research communications
κ2N,N′)bis(3,5-di-tert-butyl-o-benzoquinonato-κ2O,O′)ruthenium(II)
of (2,2′-bipyridine-aDepartment of Chemistry, College of Science, Sultan Qaboos University, PO Box 36, Al-Khod 123, Muscat, Sultanate of Oman, bDepartment of Chemistry, Indian Institute of Technology, Kanpur 208 016 UP, India, and cDepartment of General and Inorganic Chemistry, National Technical University of Ukraine, Kyiv Polytechnic Institute, 37 Prospect Peremogy, 03056 Kiev, Ukraine
*Correspondence e-mail: potaskalov@xtf.kpi.ua
In the title mononuclear complex, [Ru(C14H20O2)2(C10H8N2)], the RuII ion has a distorted octahedral coordination environment defined by two N atoms of the chelating 2,2′-bipyridine ligand and four O atoms from two 3,5-di-tert-butyl-o-benzoquinone ligands. In the crystal, the complex molecules are linked by intermolecular C—H⋯O hydrogen bonds and π–π stacking interactions between the 2,2′-bipyridine ligands [centroid–centroid distance = 3.538 (3) Å], resulting in a layer structure extending parallel to the ab plane.
Keywords: crystal structure; Ru(II) complex; π–π stacking; 3,5-di-tert-butyl-o-benzoquinone; 2,2′-bipyridine.
CCDC reference: 1533648
1. Chemical context
The coordination chemistry of o-quinone ligands has been a subject of interest since the beginning of the century, but only within the past decade have detailed studies on the composition and properties of o-quinone complexes been carried out. It has been reported that o-quinone derivatives are non-innocent electroactive ligands that can be found as neutral radical semiquinones or dianionic catecholates (Lever et al., 1988). The coordination chemistry of ruthenium complexes has been studied over the past few decades because of their versatile and diverse applications in molecular catalysis (Pagliaro et al., 2005; Ramakrishna & Bhat, 2011) and bioinorganic chemistry (van Rijt & Sadler, 2009). Ruthenium complexes with two o-quinone derivatives and one 2,2′-bipyridine (bpy) ligand, namely [Ru(bpy)(C6H4O2)2] and [Ru(bpy)(C14H20O2)2] (title compound), have been investigated by using various experimental techniques (Lever et al., 1988). Although the ruthenium metals in these complexes potentially could be in the (II), (III) or (IV) according to the oxidation states of the two o-quinone ligands, the state of the metals was confirmed to be bivalent by In order to obtain ruthenium(III) species, it was necessary to oxidize the complexes by silver perchlorate in non-aqueous media. Lever et al. (1988) concluded that the complexes are best regarded as RuII(bpy)(sq)2 (sq: semiquinone anion-radical) with significant mixing of metal and ligand orbitals through Ru–sq π back-donation, which results in elongation of the C—O bonds of o-quinone ligands. This elongation has been demonstrated for [Ru(bpy)(C6H4O2)2] by X-ray single crystal analysis, but the structure of the title compound has not previously been characterized.
2. Structural commentary
In the title compound, the RuII ion has a distorted octahedral RuN2O4 coordination environment defined by two 3,5-di-tert-butyl-o-benzosemiquinone anion-radicals and one 2,2′-bipyridine ligand (Fig. 1). The coordination environment is identified by Ru—O and Ru—N bonds (Table 1). The C—N and C—C bond lengths in the 2,2′-bipyridine ligand are normal for 2-substituted pyridine derivatives (Krämer & Fritsky, 2000; Strotmeyer et al., 2003; Moroz et al., 2012). The benzosemiquinone ligands exhibit almost equivalent C—O distances (Table 1). These bond lengths are intermediate between values expected for the semiquinone (1.29 Å) and catecholate (1.34 Å) forms (Buchanan et al., 1978). The Ru—O, Ru—N, C—O and C—C bond lengths in the title complex are very close to those observed in [Ru(bpy)(C6H4O2)2] (Lever et al., 1988).
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3. Supramolecular features
In the crystal, the complex molecules are linked via C—H⋯O hydrogen bonds (Table 2) and π–π stacking interactions between inversion-related 2,2′-bipyridine ligands [centroid–centroid distance = 3.538 (3) Å], which results in a layer structure parallel to the ab plane (Figs. 2 and 3).
4. Database survey
A search of the Cambridge Structural Database (CSD, Version 5.37, update May 2016; Groom et al., 2016) gave 14 hits for mononuclear ruthenium complexes with 3,5-di-tert-butyl-o-benzoquinone ligands in three possible catecholate, semiquinone and quinone forms (CSD refcodes: EHUMEZ, EHUMID, EHUMOJ, FAGKON, FAGKON10, FIHQOC, FIRVIL, JECHII, JECHOO, MAFHOR, SAHHUF, SOCCAO, VINZIB, WUPGUJ).
5. Synthesis and crystallization
3,5-Di-tert-butyl-o-benzoquinone (0.2 g, 0.90 mmol) was added to 20 ml dry methanol and then triethylamine (0.181 g, 1.8 mmol) was added dropwise and the resultant mixture was stirred for 5 min. Ru(bpy)2Cl2 (0.288 g, 0.45 mmol) was then added to the solution and the contents were refluxed for 6 h. After refluxing, the reaction mixture was cooled down to room temperature and the contents were filtered off. The obtained residue was washed with cold methanol and dried in vacuo (yield: 0.160 g, 70%). Slow evaporation of a solution of the compound in a CH2Cl2–MeOH mixture (1:1, v/v) yielded single crystals suitable for X-ray diffraction. Crystals of title compound gave no EPR signal at room and liquid nitrogen temperatures, and thus are diamagnetic.
