The title compound, [Ru(C12H14NO2)Cl(η6-C6H6)], exhibits a half-sandwich tripod stand structure and crystallizes in the orthorhombic space group P212121. The arene group is η6 π-coordinated to the Ru atom with a centroid-to-metal distance of 1.6590 (5) Å, with the (S)-2-(4-isopropyl-4,5-dihydrooxazol-2-yl)phenolate chelate ligand forming a bite angle of 86.88 (19)° through its N and phenolate O atoms. The pseudo-octahedral geometry assumed by the complex is completed by a chloride ligand. The coordination of the optically pure bidentate ligand induces metal centered chirality onto the complex with a Flack parameter of −0.056.
Supporting information
CCDC reference: 2372332
(
η6-Benzene)chlorido[(
S)-2-(4-isopropyl-4,5-dihydrooxazol-2-yl)phenolato]ruthenium(II)
top
Crystal data top
[Ru(C12H14NO2)Cl(C6H6)] | Dx = 1.632 Mg m−3 |
Mr = 418.87 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P212121 | Cell parameters from 1424 reflections |
a = 6.5669 (18) Å | θ = 2.6–22.4° |
b = 9.414 (3) Å | µ = 1.09 mm−1 |
c = 27.570 (9) Å | T = 293 K |
V = 1704.5 (9) Å3 | Plate, orange |
Z = 4 | 0.47 × 0.18 × 0.15 mm |
F(000) = 848 | |
Data collection top
Bruker APEXII CCD diffractometer | 2937 reflections with I > 2σ(I) |
Detector resolution: φ and ω scans pixels mm-1 | Rint = 0.053 |
Bruker APEXII CCD scans | θmax = 28.3°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Krause et al., 2015) | h = −8→6 |
Tmin = 0.662, Tmax = 0.746 | k = −12→12 |
9005 measured reflections | l = −36→26 |
4074 independent reflections | |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.045 | H-atom parameters constrained |
wR(F2) = 0.089 | w = 1/[σ2(Fo2) + (0.0264P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.98 | (Δ/σ)max = 0.002 |
4074 reflections | Δρmax = 0.66 e Å−3 |
210 parameters | Δρmin = −0.41 e Å−3 |
0 restraints | Absolute structure: Flack x determined using 934 quotients
[(I+)-(I-)]/[(I+)+(I-)]
(Parsons et al., 2013) |
Primary atom site location: dual | Absolute structure parameter: −0.05 (6) |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Refinement. The structure solution and refinement were implemented using WinGX software
program (Farrugia, 2012). The highest peak and deepest hole are
0.66 and -0.41 e Å-3, respectively,
which are 1.13 and 0.83 Å away from the ruthenium center.
The refinement of the hydrogen atoms was performed isotropically in their
idealized geometry while sitting and riding on their anisotropically refined
parent atoms with Uiso = 1.2Ueq for the aromatic and methine
protons, and Uiso = 1.5Ueq for the methyl protons. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.2589 (12) | 1.2854 (9) | 0.8188 (3) | 0.047 (2) | |
H1A | 0.379457 | 1.320678 | 0.835165 | 0.057* | |
