The complex [{La(Ph3CCOO)2(Me3AlOMe)}2] has an La2(μ-OCO)4 core, contains the carboxylate ligands in μ2-κ1 O:κ1 O′ bridging and μ2-κ2 O,O′:κ1 O semi-bridging coordination modes, and displays La—C interactions with the π-system of a phenyl ring.
Keywords: lanthanum, aluminium, triphenylacetate, π-complex, coordination compound, crystal structure
Abstract
The title compound, [Al2La2(C20H15O2)4(CH3)6(CH3O)2]·4CH3C6H5 or [{La(Ph3CCOO)2(Me3AlOMe)}2]·4CH3C6H5, was formed in a reaction between lanthanum tris(tetramethylaluminate) and triphenylacetic acid (1:1) with unintended partial oxidation. The triphenylacetate ligand exhibits μ2-κ1 O:κ1 O′ bridging and μ2-κ2 O,O′:κ1 O semi-bridging coordination modes, forming a dimeric La2(μ-OCO)4 core. The semi-bridging triphenylacetate group provides additional bonding with an La3+ cation via the π-system of one of its phenyl rings. The trimethylmethoxyaluminate anion, which is coordinated to the La3+ cation by its O atom, displays a rather long La—CMe bond. Two toluene molecules are each disordered over two orientations about centres of symmetry with site occupancy factors of 0.5. The title compound represents the first example of an LnIII complex containing both alkyl alkoxide aluminate and π-bounded arene fragments.
Chemical context
Heteroleptic tetraalkylaluminate complexes of rare-earth metals attract significant attention because of their intriguing role in the stereospecific polymerization of conjugated dienes (Anwander, 2002 ▸). Stereoregular elastomers obtained in the polymerization process of isoprene and butadiene are fundamentally important for the production of modern wear-resistant rubbers (Friebe et al., 2006 ▸). It is assumed that this type of complex plays the key role in the formation of catalytically active species. Meanwhile, little is known about the structure of such complexes (Fischbach et al., 2006a ▸, and reference therein). The exceptionally high oxidative instability of aluminate complexes is one of the reasons for the lack of information on the structures of catalytically active heteroleptic bimetallic Ln–Al complexes.
This report describes the product of unintentional oxidation of a carboxylate–aluminate La complex while reacting lanthanum tris(tetramethylaluminiumate) with the corresponding acid (Fig. 1 ▸). This reaction should have led initially to the heteroleptic triphenylacetate–tetramethylaluminate complex that is supposed to be a model of the active species in the catalyst system. The accidental partial oxidation resulted in the formation of the triphenylacetate-trimethylmethoxyaluminate lanthanum complex [{La(Ph3CCOO)2Me3AlOMe}2].
Figure 1.
Synthesis of [{La(Ph3CCOO)2Me3AlOMe}2]·4(CH3C6H5).
Structural commentary
The asymmetric unit of the title compound consists of half of the dimeric complex [{La(Ph3CCOO)2(Me3AlOMe)}2] (Fig. 2 ▸) located on an inversion centre, and three non-coordinating toluene molecules (not shown). Two of the toluene molecules are disordered over inversion centres, having 50% atomic site occupancies. The coordination polyhedron for the La3+ cation and its coordination number are rather difficult to determine. Two triphenylacetate ligands exhibit the μ2-κ1 O:κ1 O′ bridging coordination mode, but two other ligands display the μ2-κ2 O,O′:κ1 O′ semi-bridging type (Figs. 2 ▸ and 3 ▸; Table 1 ▸). The complex has an La2(μ-OCO)4 core with an La1⋯La1i distance of 4.0432 (4) Å [symmetry code: (i) −x, −y + 1, −z + 1). Unlike the bridging ligands, the semi-bridging triphenylacetates demonstrate additional La⋯C contacts with the carboxylic system (La1⋯C5, La1i⋯C5i; Fig. 3 ▸; Table 1 ▸). The La3+ cation is also coordinated by the π-system of a phenyl ring of the semi-bridging carboxylate ligand (Fig. 3 ▸, atoms C7i–C12i; Table 1 ▸). The interaction with the phenyl (Ph) group is close to symmetrical: the La⋯Phcentroid distance is 2.938 (2) Å, the normal to the Ph-ring plane is 2.9353 (16) Å, and the La⋯CPh bond lengths lie in the range 3.201 (4) to 3.318 (4) Å. Ten crystal structures exhibiting the interaction of La3+ with the π-system of an uncharged C6 aromatic ring have been found in the Cambridge Structural Database (CSD, Version 5.39, February 2018 update; Groom et al., 2016 ▸). The corresponding distances in these compounds vary from 2.93 to 3.27 Å for La⋯CAryl and from 2.61 to 2.87 Å for La⋯Arylcentroid. The La⋯Phcentroid and La⋯CPh distances in the title compound are therefore the longest, which is likely caused by steric hindrance induced by the presence of many phenyl groups within the inner coordination sphere.