6. Refinement
Crystal data, data collection and structure . H atoms of the methyl groups were located in a difference Fourier map and refined as part of rigid rotating groups, with C—H = 0.96 Å and Uiso(H) = 1.5Ueq(C). The remaining (aromatic) H atoms were placed geometrically and refined using a riding model, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C).
details are summarized in Table 3Supporting information
CCDC reference: 1533648
https://doi.org/10.1107/S205698901700281X/is5467sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S205698901700281X/is5467Isup2.hkl
Data collection: SMART (Bruker, 2003); cell
SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL2014/6 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenberg & Putz, 2006); software used to prepare material for publication: DIAMOND (Brandenberg & Putz, 2006).[Ru(C14H20O2)2(C10H8N2)] | Z = 2 |
Mr = 697.85 | F(000) = 732 |
Triclinic, P1 | Dx = 1.319 Mg m−3 |
a = 10.125 (5) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.325 (5) Å | Cell parameters from 1535 reflections |
c = 17.419 (5) Å | θ = 2.0–25.0° |
α = 76.583 (5)° | µ = 0.49 mm−1 |
β = 83.238 (5)° | T = 100 K |
γ = 85.777 (5)° | Block, red |
V = 1756.9 (13) Å3 | 0.21 × 0.17 × 0.13 mm |
Bruker SMART APEX CCD diffractometer | 6058 independent reflections |
Radiation source: fine-focus sealed tube | 4508 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
/w–scans | θmax = 25.1°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | h = −12→9 |
Tmin = 0.902, Tmax = 0.925 | k = −12→12 |
8836 measured reflections | l = −20→20 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.051 | H-atom parameters constrained |
wR(F2) = 0.142 | w = 1/[σ2(Fo2) + (0.0802P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max = 0.001 |
6058 reflections | Δρmax = 0.95 e Å−3 |
418 parameters | Δρmin = −0.48 e Å−3 |
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. |
x | y | z | Uiso*/Ueq | ||
Ru1 | 0.23460 (4) | 0.24040 (4) | 0.88962 (2) | 0.02318 (15) | |
O1 | 0.3873 (3) | 0.2156 (3) | 0.81046 (19) | 0.0282 (8) | |
O2 | 0.2021 (3) | 0.4171 (3) | 0.81903 (18) | 0.0248 (7) | |
O3 | 0.3497 (3) | 0.3434 (3) | 0.93673 (17) | 0.0230 (7) | |
O4 | 0.1382 (3) | 0.1589 (3) | 0.82104 (18) | 0.0265 (7) | |
N1 | 0.2578 (4) | 0.0644 (4) | 0.9718 (2) | 0.0218 (8) | |
N2 | 0.0725 (3) | 0.2515 (4) | 0.9701 (2) | 0.0195 (8) | |
C1 | 0.2025 (5) | 0.1849 (5) | 0.7483 (3) | 0.0302 (12) | |
C2 | 0.1427 (6) | 0.1768 (5) | 0.6815 (3) | 0.0345 (12) | |
H2 | 0.0544 | 0.1539 | 0.6868 | 0.041* | |
C3 | 0.2142 (6) | 0.2025 (5) | 0.6076 (3) | 0.0405 (14) | |
C4 | 0.1509 (6) | 0.2096 (6) | 0.5313 (3) | 0.0476 (15) | |
C5 | 0.1523 (8) | 0.3538 (7) | 0.4812 (4) | 0.071 (2) | |
H5A | 0.1063 | 0.4127 | 0.5119 | 0.107* | |
H5B | 0.1087 | 0.3594 | 0.4344 | 0.107* | |
H5C | 0.2427 | 0.3792 | 0.4662 | 0.107* | |
C6 | 0.2347 (7) | 0.1222 (6) | 0.4809 (3) | 0.0571 (18) | |
H6A | 0.3219 | 0.1562 | 0.4657 | 0.086* | |
H6B | 0.1922 | 0.1238 | 0.4343 | 0.086* | |
H6C | 0.2419 | 0.0322 | 0.5115 | 0.086* | |
C7 | 0.0131 (8) | 0.1589 (9) | 0.5479 (4) | 0.085 (3) | |
