.3824 (2) | 0.0239 (6) | |
C6 | 0.09412 (15) | 0.4609 (2) | 0.3888 (2) | 0.0233 (6) | |
C7 | 0.11582 (16) | 0.5566 (2) | 0.4301 (2) | 0.0270 (6) | |
H7A | 0.1629 | 0.5774 | 0.4606 | 0.032* | |
C8 | 0.06843 (17) | 0.6199 (2) | 0.4260 (2) | 0.0298 (6) | |
C9 | 0.00096 (16) | 0.5841 (2) | 0.3898 (2) | 0.0292 (6) | |
C10 | −0.05251 (18) | 0.6418 (3) | 0.3813 (3) | 0.0401 (8) | |
H10A | −0.0459 | 0.7108 | 0.3932 | 0.048* | |
C11 | −0.11300 (19) | 0.5991 (3) | 0.3564 (3) | 0.0494 (10) | |
H11A | −0.1489 | 0.6391 | 0.3486 | 0.059* | |
C12 | −0.12319 (18) | 0.4964 (3) | 0.3420 (3) | 0.0430 (9) | |
H12A | −0.1634 | 0.4666 | 0.3315 | 0.052* | |
C13 | −0.07485 (17) | 0.4400 (3) | 0.3431 (2) | 0.0324 (7) | |
H13A | −0.0823 | 0.3710 | 0.3316 | 0.039* | |
C14 | −0.01402 (15) | 0.4831 (2) | 0.3613 (2) | 0.0251 (6) | |
C15 | 0.09544 (15) | 0.7203 (2) | 0.4721 (2) | 0.0413 (8) | |
O1A | 0.0504 (4) | 0.7826 (5) | 0.4477 (6) | 0.084 (3) | 0.50 |
O2A | 0.1624 (2) | 0.7289 (5) | 0.5311 (4) | 0.074 (3) | 0.50 |
C16A | 0.1914 (5) | 0.8237 (5) | 0.5774 (6) | 0.062 (4) | 0.50 |
H16A | 0.1537 | 0.8731 | 0.5459 | 0.094* | 0.50 |
H16B | 0.2273 | 0.8428 | 0.5684 | 0.094* | 0.50 |
H16C | 0.2129 | 0.8196 | 0.6493 | 0.094* | 0.50 |
O1B | 0.0710 (4) | 0.7774 (5) | 0.4991 (5) | 0.076 (2) | 0.50 |
O2B | 0.1531 (2) | 0.7439 (4) | 0.4817 (4) | 0.0398 (14) | 0.50 |
C16B | 0.1860 (6) | 0.8381 (5) | 0.5268 (6) | 0.059 (3) | 0.50 |
H16D | 0.1728 | 0.8859 | 0.4738 | 0.088* | 0.50 |
H16E | 0.2373 | 0.8303 | 0.5711 | 0.088* | 0.50 |
H16F | 0.1701 | 0.8620 | 0.5659 | 0.088* | 0.50 |
C17 | 0.01197 (14) | 0.0993 (2) | 0.3024 (2) | 0.0225 (6) | |
C18 | 0.02780 (16) | 0.0150 (2) | 0.3596 (2) | 0.0275 (6) | |
H18A | 0.0233 | −0.0482 | 0.3317 | 0.033* | |
C19 | 0.05006 (17) | 0.0238 (2) | 0.4574 (2) | 0.0308 (7) | |
H19A | 0.0615 | −0.0333 | 0.4976 | 0.037* | |
C20 | 0.05562 (17) | 0.1167 (2) | 0.4962 (2) | 0.0315 (7) | |
H20A | 0.0702 | 0.1243 | 0.5630 | 0.038* | |
C21 | 0.03955 (16) | 0.1981 (2) | 0.4358 (2) | 0.0276 (6) | |
H21A | 0.0436 | 0.2619 | 0.4625 | 0.033* | |
P1 | 0.32210 (5) | 0.45126 (8) | 0.20818 (8) | 0.0460 (3) | |