Figure 2.
The molecular structure of the {La(Ph3CCOO)2(Me3AlOMe)}2 unit in the title compound with displacement ellipsoids drawn at the 30% probability level. Hydrogen atoms and toluene solvent molecules are omitted for clarity. The La—O bonds are shown with thinner solid lines. The La—C interactions are not shown. Symmetry code: (i) −x, −y + 1, −z + 1.
Figure 3.
Metal–ligand interactions within the {La(Ph3CCOO)2(Me3AlOMe)}2 unit. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen atoms are omitted, only Cipso atoms (labeled as Ph) are shown for non-coordinating phenyl groups for clarity. The Ln—C contacts are shown with thin dashed lines. Symmetry code: (i) −x, −y + 1, −z + 1.
Table 1. Selected bond lengths (Å).
| La1—O1 | 2.336 (3) | La1—C8i | 3.287 (4) |
| La1—O2 | 2.501 (3) | La1—C9i | 3.246 (4) |
| La1—O3 | 2.494 (3) | La1—C10i | 3.212 (4) |
| La1—O3i | 2.403 (2) | La1—C11i | 3.201 (4) |
| La1—O4 | 2.396 (3) | La1—C12i | 3.239 (4) |
| La1—O5i | 2.367 (3) | Al1—O1 | 1.819 (3) |
| La1—C2 | 3.042 (4) | Al1—C2 | 2.014 (4) |
| La1—C5 | 2.892 (4) | Al1—C3 | 1.990 (5) |
| La1—C7i | 3.318 (4) | Al1—C4 | 1.961 (4) |
Symmetry code: (i) 
.
The trimethylmetoxyaluminate anions are coordinated to the La3+ cations via oxygen atoms (La1—O1, La1i—O1i), and exhibit a slightly distorted tetrahedral environment about the Al atoms, with an O1—Al1—C2 angle of 100.03 (17)° and with other O—Al—C and C—Al—C bond angles ranging from 108.32 (18) to 113.2 (2)°. The small value for the O1—Al1—C2 angle is due to the additional coordination of the [Al(CH3)3(OCH3)] anion with La3+ by the C2 atom (Fig. 3 ▸). However, the La1—C2 bond length [3.042 (4) Å] is rather long compared to those of previously characterized compounds possessing the La–[(μ-Me)2AlMe2] fragment, which have La—CMe distances lying in the range 2.66 to 2.98 Å with the average value of 2.76 Å (32 compounds with 128 crystallographically independent La—CMe-Al distances retrieved from the CSD). The La1⋯Al1 distance [3.4481 (12) Å] is near to the upper boundary of the La—Al distance range in the aforementioned compounds (from 2.99 to 3.45 Å, with an average of 3.25 Å).
There is only one related compound having the La-[(Alkyl/Aryl)3Al(OAlkyl/OAryl)] motif (CSD refcode MIMPED; Giesbrecht et al., 2002 ▸) – {La(O-2,6-iPr2C6H3)[AlMe2(μ-Me)(μ-O-2,6-iPr2C6H3)]2}. The Al—O [1.864 (3), 1.848 (3) Å], La—O [2.387 (3), 2.367 (3) Å] and Al—C [2.040 (5), 2.053 (6) Å] bond lengths within the LaAl2(μ-Me)2(μ-OAryl)2 fragment are similar to those found in the LaAl(μ-Me)(μ-OMe) fragment of the complex reported herein. However, the La1—C2 distance in the title compound (Table 1 ▸) is considerably longer (by 0.24-0.28 Å) than the corresponding La—C distances in MIMPED [2.800 (5), 2.759 (5) Å], presumably due to steric reasons.
In the studied compound, the La—OMe (La1—O1) bond is the shortest, compared to the other La—O bonds, which may be due to delocalization of negative charge on the carboxy oxygen atoms and/or steric repulsion of the bulky carboxylate anion.
Supramolecular features
Weak intra- and intermolecular interactions among complex molecules and non-coordinating toluene molecules are mainly represented by the CPh—H··π type (Table 2 ▸). An interesting feature of the crystal packing is that the centres of all non-coordinating toluene molecules are located nearly in one plane parallel to the ab plane, separating 2D molecular layers of the complex (Fig. 4 ▸).
Table 2. Hydrogen-bond geometry (Å, °).