H7A | 0.0148 | 0.0718 | 0.5826 | 0.127* | |
H7B | −0.0190 | 0.1540 | 0.4990 | 0.127* | |
H7C | −0.0449 | 0.2184 | 0.5728 | 0.127* | |
C8 | 0.3507 (6) | 0.2296 (6) | 0.6035 (3) | 0.0430 (14) | |
H8 | 0.3991 | 0.2444 | 0.5537 | 0.052* | |
C9 | 0.4180 (6) | 0.2358 (5) | 0.6674 (3) | 0.0369 (13) | |
C10 | 0.5641 (6) | 0.2666 (6) | 0.6581 (3) | 0.0422 (14) | |
C11 | 0.6255 (6) | 0.2910 (7) | 0.5711 (3) | 0.0560 (17) | |
H11A | 0.7175 | 0.3104 | 0.5681 | 0.084* | |
H11B | 0.5785 | 0.3651 | 0.5399 | 0.084* | |
H11C | 0.6187 | 0.2128 | 0.5511 | 0.084* | |
C12 | 0.6420 (6) | 0.1452 (6) | 0.7054 (4) | 0.0503 (16) | |
H12A | 0.6319 | 0.0681 | 0.6850 | 0.075* | |
H12B | 0.6078 | 0.1287 | 0.7604 | 0.075* | |
H12C | 0.7347 | 0.1636 | 0.7001 | 0.075* | |
C13 | 0.5878 (6) | 0.3889 (6) | 0.6898 (3) | 0.0480 (15) | |
H13A | 0.6813 | 0.4040 | 0.6829 | 0.072* | |
H13B | 0.5562 | 0.3735 | 0.7452 | 0.072* | |
H13C | 0.5407 | 0.4657 | 0.6612 | 0.072* | |
C14 | 0.3400 (5) | 0.2136 (5) | 0.7421 (3) | 0.0330 (12) | |
C15 | 0.3032 (5) | 0.4926 (5) | 0.8173 (3) | 0.0268 (11) | |
C16 | 0.3288 (5) | 0.6132 (5) | 0.7597 (3) | 0.0265 (11) | |
C17 | 0.2379 (5) | 0.6627 (5) | 0.6931 (3) | 0.0332 (12) | |
C18 | 0.2382 (6) | 0.5619 (6) | 0.6419 (3) | 0.0406 (14) | |
H18A | 0.3282 | 0.5418 | 0.6222 | 0.061* | |
H18B | 0.1872 | 0.5984 | 0.5981 | 0.061* | |
H18C | 0.1996 | 0.4817 | 0.6731 | 0.061* | |
C19 | 0.0951 (5) | 0.6859 (6) | 0.7286 (3) | 0.0415 (14) | |
H19A | 0.0667 | 0.6064 | 0.7659 | 0.062* | |
H19B | 0.0374 | 0.7078 | 0.6869 | 0.062* | |
H19C | 0.0913 | 0.7580 | 0.7551 | 0.062* | |
C20 | 0.2839 (6) | 0.7960 (6) | 0.6391 (3) | 0.0480 (16) | |
H20A | 0.2800 | 0.8624 | 0.6700 | 0.072* | |
H20B | 0.2265 | 0.8244 | 0.5976 | 0.072* | |
H20C | 0.3737 | 0.7842 | 0.6162 | 0.072* | |
C21 | 0.4410 (5) | 0.6772 (5) | 0.7656 (3) | 0.0285 (11) | |
H21 | 0.4591 | 0.7565 | 0.7287 | 0.034* | |
C22 | 0.5310 (5) | 0.6303 (5) | 0.8242 (3) | 0.0267 (11) | |
C23 | 0.6572 (5) | 0.7058 (5) | 0.8201 (3) | 0.0293 (11) | |
C24 | 0.7223 (5) | 0.7433 (6) | 0.7339 (3) | 0.0377 (13) | |
H24A | 0.8030 | 0.7876 | 0.7323 | 0.057* | |
H24B | 0.6621 | 0.8018 | 0.7015 | 0.057* | |
H24C | 0.7424 | 0.6640 | 0.7140 | 0.057* | |
C25 | 0.6181 (6) | 0.8344 (5) | 0.8485 (3) | 0.0395 (13) | |
H25A | 0.5891 | 0.8128 | 0.9043 | 0.059* | |
H25B | 0.5470 | 0.8818 | 0.8201 | 0.059* | |
H25C | 0.6935 | 0.8892 | 0.8390 | 0.059* | |
C26 | 0.7603 (5) | 0.6276 (5) | 0.8714 (3) | 0.0350 (12) | |
H26A | 0.7264 | 0.6151 | 0.9263 | 0.052* | |
H26B | 0.8403 | 0.6759 | 0.8619 | 0.052* | |
H26C | 0.7795 | 0.5423 | 0.8583 | 0.052* | |
C27 | 0.5004 (5) | 0.5190 (4) | 0.8824 (3) | 0.0234 (10) | |
H27 | 0.5543 | 0.4899 | 0.9234 | 0.028* | |
C28 | 0.3879 (5) | 0.4494 (5) | 0.8800 (3) | 0.0263 (11) | |
C29 | 0.3592 (4) | −0.0251 (5) | 0.9692 (3) | 0.0259 (11) | |
H29 | 0.4255 | −0.0085 | 0.9268 | 0.031* | |
C30 | 0.3697 (5) | −0.1417 (5) | 1.0271 (3) | 0.0298 (11) | |
H30 | 0.4428 | −0.2010 | 1.0239 | 0.036* | |
C31 | 0.2708 (5) | −0.1692 (5) | 1.0893 (3) | 0.0290 (11) | |
H31 | 0.2759 | −0.2474 | 1.1284 | 0.035* | |
