Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807018673/bg3035sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807018673/bg3035Isup2.hkl |
CCDC reference: 646637
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.004 Å
- R factor = 0.035
- wR factor = 0.084
- Data-to-parameter ratio = 18.7
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density .... 2.41 PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.94 Ratio PLAT230_ALERT_2_C Hirshfeld Test Diff for O1 - C31 .. 6.32 su PLAT230_ALERT_2_C Hirshfeld Test Diff for C13 - C14 .. 6.93 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Ru1 - C31 .. 9.09 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Ru1 - C32 .. 6.52 su PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C14 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C10
Alert level G PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 8 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 8 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
For related literature, see: Cabeza et al. (2001); Crabtree (1985); Kakiuchi et al. (2001); Kleiman & Dubeck (1963); Murai et al. (1993).
The title compound was obtained by refluxing a mixture of Ru3(CO)12 (0.02 mmol) with imine (0.5 mmol) in toluene (2 ml) under a nitrogen atmosphere for 48 h. The product was isolated and purified by silica gel column chromatography. Green block-shaped crystals suitable for X-ray diffraction were grown from hexane.
H atoms were placed in calculated positions and made to ride on their parent atoms, with C—H = 0.95Å for aromatic, 0.99Å for methylene and 0.98Å for methyl H atoms. The latter ones were allowed to rotate around the C—C bond. In all cases, Uiso(H) = 1.2Ueq(C).
Transition metal catalyzed organic transformations involving C—H bond activation have been sought after for decades (Kleiman & Dubeck 1963; Crabtree, 1985; Murai et al., 1993). In this context, Ru and Pd complexes are most often used as catalysts, and substrates for these reactions usually contain directing groups. The proposed mechanism for these reactions involves cleavage of a C—H bond ortho to a directing group and formation of a cyclometalated intermediate (Kakiuchi et al., 2001). However, very few examples have been reported of these intermediates. Herein, we wish to report the structure of a Ru(II) complex derived from the cleavage of a C—H bond in p-methylbenzylidenebenzylamine with Ru3(CO)12, Ru(η2-(C,N)-p-MeC6H3CH=NCH2Ph)2(CO)2 (I).
As shown in Fig. 1 the Ru coordination polyhedron adopts in (I) a distorted octahedral geometry by coordination of two N atoms and two C atoms from two Schiff base molecules, and two cis-disposed carbonyl ligands. The N atoms from the Schiff bases are respectively trans to a carbonyl ligand and an aryl C atom. The Ru—N bond distances are 2.1556 (19)Å and 2.176 (2) Å, respectively, somewhat longer than those of other similar Ru(II) complexes (Cabeza et al., 2001), while Ru—C distances involving carbonyl ligands are normal. The remaining Ru—C bond distances are 2.067 (2)Å and 2.111 (2) Å. Bond angles involving the ruthenium center fall in the range 78.12 (9) (C4—Ru(1)—N(1)) to 167.99 (11)° (C31—Ru(1)—N(2)). The configurations of the two Schiff base molecules are significantly different, with dihedral angles between aromatic ring planes being 73.3 (1)° (for C1 → C6 and C10 → C15) and 86.4 (1)° (C17 → C22 and C25 → C30), respectively.
For related literature, see: Cabeza et al. (2001); Crabtree (1985); Kakiuchi et al. (2001); Kleiman & Dubeck (1963); Murai et al. (1993).