Cg1, Cg2, Cg3 and Cg4 are the centroids of the C33–C38, C39–C44, C52–C57 and C19–C24 rings, respectively.
| D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A |
|---|---|---|---|---|
| C1—H1C⋯⋯Cg1i | 0.98 | 2.69 | 3.425 (6) | 132 |
| C17—H17⋯⋯Cg2 | 0.95 | 2.71 | 3.485 (4) | 139 |
| C21—H21⋯⋯Cg3ii | 0.95 | 2.93 | 3.677 (8) | 136 |
| C29—H29⋯⋯Cg4 | 0.95 | 2.62 | 3.415 (4) | 142 |
| C32—H32⋯⋯Cg2 | 0.95 | 2.95 | 3.654 (5) | 132 |
| C44—H44⋯⋯Cg1 | 0.95 | 2.88 | 3.592 (5) | 132 |
Symmetry codes: (i) ; (ii) 
.
Figure 4.
A view along the b axis of the crystal packing of the title compound. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen atoms are omitted.
Database survey
The number of crystal structures for rare-earth compounds containing the Ln–C–Al fragment (CSD, Version 5.39, February 2018 update; Groom et al., 2016 ▸) is nearly 250 (upon exclusion of duplicated structures). They are mainly represented by 147 tetramethylaluminates with Ln-[(μ2-Me)2AlMe2] (127 structures), Ln-[(μ2-Me)AlMe2(μ2-Me)]-Ln (11 structures) and Ln-[(μ2-Me)AlMe3] (9 structures) fragments and by 16 tetraethylaluminate complexes. This number also includes 18 structures of Ln-[(Alkyl/Aryl)3Al(OAlkyl/OAryl) compounds possessing the following structural motifs: [(μ2-Me)(μ2-OCH2 tBu)AlMe2] (AVOYOA, AVOYUG, Occhipinti et al., 2011 ▸; GEQMOF, GEQMUL, Fischbach et al., 2006b ▸), [(μ2-Me)(μ2-OtBu)AlMe2] (POJNAD, Biagini et al., 1994 ▸; WAPYIV, WAPYOB, Evans et al., 1993a ▸; WEHHAS, Evans et al., 1993b ▸), [(μ2-Me)(μ2-OiPr)AlMe2] (VOLMUF, Liu et al., 2005 ▸), [(μ2-Me)(μ2-O-2,6-Ph2C6H3)AlMe2] (TULCAF, Korobkov & Gambarotta, 2009 ▸), [(μ2-Me)(μ2-O-2,6-iPr2C6H3)AlMe2] (LUQZOM, Fischbach et al., 2003 ▸; MIMPED, Giesbrecht et al., 2002 ▸; MOQYOG, Gordon et al., 2002 ▸; PETMUX, Fischbach et al., 2006c ▸), [(μ2-Et)(μ2-O-2,6-iPr2C6H3)AlEt2] (MIMPIH, Giesbrecht et al., 2002 ▸; ROCHOH, Sommerfeldt et al., 2008 ▸), [(μ2-Me)(μ2-O-2,6-tBu2-4-MeC6H2)AlMe2] (ROCGOG, Sommerfeldt et al., 2008 ▸), [(κ2 O,O′-MeOCH2CH2O)AlMe3] (GIZWAN, Evans et al., 1998 ▸). MIMPED is the only La structure among them. A related structure with the {(μ2-Me)[μ2-κO:κ2 O,O′-(OtBu)3SiO]AlMe2} motif (BEQXUR, Fischbach et al., 2004 ▸) might be also mentioned.
Crystal structures of lanthanide(III) compounds having an η6-coordinated uncharged arene system have become numerous over the last two decades, resulting in the description of over 150 crystal structures (see the CSD). Ten structures of such La(III) π-complexes are known: EZIPIM (Giesbrecht et al., 2004 ▸), MALXOM (Deacon et al., 2000 ▸), POKCAU (Gerber et al., 2008 ▸), RILBIZ, RILBUL (Hamidi et al., 2013 ▸), ROMQUG (Filatov et al., 2009 ▸), SOJHAB, SOJHEF, SOJHIJ (Filatov et al., 2008 ▸), ZIDSOV (Butcher et al., 1995 ▸). Crystallographic data for these complexes were used to compare structural parameters of the title compound in the Structural Commentary section. Known crystal structures of rare-earth triphenylacetate complexes are also not numerous, and their number is limited to 16 recent crystal structures: peroxide bis(triphenylacetate) complexes QEHBOX, QEHBUD, QEHCEO (Roitershtein et al., 2017 ▸), mono- and binuclear tris(triphenylacetate) complexes EPUNIO (Minyaev et al., 2016 ▸), RIKRIO, RIKRUA, RIKSAH, RIKSEL (Roitershtein et al., 2013 ▸), tetrakis(triphenylacetate) complexes and their adducts RIKQUZ, RIKRAG, RIKREK, RIKRIO (Roitershtein et al., 2013 ▸), triphenylacetate-tetraethylaluminate compounds RIJVIR, RIJVOX (Roitershtein et al., 2013 ▸) and heptanuclear polyligand complexes UVETAR, UVETEV (Sharples et al., 2011 ▸). The triphenylacetate ligand exhibits terminal κO and κ2 O,O′, bridging μ-κO,κO′, and semi-bridging μ-κO,κ2 O,O′ (the latter is only for the four ate complexes) coordination modes.