C32 | 0.1639 (5) | −0.0781 (5) | 1.0924 (3) | 0.0245 (11) | |
H32 | 0.0957 | −0.0949 | 1.1335 | 0.029* | |
C33 | 0.1593 (4) | 0.0378 (4) | 1.0338 (3) | 0.0210 (10) | |
C34 | 0.0541 (4) | 0.1448 (4) | 1.0321 (3) | 0.0202 (10) | |
C35 | −0.0556 (5) | 0.1385 (5) | 1.0880 (3) | 0.0250 (11) | |
H35 | −0.0676 | 0.0632 | 1.1290 | 0.030* | |
C36 | −0.1470 (5) | 0.2455 (5) | 1.0822 (3) | 0.0278 (11) | |
H36 | −0.2210 | 0.2435 | 1.1195 | 0.033* | |
C37 | −0.1272 (5) | 0.3559 (5) | 1.0201 (3) | 0.0267 (11) | |
H37 | −0.1869 | 0.4295 | 1.0157 | 0.032* | |
C38 | −0.0182 (5) | 0.3549 (5) | 0.9653 (3) | 0.0265 (11) | |
H38 | −0.0064 | 0.4285 | 0.9231 | 0.032* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ru1 | 0.0207 (2) | 0.0254 (2) | 0.0202 (2) | −0.00348 (15) | 0.00222 (14) | 0.00001 (15) |
O1 | 0.0239 (18) | 0.0285 (18) | 0.0270 (19) | −0.0015 (15) | 0.0055 (14) | 0.0005 (15) |
O2 | 0.0191 (17) | 0.0296 (18) | 0.0230 (18) | −0.0046 (14) | 0.0020 (13) | −0.0014 (14) |
O3 | 0.0200 (17) | 0.0250 (17) | 0.0208 (17) | −0.0023 (14) | 0.0014 (13) | −0.0002 (14) |
O4 | 0.0244 (18) | 0.0298 (18) | 0.0229 (18) | −0.0054 (15) | 0.0021 (14) | −0.0019 (14) |
N1 | 0.021 (2) | 0.020 (2) | 0.023 (2) | −0.0054 (17) | 0.0011 (16) | −0.0031 (17) |
N2 | 0.015 (2) | 0.022 (2) | 0.020 (2) | −0.0029 (16) | −0.0050 (15) | 0.0014 (16) |
C1 | 0.037 (3) | 0.028 (3) | 0.022 (3) | −0.006 (2) | 0.004 (2) | 0.000 (2) |
C2 | 0.041 (3) | 0.031 (3) | 0.032 (3) | −0.003 (2) | −0.004 (2) | −0.007 (2) |
C3 | 0.055 (4) | 0.037 (3) | 0.029 (3) | −0.007 (3) | 0.001 (3) | −0.009 (3) |
C4 | 0.061 (4) | 0.051 (4) | 0.033 (3) | −0.008 (3) | −0.005 (3) | −0.011 (3) |
C5 | 0.099 (6) | 0.068 (5) | 0.050 (4) | 0.016 (4) | −0.030 (4) | −0.012 (4) |
C6 | 0.088 (5) | 0.044 (4) | 0.035 (4) | −0.007 (4) | −0.002 (3) | 0.000 (3) |
C7 | 0.071 (5) | 0.143 (8) | 0.048 (4) | −0.032 (5) | −0.007 (4) | −0.026 (5) |
C8 | 0.052 (4) | 0.043 (3) | 0.030 (3) | −0.003 (3) | 0.007 (3) | −0.007 (3) |
C9 | 0.041 (3) | 0.037 (3) | 0.031 (3) | −0.001 (3) | 0.003 (2) | −0.006 (2) |
C10 | 0.046 (4) | 0.041 (3) | 0.031 (3) | 0.002 (3) | 0.017 (3) | −0.003 (3) |
C11 | 0.043 (4) | 0.079 (5) | 0.034 (3) | 0.008 (3) | 0.012 (3) | −0.001 (3) |
C12 | 0.044 (4) | 0.045 (4) | 0.050 (4) | 0.009 (3) | 0.010 (3) | 0.002 (3) |
C13 | 0.042 (4) | 0.052 (4) | 0.044 (4) | −0.004 (3) | 0.012 (3) | −0.005 (3) |
C14 | 0.044 (3) | 0.027 (3) | 0.025 (3) | −0.004 (2) | 0.003 (2) | −0.002 (2) |
C15 | 0.025 (3) | 0.027 (3) | 0.026 (3) | 0.003 (2) | 0.001 (2) | −0.006 (2) |
C16 | 0.027 (3) | 0.024 (3) | 0.026 (3) | 0.003 (2) | −0.002 (2) | −0.002 (2) |
C17 | 0.036 (3) | 0.034 (3) | 0.025 (3) | 0.002 (2) | 0.002 (2) | −0.001 (2) |
C18 | 0.045 (3) | 0.045 (3) | 0.028 (3) | −0.003 (3) | −0.012 (2) | 0.005 (3) |
C19 | 0.031 (3) | 0.055 (4) | 0.035 (3) | 0.012 (3) | −0.008 (2) | −0.006 (3) |
C20 | 0.051 (4) | 0.043 (3) | 0.044 (4) | −0.005 (3) | −0.019 (3) | 0.008 (3) |
C21 | 0.031 (3) | 0.022 (3) | 0.027 (3) | 0.000 (2) | 0.004 (2) | 0.000 (2) |
C22 | 0.027 (3) | 0.027 (3) | 0.024 (3) | 0.002 (2) | 0.003 (2) | −0.004 (2) |