Data collection: CrystalClear (Rigaku/MSC, 2004); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Fig. 1. The molecular structure of (I), showing 30% probability displacement ellipsoids. H atoms have been omitted for clarity. |
[Ru(C15H14N)2(CO)2] | F(000) = 1176 |
Mr = 573.63 | Dx = 1.384 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 6859 reflections |
a = 9.685 (3) Å | θ = 2.5–27.5° |
b = 16.813 (4) Å | µ = 0.60 mm−1 |
c = 17.126 (4) Å | T = 293 K |
β = 99.156 (5)° | Block, green |
V = 2753.3 (12) Å3 | 0.33 × 0.20 × 0.16 mm |
Z = 4 |
Rigaku Saturn70 CCD diffractometer | 6290 independent reflections |
Radiation source: fine-focus sealed tube | 5347 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.028 |
Detector resolution: 28.5714 pixels mm-1 | θmax = 27.5°, θmin = 2.5° |
CCD_Profile_fitting scans | h = −12→12 |
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2004) | k = −21→21 |
Tmin = 0.827, Tmax = 0.910 | l = −18→22 |
21246 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)] = 0.035 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.084 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0427P)2 + 0.4314P] where P = (Fo2 + 2Fc2)/3 |
6290 reflections | (Δ/σ)max = 0.001 |
336 parameters | Δρmax = 0.85 e Å−3 |
66 restraints | Δρmin = −0.35 e Å−3 |
[Ru(C15H14N)2(CO)2] | V = 2753.3 (12) Å3 |
Mr = 573.63 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.685 (3) Å | µ = 0.60 mm−1 |
b = 16.813 (4) Å | T = 293 K |
c = 17.126 (4) Å | 0.33 × 0.20 × 0.16 mm |
β = 99.156 (5)° |
Rigaku Saturn70 CCD diffractometer | 6290 independent reflections |
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2004) | 5347 reflections with I > 2σ(I) |
Tmin = 0.827, Tmax = 0.910 | Rint = 0.028 |
21246 measured reflections |
R[F2 > 2σ(F2)] = 0.035 | 66 restraints |
wR(F2) = 0.084 | H-atom parameters constrained |
S = 1.09 | Δρmax = 0.85 e Å−3 |
6290 reflections | Δρmin = −0.35 e Å−3 |
336 parameters |
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 | ||
Ru1 | 0.666953 (16) | 0.543113 (10) | 0.211497 (9) | 0.03961 (7) | |
O1 | 0.6571 (2) | 0.66359 (15) | 0.33920 (13) | 0.0899 (7) | |
O2 | 0.97164 (18) | 0.50689 (15) | 0.28032 (12) | 0.0752 (6) | |
N1 | 0.5711 (2) | 0.44267 (12) | 0.26255 (11) | 0.0491 (5) | |
N2 | 0.65760 (18) | 0.47949 (12) | 0.10133 (10) | 0.0443 (4) | |
C1 | 0.1693 (3) | 0.70533 (19) | 0.07321 (18) | 0.0735 (8) | |
H1A | 0.0858 | 0.6897 | 0.0363 | 0.088* | |
H1B | 0.2349 | 0.7325 | 0.0442 | 0.088* | |
H1C | 0.1424 | 0.7413 | 0.1132 | 0.088* | |
C2 | 0.2378 (2) | 0.63257 (16) | 0.11296 (14) | 0.0539 (6) | |
C3 | 0.3838 (2) | 0.62912 (15) | 0.13376 (13) | 0.0467 (5) | |