F1 | 0.29598 (16) | 0.3959 (3) | 0.2641 (3) | 0.1109 (15) | |
F2 | 0.28081 (16) | 0.3780 (2) | 0.1144 (2) | 0.0955 (12) | |
F3 | 0.25486 (12) | 0.5230 (2) | 0.1533 (2) | 0.0673 (8) | |
F4 | 0.36561 (14) | 0.5271 (2) | 0.29911 (18) | 0.0646 (7) | |
F5 | 0.38931 (13) | 0.38127 (18) | 0.26214 (18) | 0.0623 (7) | |
F6 | 0.34875 (12) | 0.50959 (18) | 0.15250 (17) | 0.0499 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ru1 | 0.02333 (17) | 0.01609 (16) | 0.02179 (17) | 0.000 | 0.01567 (14) | 0.000 |
N1 | 0.0252 (12) | 0.0208 (11) | 0.0247 (12) | 0.0029 (9) | 0.0170 (10) | 0.0023 (9) |
N2 | 0.0250 (12) | 0.0191 (11) | 0.0207 (11) | 0.0010 (9) | 0.0153 (10) | −0.0009 (9) |
N5 | 0.0254 (12) | 0.0207 (11) | 0.0235 (12) | 0.0016 (9) | 0.0161 (10) | 0.0022 (9) |
C1 | 0.0335 (16) | 0.0265 (15) | 0.0323 (16) | 0.0072 (12) | 0.0217 (14) | 0.0013 (12) |
C2 | 0.0339 (17) | 0.0411 (19) | 0.043 (2) | 0.0143 (15) | 0.0242 (16) | 0.0020 (15) |
C3 | 0.0253 (15) | 0.051 (2) | 0.0417 (19) | 0.0053 (15) | 0.0191 (15) | −0.0009 (16) |
C4 | 0.0261 (15) | 0.0375 (17) | 0.0310 (16) | −0.0003 (13) | 0.0165 (14) | −0.0032 (13) |
C5 | 0.0251 (14) | 0.0240 (14) | 0.0230 (14) | 0.0025 (11) | 0.0146 (12) | 0.0015 (11) |
C6 | 0.0261 (14) | 0.0222 (13) | 0.0227 (14) | 0.0008 (11) | 0.0152 (12) | −0.0001 (11) |
C7 | 0.0265 (14) | 0.0237 (14) | 0.0290 (15) | −0.0022 (11) | 0.0156 (13) | −0.0023 (12) |
C8 | 0.0359 (16) | 0.0237 (14) | 0.0286 (16) | 0.0011 (12) | 0.0187 (14) | −0.0015 (12) |
C9 | 0.0305 (16) | 0.0292 (15) | 0.0267 (15) | 0.0051 (12) | 0.0164 (13) | −0.0022 (12) |
C10 | 0.0379 (18) | 0.0387 (19) | 0.0386 (19) | 0.0108 (15) | 0.0201 (16) | −0.0084 (15) |
C11 | 0.0337 (19) | 0.063 (3) | 0.047 (2) | 0.0121 (17) | 0.0222 (17) | −0.0164 (19) |
C12 | 0.0310 (17) | 0.064 (2) | 0.0403 (19) | −0.0011 (16) | 0.0247 (16) | −0.0135 (18) |
C13 | 0.0310 (16) | 0.0401 (18) | 0.0306 (16) | −0.0026 (13) | 0.0209 (14) | −0.0076 (13) |
C14 | 0.0262 (14) | 0.0284 (15) | 0.0227 (14) | 0.0039 (11) | 0.0157 (12) | −0.0015 (11) |
C15 | 0.049 (2) | 0.0247 (16) | 0.052 (2) | −0.0010 (15) | 0.0314 (19) | −0.0082 (15) |
O1A | 0.066 (4) | 0.058 (4) | 0.103 (5) | −0.006 (3) | 0.037 (3) | −0.040 (3) |