C23 | 0.027 (3) | 0.029 (3) | 0.028 (3) | −0.005 (2) | 0.003 (2) | −0.001 (2) |
C24 | 0.028 (3) | 0.054 (4) | 0.029 (3) | −0.012 (3) | 0.001 (2) | −0.003 (3) |
C25 | 0.037 (3) | 0.037 (3) | 0.044 (3) | −0.005 (3) | −0.004 (3) | −0.008 (3) |
C26 | 0.029 (3) | 0.037 (3) | 0.036 (3) | −0.001 (2) | −0.004 (2) | −0.001 (2) |
C27 | 0.023 (3) | 0.026 (3) | 0.020 (2) | 0.002 (2) | −0.0039 (19) | −0.002 (2) |
C28 | 0.029 (3) | 0.030 (3) | 0.016 (2) | −0.001 (2) | 0.0051 (19) | −0.002 (2) |
C29 | 0.016 (2) | 0.028 (3) | 0.031 (3) | −0.001 (2) | 0.002 (2) | −0.003 (2) |
C30 | 0.023 (3) | 0.027 (3) | 0.040 (3) | −0.001 (2) | −0.006 (2) | −0.008 (2) |
C31 | 0.030 (3) | 0.020 (3) | 0.034 (3) | −0.004 (2) | −0.006 (2) | 0.004 (2) |
C32 | 0.023 (3) | 0.030 (3) | 0.020 (3) | −0.007 (2) | −0.0008 (19) | −0.002 (2) |
C33 | 0.017 (2) | 0.025 (2) | 0.022 (2) | −0.0087 (19) | 0.0000 (18) | −0.005 (2) |
C34 | 0.021 (2) | 0.021 (2) | 0.019 (2) | −0.0067 (19) | −0.0002 (18) | −0.003 (2) |
C35 | 0.026 (3) | 0.028 (3) | 0.020 (3) | −0.004 (2) | −0.002 (2) | −0.002 (2) |
C36 | 0.027 (3) | 0.035 (3) | 0.021 (3) | −0.002 (2) | 0.000 (2) | −0.005 (2) |
C37 | 0.021 (3) | 0.026 (3) | 0.032 (3) | 0.005 (2) | −0.004 (2) | −0.006 (2) |
C38 | 0.031 (3) | 0.023 (3) | 0.025 (3) | −0.006 (2) | −0.004 (2) | −0.003 (2) |
Ru1—O2 | 1.978 (3) | C16—C21 | 1.381 (6) |
Ru1—O4 | 1.988 (3) | C16—C17 | 1.536 (7) |
Ru1—O1 | 1.990 (3) | C17—C18 | 1.520 (7) |
Ru1—O3 | 1.994 (3) | C17—C19 | 1.529 (7) |
Ru1—N2 | 2.044 (4) | C17—C20 | 1.545 (7) |
Ru1—N1 | 2.053 (4) | C18—H18A | 0.9600 |
O1—C14 | 1.340 (6) | C18—H18B | 0.9600 |
O2—C15 | 1.325 (5) | C18—H18C | 0.9600 |
O3—C28 | 1.340 (5) | C19—H19A | 0.9600 |
O4—C1 | 1.332 (6) | C19—H19B | 0.9600 |
N1—C29 | 1.334 (6) | C19—H19C | 0.9600 |
N1—C33 | 1.373 (6) | C20—H20A | 0.9600 |
N2—C38 | 1.350 (6) | C20—H20B | 0.9600 |
N2—C34 | 1.359 (5) | C20—H20C | 0.9600 |
C1—C2 | 1.395 (7) | C21—C22 | 1.426 (7) |
C1—C14 | 1.431 (7) | C21—H21 | 0.9300 |
C2—C3 | 1.379 (7) | C22—C27 | 1.372 (6) |
C2—H2 | 0.9300 | C22—C23 | 1.531 (7) |
C3—C8 | 1.421 (8) | C23—C26 | 1.516 (7) |
C3—C4 | 1.526 (7) | C23—C25 | 1.532 (7) |
C4—C7 | 1.499 (9) | C23—C24 | 1.542 (7) |
C4—C5 | 1.542 (9) | C24—H24A | 0.9600 |
C4—C6 | 1.543 (9) | C24—H24B | 0.9600 |
C5—H5A | 0.9600 | C24—H24C | 0.9600 |
C5—H5B | 0.9600 | C25—H25A | 0.9600 |
C5—H5C | 0.9600 | C25—H25B | 0.9600 |
C6—H6A | 0.9600 | C25—H25C | 0.9600 |
C6—H6B | 0.9600 | C26—H26A | 0.9600 |
C6—H6C | 0.9600 | C26—H26B | 0.9600 |
C7—H7A | 0.9600 | C26—H26C | 0.9600 |
C7—H7B | 0.9600 | C27—C28 | 1.401 (6) |
C7—H7C | 0.9600 | C27—H27 | 0.9300 |
C8—C9 | 1.387 (7) | C29—C30 | 1.386 (7) |
C8—H8 | 0.9300 | C29—H29 | 0.9300 |
C9—C14 | 1.421 (7) | C30—C31 | 1.379 (7) |
C9—C10 | 1.518 (8) | C30—H30 | 0.9300 |
C10—C13 | 1.536 (8) | C31—C32 | 1.386 (7) |
C10—C11 | 1.539 (7) | C31—H31 | 0.9300 |
C10—C12 | 1.550 (8) | C32—C33 | 1.382 (6) |
C11—H11A | 0.9600 | C32—H32 | 0.9300 |
C11—H11B | 0.9600 | C33—C34 | 1.474 (6) |
C11—H11C | 0.9600 | C34—C35 | 1.384 (6) |
C12—H12A | 0.9600 | C35—C36 | 1.381 (7) |
C12—H12B | 0.9600 | C35—H35 | 0.9300 |