H1B | 0.267789 | 1.309492 | 0.784613 | 0.057* | |
C2 | 0.2375 (11) | 1.1261 (8) | 0.8256 (2) | 0.0362 (17) | |
H2 | 0.364617 | 1.086811 | 0.838471 | 0.043* | |
C3 | 0.1761 (10) | 1.0454 (9) | 0.7791 (2) | 0.0409 (19) | |
H3 | 0.137753 | 0.948622 | 0.788452 | 0.049* | |
C4 | −0.0048 (18) | 1.1122 (8) | 0.7531 (2) | 0.0508 (17) | |
H4A | 0.030043 | 1.206761 | 0.743036 | 0.076* | |
H4B | −0.119213 | 1.115928 | 0.774774 | 0.076* | |
H4C | −0.039225 | 1.056171 | 0.725238 | 0.076* | |
C5 | 0.3629 (12) | 1.0355 (12) | 0.7454 (3) | 0.070 (3) | |
H5A | 0.333602 | 0.971968 | 0.719131 | 0.105* | |
H5B | 0.477509 | 1.000471 | 0.763443 | 0.105* | |
H5C | 0.393965 | 1.128034 | 0.732786 | 0.105* | |
C6 | −0.0089 (13) | 1.2403 (6) | 0.86639 (19) | 0.0312 (13) | |
C7 | −0.1874 (9) | 1.2786 (7) | 0.8950 (2) | 0.0316 (16) | |
C8 | −0.2721 (11) | 1.4153 (8) | 0.8885 (2) | 0.0394 (17) | |
H8 | −0.212165 | 1.477639 | 0.866531 | 0.047* | |
C9 | −0.4400 (11) | 1.4573 (9) | 0.9137 (3) | 0.053 (2) | |
H9 | −0.498466 | 1.545825 | 0.908180 | 0.064* | |
C10 | −0.5219 (15) | 1.3655 (9) | 0.9478 (3) | 0.056 (2) | |
H10 | −0.632514 | 1.395362 | 0.966250 | 0.067* | |
C11 | −0.4456 (10) | 1.2333 (9) | 0.9552 (3) | 0.047 (2) | |
H11 | −0.506447 | 1.174317 | 0.978042 | 0.057* | |
C12 | −0.2755 (10) | 1.1833 (8) | 0.9288 (2) | 0.0319 (16) | |
C13 | 0.2044 (11) | 0.9128 (8) | 0.9641 (2) | 0.0424 (19) | |
H13 | 0.238607 | 0.979015 | 0.987744 | 0.051* | |
C14 | 0.0350 (12) | 0.8234 (7) | 0.9705 (2) | 0.042 (2) | |
H14 | −0.041486 | 0.830265 | 0.998837 | 0.050* | |
C15 | −0.0200 (14) | 0.7245 (7) | 0.9352 (2) | 0.0456 (18) | |
H15 | −0.130235 | 0.664262 | 0.940233 | 0.055* | |
C16 | 0.0933 (11) | 0.7167 (8) | 0.8916 (3) | 0.047 (2) | |
H16 | 0.052812 | 0.654450 | 0.867215 | 0.057* | |
C17 | 0.2667 (11) | 0.8025 (8) | 0.8847 (3) | 0.0443 (19) | |
H17 | 0.343741 | 0.794385 | 0.856557 | 0.053* | |
C18 | 0.3229 (10) | 0.9013 (8) | 0.9212 (3) | 0.043 (2) | |
H18 | 0.437009 | 0.958522 | 0.916953 | 0.052* | |
N1 | 0.0747 (7) | 1.1175 (6) | 0.86312 (18) | 0.0311 (14) | |
O1 | −0.2134 (7) | 1.0558 (5) | 0.93758 (15) | 0.0381 (11) | |
O2 | 0.0756 (7) | 1.3444 (5) | 0.84022 (17) | 0.0456 (14) | |
Cl1 | −0.2594 (3) | 0.8953 (2) | 0.84198 (6) | 0.0507 (5) | |
Ru1 | 0.00224 (9) | 0.93480 (5) | 0.90217 (2) | 0.02858 (14) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.044 (5) | 0.057 (5) | 0.040 (4) | −0.015 (4) | 0.012 (4) | 0.001 (4) |
C2 | 0.027 (4) | 0.054 (5) | 0.027 (3) | 0.001 (4) | 0.008 (3) | 0.000 (3) |
C3 | 0.040 (4) | 0.047 (5) | 0.036 (4) | 0.006 (4) | 0.010 (3) | −0.003 (4) |
C4 | 0.052 (4) | 0.061 (5) | 0.039 (3) | −0.005 (8) | −0.013 (4) | −0.001 (3) |
C5 | 0.061 (6) | 0.106 (9) | 0.044 (5) | 0.030 (6) | 0.012 (4) | −0.004 (5) |