H3A | 0.4382 | 0.6721 | 0.1194 | 0.056* | |
C4 | 0.4520 (2) | 0.56516 (14) | 0.17458 (13) | 0.0441 (5) | |
C5 | 0.3664 (2) | 0.50282 (16) | 0.19466 (14) | 0.0502 (5) | |
C6 | 0.2212 (3) | 0.50428 (19) | 0.17314 (16) | 0.0627 (7) | |
H6A | 0.1661 | 0.4611 | 0.1863 | 0.075* | |
C7 | 0.1583 (3) | 0.56926 (19) | 0.13246 (17) | 0.0640 (7) | |
H7A | 0.0596 | 0.5705 | 0.1177 | 0.077* | |
C8 | 0.4383 (3) | 0.43938 (16) | 0.24164 (15) | 0.0556 (6) | |
H8A | 0.3871 | 0.3954 | 0.2569 | 0.067* | |
C9 | 0.6414 (3) | 0.37917 (15) | 0.31463 (14) | 0.0581 (6) | |
H9A | 0.7336 | 0.3676 | 0.2992 | 0.070* | |
H9B | 0.5846 | 0.3300 | 0.3070 | 0.070* | |
C10 | 0.6618 (3) | 0.40231 (15) | 0.40034 (14) | 0.0568 (6) | |
C11 | 0.7827 (4) | 0.4365 (2) | 0.43649 (19) | 0.0815 (9) | |
H11A | 0.8547 | 0.4477 | 0.4063 | 0.098* | |
C12 | 0.8031 (6) | 0.4554 (2) | 0.5160 (2) | 0.1053 (13) | |
H12A | 0.8890 | 0.4783 | 0.5401 | 0.126* | |
C13 | 0.7030 (7) | 0.4417 (2) | 0.5583 (2) | 0.1127 (15) | |
H13A | 0.7167 | 0.4566 | 0.6125 | 0.135* | |
C14 | 0.5816 (6) | 0.4068 (3) | 0.5261 (3) | 0.1253 (17) | |
H14A | 0.5114 | 0.3966 | 0.5578 | 0.150* | |
C15 | 0.5590 (4) | 0.3853 (3) | 0.4445 (2) | 0.0976 (12) | |
H15A | 0.4748 | 0.3599 | 0.4213 | 0.117* | |
C16 | 0.8430 (4) | 0.84485 (18) | 0.1159 (2) | 0.0879 (10) | |
H16A | 0.8169 | 0.8794 | 0.0698 | 0.106* | |
H16B | 0.9448 | 0.8455 | 0.1316 | 0.106* | |
H16C | 0.7983 | 0.8641 | 0.1597 | 0.106* | |
C17 | 0.7953 (3) | 0.76125 (16) | 0.09517 (18) | 0.0620 (7) | |
C18 | 0.7899 (3) | 0.73321 (19) | 0.01830 (18) | 0.0692 (8) | |
H18A | 0.8117 | 0.7679 | −0.0218 | 0.083* | |
C19 | 0.7533 (3) | 0.65603 (19) | 0.00026 (15) | 0.0632 (7) | |
H19A | 0.7491 | 0.6372 | −0.0524 | 0.076* | |
C20 | 0.7220 (2) | 0.60473 (15) | 0.05940 (13) | 0.0484 (5) | |
C21 | 0.7236 (2) | 0.63084 (14) | 0.13826 (13) | 0.0428 (5) | |
C22 | 0.7614 (2) | 0.70990 (15) | 0.15326 (15) | 0.0512 (5) | |
H22A | 0.7643 | 0.7298 | 0.2054 | 0.061* | |
C23 | 0.6840 (2) | 0.52299 (15) | 0.04390 (13) | 0.0505 (5) | |
H23A | 0.6785 | 0.5016 | −0.0078 | 0.061* | |
C24 | 0.6183 (3) | 0.39617 (15) | 0.08596 (14) | 0.0542 (6) | |
H24A | 0.6056 | 0.3865 | 0.0282 | 0.065* | |
H24B | 0.5276 | 0.3862 | 0.1038 | 0.065* | |
C25 | 0.7248 (3) | 0.33834 (15) | 0.12673 (14) | 0.0533 (6) | |
C26 | 0.8671 (3) | 0.35274 (18) | 0.13351 (17) | 0.0670 (7) | |
H26A | 0.8993 | 0.4011 | 0.1142 | 0.080* | |
C27 | 0.9623 (4) | 0.2969 (2) | 0.1684 (2) | 0.0945 (11) | |
H27A | 1.0598 | 0.3064 | 0.1718 | 0.113* | |
C28 | 0.9154 (5) | 0.2271 (2) | 0.1983 (2) | 0.1035 (13) | |
H28A | 0.9808 | 0.1893 | 0.2235 | 0.124* | |
C29 | 0.7769 (5) | 0.2127 (2) | 0.19186 (19) | 0.0909 (11) | |