C12—H12C | 0.9600 | C36—C37 | 1.385 (7) |
C13—H13A | 0.9600 | C36—H36 | 0.9300 |
C13—H13B | 0.9600 | C37—C38 | 1.373 (7) |
C13—H13C | 0.9600 | C37—H37 | 0.9300 |
C15—C16 | 1.425 (6) | C38—H38 | 0.9300 |
C15—C28 | 1.438 (6) | ||
O2—Ru1—O4 | 89.04 (13) | C21—C16—C15 | 116.4 (4) |
O2—Ru1—O1 | 86.32 (13) | C21—C16—C17 | 123.2 (4) |
O4—Ru1—O1 | 81.90 (13) | C15—C16—C17 | 120.3 (4) |
O2—Ru1—O3 | 82.41 (12) | C18—C17—C19 | 108.6 (4) |
O4—Ru1—O3 | 167.90 (12) | C18—C17—C16 | 111.1 (4) |
O1—Ru1—O3 | 88.99 (13) | C19—C17—C16 | 110.1 (4) |
O2—Ru1—N2 | 96.44 (14) | C18—C17—C20 | 108.2 (4) |
O4—Ru1—N2 | 94.41 (13) | C19—C17—C20 | 107.9 (4) |
O1—Ru1—N2 | 175.38 (14) | C16—C17—C20 | 110.9 (4) |
O3—Ru1—N2 | 95.04 (13) | C17—C18—H18A | 109.5 |
O2—Ru1—N1 | 174.28 (14) | C17—C18—H18B | 109.5 |
O4—Ru1—N1 | 93.75 (14) | H18A—C18—H18B | 109.5 |
O1—Ru1—N1 | 99.00 (14) | C17—C18—H18C | 109.5 |
O3—Ru1—N1 | 95.53 (13) | H18A—C18—H18C | 109.5 |
N2—Ru1—N1 | 78.39 (15) | H18B—C18—H18C | 109.5 |
C14—O1—Ru1 | 108.6 (3) | C17—C19—H19A | 109.5 |
C15—O2—Ru1 | 109.2 (3) | C17—C19—H19B | 109.5 |
C28—O3—Ru1 | 107.3 (3) | H19A—C19—H19B | 109.5 |
C1—O4—Ru1 | 108.0 (3) | C17—C19—H19C | 109.5 |
C29—N1—C33 | 118.2 (4) | H19A—C19—H19C | 109.5 |
C29—N1—Ru1 | 125.3 (3) | H19B—C19—H19C | 109.5 |
C33—N1—Ru1 | 116.5 (3) | C17—C20—H20A | 109.5 |
C38—N2—C34 | 118.0 (4) | C17—C20—H20B | 109.5 |
C38—N2—Ru1 | 125.1 (3) | H20A—C20—H20B | 109.5 |
C34—N2—Ru1 | 116.9 (3) | C17—C20—H20C | 109.5 |
O4—C1—C2 | 122.4 (5) | H20A—C20—H20C | 109.5 |
O4—C1—C14 | 116.6 (4) | H20B—C20—H20C | 109.5 |
C2—C1—C14 | 120.9 (5) | C16—C21—C22 | 124.5 (4) |
C3—C2—C1 | 120.2 (5) | C16—C21—H21 | 117.7 |
C3—C2—H2 | 119.9 | C22—C21—H21 | 117.7 |
C1—C2—H2 | 119.9 | C27—C22—C21 | 118.4 (4) |
C2—C3—C8 | 117.5 (5) | C27—C22—C23 | 122.6 (4) |
C2—C3—C4 | 122.8 (5) | C21—C22—C23 | 119.0 (4) |
C8—C3—C4 | 119.7 (5) | C26—C23—C22 | 113.5 (4) |
C7—C4—C3 | 111.8 (5) | C26—C23—C25 | 108.0 (4) |
C7—C4—C5 | 111.7 (6) | C22—C23—C25 | 108.4 (4) |
C3—C4—C5 | 109.3 (5) | C26—C23—C24 | 108.1 (4) |
C7—C4—C6 | 107.2 (6) | C22—C23—C24 | 110.2 (4) |
C3—C4—C6 | 109.9 (5) | C25—C23—C24 | 108.4 (4) |
C5—C4—C6 | 106.7 (5) | C23—C24—H24A | 109.5 |
C4—C5—H5A | 109.5 | C23—C24—H24B | 109.5 |
C4—C5—H5B | 109.5 | H24A—C24—H24B | 109.5 |
H5A—C5—H5B | 109.5 | C23—C24—H24C | 109.5 |
C4—C5—H5C | 109.5 | H24A—C24—H24C | 109.5 |
H5A—C5—H5C | 109.5 | H24B—C24—H24C | 109.5 |
H5B—C5—H5C | 109.5 | C23—C25—H25A | 109.5 |
C4—C6—H6A | 109.5 | C23—C25—H25B | 109.5 |
C4—C6—H6B | 109.5 | H25A—C25—H25B | 109.5 |
H6A—C6—H6B | 109.5 | C23—C25—H25C | 109.5 |
C4—C6—H6C | 109.5 | H25A—C25—H25C | 109.5 |
H6A—C6—H6C | 109.5 | H25B—C25—H25C | 109.5 |
H6B—C6—H6C | 109.5 | C23—C26—H26A | 109.5 |
C4—C7—H7A | 109.5 | C23—C26—H26B | 109.5 |
C4—C7—H7B | 109.5 | H26A—C26—H26B | 109.5 |
H7A—C7—H7B | 109.5 | C23—C26—H26C | 109.5 |
C4—C7—H7C | 109.5 | H26A—C26—H26C | 109.5 |
H7A—C7—H7C | 109.5 | H26B—C26—H26C | 109.5 |
H7B—C7—H7C | 109.5 | C22—C27—C28 | 119.8 (4) |
C9—C8—C3 | 125.6 (5) | C22—C27—H27 | 120.1 |
C9—C8—H8 | 117.2 | C28—C27—H27 | 120.1 |
C3—C8—H8 | 117.2 | O3—C28—C27 | 122.7 (4) |