C6 | 0.041 (4) | 0.028 (3) | 0.025 (3) | −0.010 (5) | −0.001 (4) | −0.001 (2) |
C7 | 0.027 (4) | 0.037 (4) | 0.030 (4) | 0.000 (3) | 0.000 (3) | −0.012 (3) |
C8 | 0.045 (4) | 0.038 (4) | 0.036 (4) | 0.003 (4) | −0.008 (3) | −0.004 (3) |
C9 | 0.054 (6) | 0.048 (5) | 0.058 (5) | 0.017 (4) | −0.015 (4) | −0.021 (4) |
C10 | 0.045 (5) | 0.066 (5) | 0.055 (4) | 0.011 (6) | 0.008 (5) | −0.026 (4) |
C11 | 0.043 (6) | 0.049 (5) | 0.051 (4) | 0.002 (4) | 0.014 (3) | −0.017 (4) |
C12 | 0.029 (4) | 0.038 (4) | 0.029 (3) | −0.001 (3) | 0.003 (3) | −0.013 (3) |
C13 | 0.040 (4) | 0.047 (5) | 0.040 (4) | −0.002 (4) | −0.014 (3) | 0.008 (4) |
C14 | 0.050 (6) | 0.041 (4) | 0.035 (3) | −0.003 (4) | 0.007 (4) | 0.012 (3) |
C15 | 0.046 (5) | 0.035 (4) | 0.056 (4) | −0.010 (5) | 0.008 (5) | 0.013 (3) |
C16 | 0.052 (5) | 0.035 (4) | 0.056 (5) | 0.001 (4) | 0.001 (4) | −0.003 (4) |
C17 | 0.029 (4) | 0.045 (5) | 0.059 (5) | 0.008 (4) | 0.009 (4) | 0.001 (4) |
C18 | 0.027 (4) | 0.044 (5) | 0.059 (5) | 0.001 (3) | −0.004 (3) | 0.010 (4) |
N1 | 0.019 (3) | 0.047 (4) | 0.028 (3) | −0.008 (3) | 0.005 (2) | 0.001 (3) |
O1 | 0.039 (3) | 0.037 (3) | 0.039 (2) | 0.001 (3) | 0.017 (2) | −0.002 (2) |
O2 | 0.049 (3) | 0.043 (3) | 0.046 (3) | −0.007 (2) | 0.012 (2) | 0.008 (2) |
Cl1 | 0.0276 (10) | 0.0772 (16) | 0.0475 (10) | −0.0096 (10) | −0.0033 (8) | −0.0106 (10) |
Ru1 | 0.0237 (2) | 0.0325 (2) | 0.0295 (2) | −0.0020 (4) | 0.0034 (3) | −0.0008 (2) |
Geometric parameters (Å, º) top
C1—O2 | 1.452 (8) | C9—C10 | 1.386 (11) |
C1—C2 | 1.519 (10) | C9—H9 | 0.9300 |
C1—H1A | 0.9700 | C10—C11 | 1.357 (11) |
C1—H1B | 0.9700 | C10—H10 | 0.9300 |
C2—N1 | 1.490 (7) | C11—C12 | 1.414 (9) |
C2—C3 | 1.542 (9) | C11—H11 | 0.9300 |
C2—H2 | 0.9800 | C12—O1 | 1.291 (8) |
C3—C4 | 1.523 (12) | C13—C14 | 1.406 (9) |
C3—C5 | 1.541 (9) | C13—C18 | 1.420 (9) |
C3—H3 | 0.9800 | C13—H13 | 0.9300 |
C4—H4A | 0.9600 | C14—C15 | 1.396 (9) |
C4—H4B | 0.9600 | C14—H14 | 0.9300 |
C4—H4C | 0.9600 | C15—C16 | 1.416 (10) |
C5—H5A | 0.9600 | C15—H15 | 0.9300 |
C5—H5B | 0.9600 | C16—C17 | 1.409 (10) |
C5—H5C | 0.9600 | C16—H16 | 0.9300 |
C6—N1 | 1.282 (8) | C17—C18 | 1.418 (10) |
C6—O2 | 1.338 (7) | C17—H17 | 0.9300 |
C6—C7 | 1.458 (10) | C18—H18 | 0.9300 |
C7—C8 | 1.413 (9) | N1—Ru1 | 2.084 (6) |
C7—C12 | 1.418 (9) | O1—Ru1 | 2.063 (5) |
C8—C9 | 1.363 (9) | Cl1—Ru1 | 2.4176 (19) |
C8—H8 | 0.9300 | | |
| | | |
O2—C1—C2 | 104.5 (6) | C8—C9—C10 | 118.6 (8) |
O2—C1—H1A | 110.9 | C8—C9—H9 | 120.7 |
C2—C1—H1A | 110.9 | C10—C9—H9 | 120.7 |
O2—C1—H1B | 110.9 | C11—C10—C9 | 122.0 (8) |
C2—C1—H1B | 110.9 | C11—C10—H10 | 119.0 |
H1A—C1—H1B | 108.9 | C9—C10—H10 | 119.0 |
N1—C2—C1 | 101.9 (6) | C10—C11—C12 | 121.4 (8) |