H29A | 0.7451 | 0.1645 | 0.2120 | 0.109* | |
C30 | 0.6814 (4) | 0.26767 (17) | 0.15608 (17) | 0.0722 (8) | |
H30A | 0.5842 | 0.2567 | 0.1516 | 0.087* | |
C31 | 0.6608 (3) | 0.61511 (17) | 0.29255 (14) | 0.0560 (6) | |
C32 | 0.8588 (2) | 0.51820 (15) | 0.25146 (13) | 0.0490 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ru1 | 0.03367 (10) | 0.04795 (12) | 0.03712 (11) | −0.00101 (7) | 0.00534 (7) | −0.00166 (7) |
O1 | 0.0984 (16) | 0.1024 (18) | 0.0723 (13) | −0.0069 (13) | 0.0236 (12) | −0.0440 (13) |
O2 | 0.0395 (10) | 0.1078 (17) | 0.0765 (13) | 0.0074 (10) | 0.0033 (9) | 0.0094 (12) |
N1 | 0.0520 (12) | 0.0533 (12) | 0.0433 (10) | −0.0021 (9) | 0.0112 (9) | 0.0027 (8) |
N2 | 0.0373 (9) | 0.0542 (11) | 0.0407 (10) | −0.0021 (8) | 0.0044 (7) | −0.0060 (8) |
C1 | 0.0550 (16) | 0.077 (2) | 0.083 (2) | 0.0204 (14) | −0.0055 (14) | −0.0101 (15) |
C2 | 0.0405 (12) | 0.0696 (16) | 0.0508 (13) | 0.0089 (11) | 0.0047 (10) | −0.0131 (11) |
C3 | 0.0383 (11) | 0.0556 (14) | 0.0460 (12) | 0.0013 (10) | 0.0063 (9) | −0.0079 (10) |
C4 | 0.0344 (10) | 0.0577 (13) | 0.0411 (11) | −0.0015 (9) | 0.0088 (9) | −0.0057 (9) |
C5 | 0.0401 (12) | 0.0606 (15) | 0.0518 (13) | −0.0072 (11) | 0.0129 (10) | −0.0032 (11) |
C6 | 0.0418 (13) | 0.0788 (19) | 0.0696 (17) | −0.0115 (13) | 0.0157 (12) | −0.0039 (14) |
C7 | 0.0327 (11) | 0.086 (2) | 0.0727 (17) | −0.0002 (12) | 0.0074 (11) | −0.0159 (15) |
C8 | 0.0537 (14) | 0.0619 (16) | 0.0539 (14) | −0.0130 (12) | 0.0171 (11) | 0.0017 (11) |
C9 | 0.0686 (16) | 0.0514 (15) | 0.0550 (14) | 0.0034 (12) | 0.0125 (12) | 0.0064 (11) |
C10 | 0.0706 (16) | 0.0516 (14) | 0.0500 (14) | 0.0111 (12) | 0.0148 (12) | 0.0112 (10) |
C11 | 0.098 (2) | 0.082 (2) | 0.0645 (19) | −0.0137 (19) | 0.0116 (17) | 0.0010 (15) |
C12 | 0.149 (4) | 0.088 (3) | 0.074 (2) | −0.018 (2) | 0.002 (2) | −0.0047 (17) |
C13 | 0.188 (5) | 0.085 (3) | 0.065 (2) | 0.025 (3) | 0.021 (3) | 0.0027 (18) |
C14 | 0.149 (4) | 0.157 (4) | 0.086 (3) | 0.048 (3) | 0.066 (3) | 0.041 (3) |
C15 | 0.084 (2) | 0.140 (3) | 0.074 (2) | 0.017 (2) | 0.0270 (17) | 0.031 (2) |
C16 | 0.083 (2) | 0.0567 (19) | 0.127 (3) | −0.0069 (16) | 0.025 (2) | 0.0144 (17) |
C17 | 0.0410 (13) | 0.0550 (15) | 0.089 (2) | 0.0005 (11) | 0.0065 (12) | 0.0140 (13) |
C18 | 0.0529 (15) | 0.079 (2) | 0.0744 (19) | −0.0042 (14) | 0.0070 (13) | 0.0331 (15) |
C19 | 0.0528 (14) | 0.086 (2) | 0.0499 (14) | −0.0070 (14) | 0.0045 (11) | 0.0145 (13) |
C20 | 0.0350 (11) | 0.0648 (15) | 0.0446 (12) | −0.0007 (10) | 0.0046 (9) | 0.0055 (10) |
C21 | 0.0281 (9) | 0.0520 (13) | 0.0477 (12) | 0.0016 (9) | 0.0036 (8) | 0.0043 (9) |
C22 | 0.0397 (11) | 0.0519 (14) | 0.0619 (14) | 0.0008 (10) | 0.0074 (10) | 0.0018 (11) |