C8—C9—C14 | 115.3 (5) | O3—C28—C15 | 116.2 (4) |
C8—C9—C10 | 122.5 (5) | C27—C28—C15 | 121.1 (4) |
C14—C9—C10 | 122.2 (5) | N1—C29—C30 | 122.5 (4) |
C9—C10—C13 | 112.5 (5) | N1—C29—H29 | 118.7 |
C9—C10—C11 | 112.4 (5) | C30—C29—H29 | 118.7 |
C13—C10—C11 | 107.8 (5) | C31—C30—C29 | 119.5 (5) |
C9—C10—C12 | 108.7 (5) | C31—C30—H30 | 120.3 |
C13—C10—C12 | 107.9 (5) | C29—C30—H30 | 120.3 |
C11—C10—C12 | 107.3 (5) | C30—C31—C32 | 118.7 (5) |
C10—C11—H11A | 109.5 | C30—C31—H31 | 120.7 |
C10—C11—H11B | 109.5 | C32—C31—H31 | 120.7 |
H11A—C11—H11B | 109.5 | C33—C32—C31 | 119.6 (4) |
C10—C11—H11C | 109.5 | C33—C32—H32 | 120.2 |
H11A—C11—H11C | 109.5 | C31—C32—H32 | 120.2 |
H11B—C11—H11C | 109.5 | N1—C33—C32 | 121.5 (4) |
C10—C12—H12A | 109.5 | N1—C33—C34 | 113.6 (4) |
C10—C12—H12B | 109.5 | C32—C33—C34 | 124.8 (4) |
H12A—C12—H12B | 109.5 | N2—C34—C35 | 121.9 (4) |
C10—C12—H12C | 109.5 | N2—C34—C33 | 114.5 (4) |
H12A—C12—H12C | 109.5 | C35—C34—C33 | 123.6 (4) |
H12B—C12—H12C | 109.5 | C36—C35—C34 | 119.1 (4) |
C10—C13—H13A | 109.5 | C36—C35—H35 | 120.4 |
C10—C13—H13B | 109.5 | C34—C35—H35 | 120.4 |
H13A—C13—H13B | 109.5 | C35—C36—C37 | 119.2 (5) |
C10—C13—H13C | 109.5 | C35—C36—H36 | 120.4 |
H13A—C13—H13C | 109.5 | C37—C36—H36 | 120.4 |
H13B—C13—H13C | 109.5 | C38—C37—C36 | 119.0 (4) |
O1—C14—C9 | 124.0 (5) | C38—C37—H37 | 120.5 |
O1—C14—C1 | 115.6 (4) | C36—C37—H37 | 120.5 |
C9—C14—C1 | 120.4 (5) | N2—C38—C37 | 122.7 (4) |
O2—C15—C16 | 124.3 (4) | N2—C38—H38 | 118.7 |
O2—C15—C28 | 116.2 (4) | C37—C38—H38 | 118.7 |
C16—C15—C28 | 119.5 (4) | ||
Ru1—O4—C1—C2 | −160.9 (4) | C17—C16—C21—C22 | −176.7 (5) |
Ru1—O4—C1—C14 | 23.0 (5) | C16—C21—C22—C27 | −4.8 (7) |
O4—C1—C2—C3 | −178.9 (5) | C16—C21—C22—C23 | 175.5 (5) |
C14—C1—C2—C3 | −3.0 (8) | C27—C22—C23—C26 | 15.3 (7) |
C1—C2—C3—C8 | 3.5 (8) | C21—C22—C23—C26 | −165.0 (4) |
C1—C2—C3—C4 | −173.5 (5) | C27—C22—C23—C25 | −104.6 (5) |
C2—C3—C4—C7 | −11.4 (9) | C21—C22—C23—C25 | 75.1 (6) |
C8—C3—C4—C7 | 171.7 (6) | C27—C22—C23—C24 | 136.8 (5) |
C2—C3—C4—C5 | 112.8 (6) | C21—C22—C23—C24 | −43.5 (6) |
C8—C3—C4—C5 | −64.1 (7) | C21—C22—C27—C28 | 4.4 (7) |
C2—C3—C4—C6 | −130.4 (6) | C23—C22—C27—C28 | −175.9 (4) |
C8—C3—C4—C6 | 52.7 (7) | Ru1—O3—C28—C27 | −158.8 (4) |
C2—C3—C8—C9 | −1.8 (9) | Ru1—O3—C28—C15 | 23.9 (5) |
C4—C3—C8—C9 | 175.3 (6) | C22—C27—C28—O3 | −177.2 (4) |
C3—C8—C9—C14 | −0.5 (8) | C22—C27—C28—C15 | 0.0 (7) |
C3—C8—C9—C10 | −179.4 (5) | O2—C15—C28—O3 | −4.9 (6) |
C8—C9—C10—C13 | 122.6 (6) | C16—C15—C28—O3 | 173.0 (4) |
C14—C9—C10—C13 | −56.3 (7) | O2—C15—C28—C27 | 177.7 (4) |
C8—C9—C10—C11 | 0.7 (8) | C16—C15—C28—C27 | −4.4 (7) |
C14—C9—C10—C11 | −178.2 (5) | C33—N1—C29—C30 | −1.2 (6) |
C8—C9—C10—C12 | −117.9 (6) | Ru1—N1—C29—C30 | 179.4 (3) |
C14—C9—C10—C12 | 63.2 (7) | N1—C29—C30—C31 | 1.4 (7) |
Ru1—O1—C14—C9 | 161.2 (4) | C29—C30—C31—C32 | −0.5 (7) |
Ru1—O1—C14—C1 | −19.8 (5) | C30—C31—C32—C33 | −0.5 (7) |
C8—C9—C14—O1 | 180.0 (5) | C29—N1—C33—C32 | 0.1 (6) |
C10—C9—C14—O1 | −1.0 (8) | Ru1—N1—C33—C32 | 179.5 (3) |
C8—C9—C14—C1 | 1.0 (8) | C29—N1—C33—C34 | 178.4 (4) |