O2A | 0.042 (3) | 0.031 (3) | 0.066 (5) | 0.007 (2) | −0.012 (3) | −0.018 (4) |
C16A | 0.041 (4) | 0.012 (3) | 0.065 (7) | 0.000 (3) | −0.005 (5) | −0.010 (4) |
O1B | 0.063 (4) | 0.064 (4) | 0.109 (5) | −0.026 (3) | 0.054 (3) | −0.066 (3) |
O2B | 0.025 (2) | 0.020 (2) | 0.042 (3) | −0.0009 (19) | 0.003 (2) | −0.003 (3) |
C16B | 0.046 (5) | 0.038 (4) | 0.072 (7) | −0.019 (4) | 0.024 (6) | −0.011 (5) |
C17 | 0.0236 (13) | 0.0202 (13) | 0.0269 (15) | −0.0004 (10) | 0.0169 (12) | 0.0014 (11) |
C18 | 0.0312 (15) | 0.0217 (14) | 0.0337 (16) | 0.0014 (12) | 0.0216 (14) | 0.0023 (12) |
C19 | 0.0351 (16) | 0.0282 (16) | 0.0342 (17) | 0.0054 (13) | 0.0234 (15) | 0.0103 (13) |
C20 | 0.0384 (17) | 0.0343 (16) | 0.0256 (15) | 0.0045 (13) | 0.0211 (14) | 0.0050 (13) |
C21 | 0.0347 (16) | 0.0268 (15) | 0.0246 (14) | 0.0017 (12) | 0.0195 (13) | −0.0006 (12) |
P1 | 0.0314 (5) | 0.0522 (6) | 0.0388 (5) | −0.0050 (4) | 0.0126 (4) | 0.0164 (4) |
F1 | 0.0612 (18) | 0.154 (3) | 0.112 (3) | 0.0034 (19) | 0.0488 (19) | 0.085 (3) |
F2 | 0.0724 (19) | 0.0656 (19) | 0.0635 (18) | −0.0253 (15) | −0.0050 (15) | 0.0033 (14) |
F3 | 0.0355 (12) | 0.096 (2) | 0.0715 (17) | 0.0131 (12) | 0.0328 (12) | 0.0428 (15) |
F4 | 0.0654 (16) | 0.0776 (18) | 0.0435 (13) | 0.0081 (14) | 0.0287 (13) | 0.0003 (12) |
F5 | 0.0522 (14) | 0.0529 (14) | 0.0510 (14) | 0.0084 (11) | 0.0143 (12) | 0.0092 (11) |
F6 | 0.0484 (12) | 0.0569 (14) | 0.0518 (13) | −0.0011 (11) | 0.0340 (11) | 0.0093 (11) |
Ru1—N5 | 2.043 (2) | C12—H12A | 0.9500 |
Ru1—N1 | 2.062 (2) | C13—C14 | 1.409 (4) |
Ru1—N2 | 2.119 (2) | C13—H13A | 0.9500 |
N1—C1 | 1.353 (4) | C15—O1B | 1.202 (5) |
N1—C5 | 1.358 (4) | C15—O1A | 1.223 (5) |
N2—C6 | 1.341 (4) | C15—O2A | 1.277 (5) |
N2—C14 | 1.387 (4) | C15—O2B | 1.316 (4) |
N5—C21 | 1.342 (4) | O2A—C16A | 1.444 (5) |
N5—C17 | 1.360 (4) | C16A—H16A | 0.9800 |
C1—C2 | 1.376 (5) | C16A—H16B | 0.9800 |
C1—H1A | 0.9500 | C16A—H16C | 0.9800 |
C2—C3 | 1.380 (5) | O2B—C16B | 1.450 (5) |
C2—H2A | 0.9500 | C16B—H16D | 0.9800 |
C3—C4 | 1.385 (5) | C16B—H16E | 0.9800 |
C3—H3A | 0.9500 | C16B—H16F | 0.9800 |
C4—C5 | 1.386 (4) | C17—C18 | 1.386 (4) |