C23 | 0.0430 (12) | 0.0691 (16) | 0.0391 (12) | −0.0019 (11) | 0.0058 (9) | −0.0036 (10) |
C24 | 0.0514 (13) | 0.0592 (15) | 0.0512 (13) | −0.0098 (11) | 0.0055 (10) | −0.0122 (11) |
C25 | 0.0662 (15) | 0.0485 (13) | 0.0455 (13) | −0.0071 (11) | 0.0095 (11) | −0.0112 (10) |
C26 | 0.0646 (16) | 0.0587 (17) | 0.0748 (18) | −0.0008 (13) | 0.0023 (13) | −0.0020 (13) |
C27 | 0.084 (2) | 0.076 (2) | 0.114 (3) | 0.0108 (18) | −0.0137 (19) | −0.0072 (19) |
C28 | 0.141 (4) | 0.061 (2) | 0.096 (3) | 0.021 (2) | −0.022 (2) | −0.0041 (17) |
C29 | 0.143 (3) | 0.0514 (18) | 0.073 (2) | −0.011 (2) | 0.001 (2) | −0.0029 (14) |
C30 | 0.095 (2) | 0.0563 (17) | 0.0665 (17) | −0.0171 (15) | 0.0172 (15) | −0.0121 (13) |
C31 | 0.0477 (13) | 0.0719 (17) | 0.0490 (14) | −0.0028 (12) | 0.0093 (10) | −0.0050 (12) |
C32 | 0.0418 (12) | 0.0614 (15) | 0.0446 (12) | −0.0001 (10) | 0.0089 (10) | 0.0025 (10) |
Ru1—C31 | 1.850 (3) | C12—H12A | 0.9500 |
Ru1—C32 | 1.921 (2) | C13—C14 | 1.351 (7) |
Ru1—C21 | 2.066 (2) | C13—H13A | 0.9500 |
Ru1—C4 | 2.110 (2) | C14—C15 | 1.427 (6) |
Ru1—N2 | 2.1583 (18) | C14—H14A | 0.9500 |
Ru1—N1 | 2.1763 (19) | C15—H15A | 0.9500 |
O1—C31 | 1.146 (3) | C16—C17 | 1.504 (4) |
O2—C32 | 1.142 (3) | C16—H16A | 0.9800 |
N1—C8 | 1.280 (3) | C16—H16B | 0.9800 |
N1—C9 | 1.485 (3) | C16—H16C | 0.9800 |
N2—C23 | 1.284 (3) | C17—C18 | 1.392 (4) |
N2—C24 | 1.464 (3) | C17—C22 | 1.395 (4) |
C1—C2 | 1.502 (4) | C18—C19 | 1.368 (4) |
C1—H1A | 0.9800 | C18—H18A | 0.9500 |
C1—H1B | 0.9800 | C19—C20 | 1.400 (3) |
C1—H1C | 0.9800 | C19—H19A | 0.9500 |
C2—C7 | 1.385 (4) | C20—C21 | 1.418 (3) |
C2—C3 | 1.403 (3) | C20—C23 | 1.437 (3) |
C3—C4 | 1.391 (3) | C21—C22 | 1.392 (3) |
C3—H3A | 0.9500 | C22—H22A | 0.9500 |
C4—C5 | 1.412 (3) | C23—H23A | 0.9500 |
C5—C6 | 1.396 (3) | C24—C25 | 1.506 (4) |
C5—C8 | 1.446 (4) | C24—H24A | 0.9900 |
C6—C7 | 1.384 (4) | C24—H24B | 0.9900 |
C6—H6A | 0.9500 | C25—C30 | 1.382 (4) |
C7—H7A | 0.9500 | C25—C26 | 1.385 (4) |
C8—H8A | 0.9500 | C26—C27 | 1.384 (4) |
C9—C10 | 1.501 (4) | C26—H26A | 0.9500 |
C9—H9A | 0.9900 | C27—C28 | 1.386 (5) |
C9—H9B | 0.9900 | C27—H27A | 0.9500 |
C10—C11 | 1.362 (4) | C28—C29 | 1.350 (5) |
C10—C15 | 1.373 (4) | C28—H28A | 0.9500 |
C11—C12 | 1.381 (5) | C29—C30 | 1.381 (5) |
C11—H11A | 0.9500 | C29—H29A | 0.9500 |
C12—C13 | 1.319 (6) | C30—H30A | 0.9500 |
C31—Ru1—C32 | 91.14 (11) | C12—C13—C14 | 121.3 (4) |
C31—Ru1—C21 | 91.82 (11) | C12—C13—H13A | 119.3 |
C32—Ru1—C21 | 92.11 (9) | C14—C13—H13A | 119.3 |
C31—Ru1—C4 | 87.82 (10) | C13—C14—C15 | 119.8 (4) |
C32—Ru1—C4 | 175.66 (9) | C13—C14—H14A | 120.1 |
C21—Ru1—C4 | 92.13 (8) | C15—C14—H14A | 120.1 |