C10—C9—C14—C1 | 180.0 (5) | Ru1—N1—C33—C34 | −2.1 (5) |
O4—C1—C14—O1 | −2.3 (7) | C31—C32—C33—N1 | 0.8 (6) |
C2—C1—C14—O1 | −178.4 (4) | C31—C32—C33—C34 | −177.4 (4) |
O4—C1—C14—C9 | 176.8 (4) | C38—N2—C34—C35 | 1.8 (6) |
C2—C1—C14—C9 | 0.7 (8) | Ru1—N2—C34—C35 | −176.8 (3) |
Ru1—O2—C15—C16 | 165.0 (4) | C38—N2—C34—C33 | −178.7 (4) |
Ru1—O2—C15—C28 | −17.2 (5) | Ru1—N2—C34—C33 | 2.7 (5) |
O2—C15—C16—C21 | −178.2 (4) | N1—C33—C34—N2 | −0.4 (5) |
C28—C15—C16—C21 | 4.0 (7) | C32—C33—C34—N2 | 177.9 (4) |
O2—C15—C16—C17 | −1.0 (7) | N1—C33—C34—C35 | 179.1 (4) |
C28—C15—C16—C17 | −178.8 (4) | C32—C33—C34—C35 | −2.6 (7) |
C21—C16—C17—C18 | 116.4 (5) | N2—C34—C35—C36 | −2.1 (6) |
C15—C16—C17—C18 | −60.6 (6) | C33—C34—C35—C36 | 178.5 (4) |
C21—C16—C17—C19 | −123.2 (5) | C34—C35—C36—C37 | 0.6 (7) |
C15—C16—C17—C19 | 59.8 (6) | C35—C36—C37—C38 | 1.1 (7) |
C21—C16—C17—C20 | −4.0 (7) | C34—N2—C38—C37 | −0.1 (6) |
C15—C16—C17—C20 | 179.0 (5) | Ru1—N2—C38—C37 | 178.4 (3) |
C15—C16—C21—C22 | 0.4 (7) | C36—C37—C38—N2 | −1.3 (7) |
D—H···A | D—H | H···A | D···A | D—H···A |
C30—H30···O3i | 0.93 | 2.54 | 3.427 (6) | 159 |
C32—H32···O4ii | 0.93 | 2.49 | 3.322 (6) | 148 |
C35—H35···O4ii | 0.93 | 2.39 | 3.232 (6) | 151 |
Symmetry codes: (i) −x+1, −y, −z+2; (ii) −x, −y, −z+2. |
Acknowledgements
The authors are grateful to Dr Igor Fritsky and Dr Musheer Ahmad for important discussions.
Funding information
Funding for this research was provided by: National Taras Shevchenko University, Department of Chemistry
References
Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115–119. Web of Science CrossRef CAS IUCr Journals Google Scholar
Brandenberg, K. & Putz, H. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2003). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Buchanan, R. M., Kessel, S. L., Downs, H. H., Pierpont, C. G. & Hendrickson, D. N. (1978). J. Am. Chem. Soc. 100, 7894–7900. CrossRef CAS Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CSD CrossRef IUCr Journals Google Scholar
Krämer, R. & Fritsky, I. O. (2000). Eur. J. Org. Chem. pp. 3505–3510. Google Scholar
Lever, A. B. P., Auburn, P. R., Dodsworth, E. S., Haga, M. A., Liu, W., Melnik, M. & Nevin, W. A. (1988). J. Am. Chem. Soc. 110, 8076–8084. CrossRef CAS Google Scholar
Moroz, Y. S., Demeshko, S., Haukka, M., Mokhir, A., Mitra, U., Stocker, M., Müller, P., Meyer, F. & Fritsky, I. O. (2012). Inorg. Chem. 51, 7445–7447. Web of Science CSD CrossRef CAS PubMed Google Scholar
Pagliaro, M., Campestrini, S. & Ciriminna, R. (2005). Chem. Soc. Rev. 34, 837–845. Web of Science CrossRef PubMed CAS Google Scholar
Ramakrishna, D. & Bhat, B. R. (2011). Inorg. Chem. Commun. 14, 155–158. CrossRef CAS Google Scholar
Rijt, S. H. van & Sadler, P. J. (2009). Drug Discov. Today, 14, 1089–1097. Web of Science PubMed Google Scholar
Sheldrick, G. M. (2004). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Strotmeyer, K. P., Fritsky, I. O., Ott, R., Pritzkow, H. & Krämer, R. (2003). Supramol. Chem. 15, 529–547. Web of Science CSD CrossRef CAS Google Scholar
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