C4—H4A | 0.9500 | C17—C17i | 1.474 (6) |
C5—C6 | 1.470 (4) | C18—C19 | 1.380 (4) |
C6—C7 | 1.413 (4) | C18—H18A | 0.9500 |
C7—C8 | 1.381 (4) | C19—C20 | 1.385 (5) |
C7—H7A | 0.9500 | C19—H19A | 0.9500 |
C8—C9 | 1.414 (4) | C20—C21 | 1.384 (4) |
C8—C15 | 1.505 (4) | C20—H20A | 0.9500 |
C9—C10 | 1.421 (4) | C21—H21A | 0.9500 |
C9—C14 | 1.423 (4) | P1—F1 | 1.579 (3) |
C10—C11 | 1.359 (6) | P1—F5 | 1.591 (3) |
C10—H10A | 0.9500 | P1—F4 | 1.593 (3) |
C11—C12 | 1.409 (6) | P1—F2 | 1.596 (3) |
C11—H11A | 0.9500 | P1—F6 | 1.605 (2) |
C12—C13 | 1.367 (5) | P1—F3 | 1.605 (3) |
N5i—Ru1—N5 | 78.81 (13) | N2—C14—C13 | 118.9 (3) |
N5i—Ru1—N1 | 96.89 (9) | N2—C14—C9 | 121.8 (3) |
N5—Ru1—N1 | 86.50 (9) | C13—C14—C9 | 119.3 (3) |
N1i—Ru1—N1 | 175.62 (13) | O1B—C15—O1A | 32.9 (3) |
N5i—Ru1—N2 | 174.35 (9) | O1B—C15—O2A | 108.0 (5) |
N5—Ru1—N2 | 100.15 (9) | O1A—C15—O2A | 128.8 (6) |
N1i—Ru1—N2 | 99.14 (9) | O1B—C15—O2B | 119.7 (5) |
N1—Ru1—N2 | 77.48 (9) | O1A—C15—O2B | 120.5 (5) |
N2—Ru1—N2i | 81.42 (12) | O2A—C15—O2B | 33.1 (3) |
C1—N1—C5 | 118.1 (3) | O1B—C15—C8 | 128.3 (5) |
C1—N1—Ru1 | 125.8 (2) | O1A—C15—C8 | 115.8 (4) |
C5—N1—Ru1 | 116.00 (18) | O2A—C15—C8 | 115.3 (4) |
C6—N2—C14 | 117.7 (2) | O2B—C15—C8 | 112.1 (3) |
C6—N2—Ru1 | 112.81 (18) | C15—O2A—C16A | 117.8 (6) |
C14—N2—Ru1 | 127.13 (19) | O2A—C16A—H16A | 109.5 |
C21—N5—C17 | 118.7 (2) | O2A—C16A—H16B | 109.5 |
C21—N5—Ru1 | 125.0 (2) | H16A—C16A—H16B | 109.5 |
C17—N5—Ru1 | 116.23 (18) | O2A—C16A—H16C | 109.5 |
N1—C1—C2 | 122.3 (3) | H16A—C16A—H16C | 109.5 |
N1—C1—H1A | 118.8 | H16B—C16A—H16C | 109.5 |
C2—C1—H1A | 118.8 | C15—O2B—C16B | 118.3 (7) |
C1—C2—C3 | 119.5 (3) | O2B—C16B—H16D | 109.5 |
C1—C2—H2A | 120.2 | O2B—C16B—H16E | 109.5 |
C3—C2—H2A | 120.2 | H16D—C16B—H16E | 109.5 |
C2—C3—C4 | 118.9 (3) | O2B—C16B—H16F | 109.5 |
C2—C3—H3A | 120.6 | H16D—C16B—H16F | 109.5 |
C4—C3—H3A | 120.6 | H16E—C16B—H16F | 109.5 |
C3—C4—C5 | 119.2 (3) | N5—C17—C18 | 121.3 (3) |
C3—C4—H4A | 120.4 | N5—C17—C17i | 114.27 (15) |
C5—C4—H4A | 120.4 | C18—C17—C17i | 124.38 (17) |
N1—C5—C4 | 122.0 (3) | C19—C18—C17 | 119.4 (3) |
N1—C5—C6 | 114.2 (2) | C19—C18—H18A | 120.3 |