C31—Ru1—N2 | 168.09 (10) | C10—C15—C14 | 118.4 (4) |
C32—Ru1—N2 | 96.14 (8) | C10—C15—H15A | 120.8 |
C21—Ru1—N2 | 78.54 (8) | C14—C15—H15A | 120.8 |
C4—Ru1—N2 | 85.58 (8) | C17—C16—H16A | 109.5 |
C31—Ru1—N1 | 98.03 (10) | C17—C16—H16B | 109.5 |
C32—Ru1—N1 | 97.92 (9) | H16A—C16—H16B | 109.5 |
C21—Ru1—N1 | 165.76 (8) | C17—C16—H16C | 109.5 |
C4—Ru1—N1 | 78.06 (8) | H16A—C16—H16C | 109.5 |
N2—Ru1—N1 | 90.31 (7) | H16B—C16—H16C | 109.5 |
C8—N1—C9 | 118.8 (2) | C18—C17—C22 | 119.2 (3) |
C8—N1—Ru1 | 113.26 (16) | C18—C17—C16 | 120.2 (3) |
C9—N1—Ru1 | 127.94 (16) | C22—C17—C16 | 120.6 (3) |
C23—N2—C24 | 119.02 (19) | C19—C18—C17 | 120.3 (2) |
C23—N2—Ru1 | 113.68 (16) | C19—C18—H18A | 119.8 |
C24—N2—Ru1 | 127.22 (14) | C17—C18—H18A | 119.8 |
C2—C1—H1A | 109.5 | C18—C19—C20 | 120.0 (3) |
C2—C1—H1B | 109.5 | C18—C19—H19A | 120.0 |
H1A—C1—H1B | 109.5 | C20—C19—H19A | 120.0 |
C2—C1—H1C | 109.5 | C19—C20—C21 | 121.9 (2) |
H1A—C1—H1C | 109.5 | C19—C20—C23 | 122.3 (2) |
H1B—C1—H1C | 109.5 | C21—C20—C23 | 115.8 (2) |
C7—C2—C3 | 118.9 (2) | C22—C21—C20 | 115.7 (2) |
C7—C2—C1 | 120.8 (2) | C22—C21—Ru1 | 131.09 (17) |
C3—C2—C1 | 120.2 (2) | C20—C21—Ru1 | 113.18 (17) |
C4—C3—C2 | 122.6 (2) | C21—C22—C17 | 123.0 (2) |
C4—C3—H3A | 118.7 | C21—C22—H22A | 118.5 |
C2—C3—H3A | 118.7 | C17—C22—H22A | 118.5 |
C3—C4—C5 | 116.5 (2) | N2—C23—C20 | 118.7 (2) |
C3—C4—Ru1 | 130.81 (17) | N2—C23—H23A | 120.7 |
C5—C4—Ru1 | 112.71 (17) | C20—C23—H23A | 120.7 |
C6—C5—C4 | 121.9 (2) | N2—C24—C25 | 113.28 (19) |
C6—C5—C8 | 122.4 (2) | N2—C24—H24A | 108.9 |
C4—C5—C8 | 115.7 (2) | C25—C24—H24A | 108.9 |
C7—C6—C5 | 119.4 (3) | N2—C24—H24B | 108.9 |
C7—C6—H6A | 120.3 | C25—C24—H24B | 108.9 |
C5—C6—H6A | 120.3 | H24A—C24—H24B | 107.7 |
C6—C7—C2 | 120.7 (2) | C30—C25—C26 | 118.4 (3) |
C6—C7—H7A | 119.6 | C30—C25—C24 | 119.9 (3) |
C2—C7—H7A | 119.6 | C26—C25—C24 | 121.7 (2) |
N1—C8—C5 | 119.8 (2) | C27—C26—C25 | 120.2 (3) |
N1—C8—H8A | 120.1 | C27—C26—H26A | 119.9 |
C5—C8—H8A | 120.1 | C25—C26—H26A | 119.9 |
N1—C9—C10 | 112.2 (2) | C26—C27—C28 | 120.0 (4) |
N1—C9—H9A | 109.2 | C26—C27—H27A | 120.0 |
C10—C9—H9A | 109.2 | C28—C27—H27A | 120.0 |
N1—C9—H9B | 109.2 | C29—C28—C27 | 120.1 (3) |
C10—C9—H9B | 109.2 | C29—C28—H28A | 120.0 |
H9A—C9—H9B | 107.9 | C27—C28—H28A | 120.0 |
C11—C10—C15 | 118.9 (3) | C28—C29—C30 | 120.2 (3) |
C11—C10—C9 | 121.6 (3) | C28—C29—H29A | 119.9 |
C15—C10—C9 | 119.4 (3) | C30—C29—H29A | 119.9 |
C10—C11—C12 | 121.5 (4) | C29—C30—C25 | 121.1 (3) |
C10—C11—H11A | 119.2 | C29—C30—H30A | 119.5 |
C12—C11—H11A | 119.2 | C25—C30—H30A | 119.5 |
C13—C12—C11 | 119.9 (4) | O1—C31—Ru1 | 175.5 (3) |
C13—C12—H12A | 120.0 | O2—C32—Ru1 | 174.6 (2) |