N1—C2—C3 | 111.3 (5) | C10—C11—H11 | 119.3 |
C1—C2—C3 | 114.1 (6) | C12—C11—H11 | 119.3 |
N1—C2—H2 | 109.8 | O1—C12—C11 | 117.5 (7) |
C1—C2—H2 | 109.8 | O1—C12—C7 | 125.7 (6) |
C3—C2—H2 | 109.8 | C11—C12—C7 | 116.7 (7) |
C4—C3—C5 | 111.3 (6) | C14—C13—C18 | 119.6 (7) |
C4—C3—C2 | 113.0 (6) | C14—C13—H13 | 120.2 |
C5—C3—C2 | 108.8 (6) | C18—C13—H13 | 120.2 |
C4—C3—H3 | 107.9 | C15—C14—C13 | 121.0 (7) |
C5—C3—H3 | 107.9 | C15—C14—H14 | 119.5 |
C2—C3—H3 | 107.9 | C13—C14—H14 | 119.5 |
C3—C4—H4A | 109.5 | C14—C15—C16 | 119.5 (7) |
C3—C4—H4B | 109.5 | C14—C15—H15 | 120.3 |
H4A—C4—H4B | 109.5 | C16—C15—H15 | 120.3 |
C3—C4—H4C | 109.5 | C17—C16—C15 | 120.6 (7) |
H4A—C4—H4C | 109.5 | C17—C16—H16 | 119.7 |
H4B—C4—H4C | 109.5 | C15—C16—H16 | 119.7 |
C3—C5—H5A | 109.5 | C16—C17—C18 | 119.5 (7) |
C3—C5—H5B | 109.5 | C16—C17—H17 | 120.3 |
H5A—C5—H5B | 109.5 | C18—C17—H17 | 120.3 |
C3—C5—H5C | 109.5 | C17—C18—C13 | 119.8 (7) |
H5A—C5—H5C | 109.5 | C17—C18—H18 | 120.1 |
H5B—C5—H5C | 109.5 | C13—C18—H18 | 120.1 |
N1—C6—O2 | 116.4 (7) | C6—N1—C2 | 107.9 (6) |
N1—C6—C7 | 127.3 (6) | C6—N1—Ru1 | 127.6 (4) |
O2—C6—C7 | 116.3 (6) | C2—N1—Ru1 | 124.5 (5) |
C8—C7—C12 | 120.0 (6) | C12—O1—Ru1 | 129.9 (4) |
C8—C7—C6 | 118.3 (6) | C6—O2—C1 | 106.5 (6) |
C12—C7—C6 | 121.8 (6) | O1—Ru1—N1 | 86.9 (2) |
C9—C8—C7 | 121.2 (7) | O1—Ru1—Cl1 | 85.52 (14) |
C9—C8—H8 | 119.4 | N1—Ru1—Cl1 | 86.26 (15) |
C7—C8—H8 | 119.4 | | |
| | | |
O2—C1—C2—N1 | −16.4 (7) | C6—C7—C12—C11 | 178.7 (6) |
O2—C1—C2—C3 | 103.6 (6) | C18—C13—C14—C15 | −0.7 (11) |
N1—C2—C3—C4 | 65.7 (8) | C13—C14—C15—C16 | −1.7 (11) |
C1—C2—C3—C4 | −48.8 (9) | C14—C15—C16—C17 | 3.3 (11) |
N1—C2—C3—C5 | −170.2 (6) | C15—C16—C17—C18 | −2.5 (11) |
C1—C2—C3—C5 | 75.2 (8) | C16—C17—C18—C13 | 0.1 (11) |
N1—C6—C7—C8 | −171.5 (7) | C14—C13—C18—C17 | 1.5 (11) |
O2—C6—C7—C8 | 7.7 (9) | O2—C6—N1—C2 | −5.5 (8) |
N1—C6—C7—C12 | 8.9 (11) | C7—C6—N1—C2 | 173.7 (6) |
O2—C6—C7—C12 | −172.0 (6) | O2—C6—N1—Ru1 | 174.7 (4) |
C12—C7—C8—C9 | −0.9 (10) | C7—C6—N1—Ru1 | −6.2 (10) |
C6—C7—C8—C9 | 179.4 (6) | C1—C2—N1—C6 | 13.7 (7) |
C7—C8—C9—C10 | 2.9 (11) | C3—C2—N1—C6 | −108.3 (7) |
C8—C9—C10—C11 | −3.0 (13) | C1—C2—N1—Ru1 | −166.5 (4) |
C9—C10—C11—C12 | 1.1 (13) | C3—C2—N1—Ru1 | 71.5 (7) |
C10—C11—C12—O1 | −179.3 (7) | C11—C12—O1—Ru1 | 171.7 (4) |
C10—C11—C12—C7 | 0.9 (10) | C7—C12—O1—Ru1 | −8.6 (10) |
C8—C7—C12—O1 | 179.3 (6) | N1—C6—O2—C1 | −5.9 (8) |
C6—C7—C12—O1 | −1.1 (10) | C7—C6—O2—C1 | 174.8 (6) |
C8—C7—C12—C11 | −1.0 (9) | C2—C1—O2—C6 | 14.2 (7) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8···O2 | 0.93 | 2.38 | 2.725 (9) | 102 |
C17—H17···Cl1i | 0.93 | 2.80 | 3.440 (8) | 127 |
C18—H18···O1i | 0.93 | 2.54 | 3.405 (8) | 156 |
Symmetry code: (i) x+1, y, z. |