C4—C5—C6 | 123.9 (3) | C17—C18—H18A | 120.3 |
N2—C6—C7 | 122.5 (3) | C18—C19—C20 | 119.3 (3) |
N2—C6—C5 | 115.7 (2) | C18—C19—H19A | 120.4 |
C7—C6—C5 | 121.8 (3) | C20—C19—H19A | 120.4 |
C8—C7—C6 | 119.8 (3) | C21—C20—C19 | 118.7 (3) |
C8—C7—H7A | 120.1 | C21—C20—H20A | 120.6 |
C6—C7—H7A | 120.1 | C19—C20—H20A | 120.6 |
C7—C8—C9 | 119.1 (3) | N5—C21—C20 | 122.6 (3) |
C7—C8—C15 | 116.8 (3) | N5—C21—H21A | 118.7 |
C9—C8—C15 | 123.7 (3) | C20—C21—H21A | 118.7 |
C8—C9—C10 | 124.5 (3) | F1—P1—F5 | 89.80 (17) |
C8—C9—C14 | 117.7 (3) | F1—P1—F4 | 90.5 (2) |
C10—C9—C14 | 117.8 (3) | F5—P1—F4 | 89.37 (14) |
C11—C10—C9 | 120.6 (3) | F1—P1—F2 | 93.0 (2) |
C11—C10—H10A | 119.7 | F5—P1—F2 | 90.07 (16) |
C9—C10—H10A | 119.7 | F4—P1—F2 | 176.52 (18) |
C10—C11—C12 | 121.0 (3) | F1—P1—F6 | 178.8 (2) |
C10—C11—H11A | 119.5 | F5—P1—F6 | 90.76 (14) |
C12—C11—H11A | 119.5 | F4—P1—F6 | 88.50 (14) |
C13—C12—C11 | 119.6 (3) | F2—P1—F6 | 88.08 (17) |
C13—C12—H12A | 120.2 | F1—P1—F3 | 91.04 (16) |
C11—C12—H12A | 120.2 | F5—P1—F3 | 179.12 (15) |
C12—C13—C14 | 120.7 (3) | F4—P1—F3 | 90.38 (16) |
C12—C13—H13A | 119.7 | F2—P1—F3 | 90.13 (17) |
C14—C13—H13A | 119.7 | F6—P1—F3 | 88.39 (13) |
Symmetry code: (i) −x, y, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Ru(C16H12N2O2)2(C10H8N2)](PF6)2 |
Mr | 1075.75 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 150 |
a, b, c (Å) | 23.6702 (5), 13.5602 (3), 16.6057 (4) |
β (°) | 126.7172 (11) |
V (Å3) | 4272.49 (17) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.55 |
Crystal size (mm) | 0.35 × 0.13 × 0.08 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.832, 0.958 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15700, 4797, 4271 |
Rint | 0.024 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.110, 1.12 |
No. of reflections | 4797 |
No. of parameters | 330 |
No. of restraints | 34 |
H-atom treatment | H-atom parameters constrained |
w = 1/[σ2(Fo2) + (0.0477P)2 + 12.6286P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 1.18, −1.04 |
Computer programs: COLLECT (Nonius BV, 2001), DENZO-SMN (Otwinowski & Minor, 1997), DENZO-SMN, SHELXTL (Sheldrick 1999), SHELXTL.