C11—C12—H12A | 120.0 |
Experimental details
Crystal data | |
Chemical formula | [Ru(C15H14N)2(CO)2] |
Mr | 573.63 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 9.685 (3), 16.813 (4), 17.126 (4) |
β (°) | 99.156 (5) |
V (Å3) | 2753.3 (12) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.60 |
Crystal size (mm) | 0.33 × 0.20 × 0.16 |
Data collection | |
Diffractometer | Rigaku Saturn70 CCD |
Absorption correction | Multi-scan (CrystalClear; Rigaku/MSC, 2004) |
Tmin, Tmax | 0.827, 0.910 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 21246, 6290, 5347 |
Rint | 0.028 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.084, 1.09 |
No. of reflections | 6290 |
No. of parameters | 336 |
No. of restraints | 66 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.85, −0.35 |
Computer programs: CrystalClear (Rigaku/MSC, 2004), CrystalClear, SHELXTL (Sheldrick, 1997), SHELXTL.
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Transition metal catalyzed organic transformations involving C—H bond activation have been sought after for decades (Kleiman & Dubeck 1963; Crabtree, 1985; Murai et al., 1993). In this context, Ru and Pd complexes are most often used as catalysts, and substrates for these reactions usually contain directing groups. The proposed mechanism for these reactions involves cleavage of a C—H bond ortho to a directing group and formation of a cyclometalated intermediate (Kakiuchi et al., 2001). However, very few examples have been reported of these intermediates. Herein, we wish to report the structure of a Ru(II) complex derived from the cleavage of a C—H bond in p-methylbenzylidenebenzylamine with Ru3(CO)12, Ru(η2-(C,N)-p-MeC6H3CH=NCH2Ph)2(CO)2 (I).
As shown in Fig. 1 the Ru coordination polyhedron adopts in (I) a distorted octahedral geometry by coordination of two N atoms and two C atoms from two Schiff base molecules, and two cis-disposed carbonyl ligands. The N atoms from the Schiff bases are respectively trans to a carbonyl ligand and an aryl C atom. The Ru—N bond distances are 2.1556 (19)Å and 2.176 (2) Å, respectively, somewhat longer than those of other similar Ru(II) complexes (Cabeza et al., 2001), while Ru—C distances involving carbonyl ligands are normal. The remaining Ru—C bond distances are 2.067 (2)Å and 2.111 (2) Å. Bond angles involving the ruthenium center fall in the range 78.12 (9) (C4—Ru(1)—N(1)) to 167.99 (11)° (C31—Ru(1)—N(2)). The configurations of the two Schiff base molecules are significantly different, with dihedral angles between aromatic ring planes being 73.3 (1)° (for C1 → C6 and C10 → C15) and 86.4 (1)° (C17 → C22 and C25 → C30), respectively.