Ru1—N5 | 2.043 (2) | N2—C6 | 1.341 (4) |
Ru1—N1 | 2.062 (2) | N2—C14 | 1.387 (4) |
Ru1—N2 | 2.119 (2) | N5—C21 | 1.342 (4) |
N1—C1 | 1.353 (4) | N5—C17 | 1.360 (4) |
N1—C5 | 1.358 (4) | ||
N5i—Ru1—N5 | 78.81 (13) | N1—Ru1—N2 | 77.48 (9) |
N5i—Ru1—N1 | 96.89 (9) | N2—Ru1—N2i | 81.42 (12) |
N5—Ru1—N1 | 86.50 (9) | C1—N1—C5 | 118.1 (3) |
N1i—Ru1—N1 | 175.62 (13) | C5—N1—Ru1 | 116.00 (18) |
N5i—Ru1—N2 | 174.35 (9) | C6—N2—C14 | 117.7 (2) |
N5—Ru1—N2 | 100.15 (9) | C14—N2—Ru1 | 127.13 (19) |
N1i—Ru1—N2 | 99.14 (9) | C21—N5—Ru1 | 125.0 (2) |
Symmetry code: (i) −x, y, −z+1/2. |
In our continuing effort to synthesize and characterize multi-chromophore electroactive ruthenium(II)-containing polymeric systems, we have prepared novel ruthenium(II) complexes containing difunctional bipyridyl-like ligands. These complexes have been covalently attached into polymeric (Farah & Pietro, 1999, 2000; Farah et al., 2000) and CdS nanocluster assemblies (Veinot et al., 2000) through appropriate chemical modification. Detailed structural information is important in achieving a better understanding of the different photochemical, photophysical and electrochemical properties of the ruthenium chromophores (Juris et al., 1988). In light of these considerations, we describe here the synthesis and single-crystal structure of the title complex, (I).
This complex contains two functionalizable sites which make it an ideal synthon for the construction of polymetallic and transition-metal-containing dendrimers. The geometry of the dication is that of a distorted octahedron. When the four atoms consisting of N2, N5 and their symmetry equivalents [N2i and N5i; symmetry code: (i) -x, y, 1/2 - z] are considered to make the plane (with trans N1 and N1i), the average mean deviation from this plane is 0.1005 Å, with the Ru atom lying in it. The trans bond angle N1—Ru—N1i is 175.62 (13)°. None of the equatorial cis angles is close to the idealized value of 90°. The N2—Ru—N2i angle is found to be 81.42 (12)°, while the N5—Ru—N5i angle is 78.81 (13)°. Alternatively, if a plane is considered to pass through N1, N1i, N2 and N5i, the Ru atom lies 0.0212 Å above it, the trans bond angle N5—Ru—N2i is 174.35 (9)° and the two angles N1—Ru—N2 and N5i—Ru—N1i are 77.48 (9) and 86.50 (9)°, respectively. The steric interaction between the bulky 2-(2-pyridyl)-4-methoxycarbonylquinoline ligand and the bipyridine ligand results in an extension of the Ru—N2 distance in the quinoline moiety. This bond length of 2.119 (2) Å is longer than Ru—N1 as well as the value observed for Ru(bpy)32+ (Ichida et al., 1989). Consequently, the N1—Ru—N2 has the smallest bite angle of 77.48 (9)° to compensate for this effect. This finding may be related to the distorted structure of the complex and the different rigidity of the 2-(2-pyridyl)-4-methoxycarbonylquinoline ligand and the bipyridine. Similar distortions has been found in the solid state for polypyridyl ruthenium(II) complexes with rigid and sterically hindered ligand (Rillema et al., 1979). The Ru—N distance in the bipyridine ligand is shortened [versus Ru(bpy)32+] (Ichida et al., 1989) to account for the withdrawn electron density.