Up to date, no complex has been reported that has both an η6-coordinated arene ligand and the mixed-ligand alkyl-alkoxide aluminate anion.
Synthesis and crystallization
Synthetic operations were carried out under a purified argon atmosphere. Toluene was distilled from sodium/benzophenone ketyl, hexane was distilled from Na/K alloy. Triphenylacetic acid was purified by azeotrope removal of water from its toluene solution with a Dean–Stark trap, followed by crystallization from a cold saturated solution and then by vacuum drying. The complex La(AlMe4)3 was prepared according to the literature procedure (Zimmermann et al., 2007 ▸).
A solution of Ph3CCOOH (0.144 g, 0.50 mmol) in toluene (20 ml) was added to a stirred solution of La(AlMe4)3 (0.196 g, 0.49 mmol) in toluene (10 ml), producing a suspension, which was stirred overnight at room temperature. The precipitate was removed by decantation and the solution was concentrated to a volume of 10 ml. Slow and careful layering of hexane (40 ml) on the top of the residual solution resulted in the formation of an inseparable compound mixture and a few colourless crystals suitable for X-ray single crystal diffraction analysis.
Refinement
Crystal data, data collection and structure refinement details are summarized in Table 3 ▸. The hydrogen atom were positioned geometrically (C—H = 0.95 Å for aromatic, 0.98 Å for methyl H atoms) and refined as riding atoms with U iso(H) = 1.5U eq(C) for methyl or 1.2U eq(C) for aromatic H atoms. A rotating group model was applied for methyl groups. Three reflections (100, 010, 001) were affected by the beam stop, and were therefore omitted from the refinement. Two non-coordinating toluene molecules disordered over inversion centres with occupancy factors of 0.5 were modelled by fitting the phenyl rings to regular hexagons, by constraining the Cipso—CMe bond distances to 1.52 (1) Å, and by using equal anisotropic displacement parameters for atoms C52, C53, C54, C55, C60, C62 and C65.
Table 3. Experimental details.
| Crystal data | |
| Chemical formula | [Al2La2(CH3)6(C20H15O2)4(CH3O)2]·4C7H8 |
| M r | 2001.86 |
| Crystal system, space group | Triclinic, P
|
| Temperature (K) | 100 |
| a, b, c (Å) | 13.8404 (6), 14.2089 (6), 14.6084 (7) |
| α, β, γ (°) | 73.198 (1), 81.968 (1), 63.523 (1) |
| V (Å3) | 2461.54 (19) |
| Z | 1 |
| Radiation type | Mo Kα |
| μ (mm−1) | 0.93 |
| Crystal size (mm) | 0.43 × 0.17 × 0.14 |
| Data collection | |
| Diffractometer | Bruker APEXII CCD |
| Absorption correction | Multi-scan (SADABS; Bruker, 2008 ▸) |
| T min, T max | 0.713, 0.848 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 30779, 13082, 10174 |
| R int | 0.065 |
| (sin θ/λ)max (Å−1) | 0.682 |
| Refinement | |
| R[F 2 > 2σ(F 2)], wR(F 2), S | 0.049, 0.111, 1.01 |
| No. of reflections | 13082 |
| No. of parameters | 596 |
| No. of restraints | 2 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 1.25, −1.36 |
Supplementary Material
Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989018015876/rz5247sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989018015876/rz5247Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989018015876/rz5247Isup3.cdx
CCDC reference: 1877930
Additional supporting information: crystallographic information; 3D view; checkCIF report
supplementary crystallographic information
Crystal data
| [Al2La2(CH3)6(C20H15O2)4(CH3O)2]·4C7H8 | Z = 1 |
| Mr = 2001.86 | F(000) = 1032 |
| Triclinic, P1 | Dx = 1.350 Mg m−3 |
| a = 13.8404 (6) Å | Mo Kα radiation, λ = 0.71073 Å |
| b = 14.2089 (6) Å | Cell parameters from 4587 reflections |
| c = 14.6084 (7) Å | θ = 2.5–27.3° |
| α = 73.198 (1)° | µ = 0.93 mm−1 |
| β = 81.968 (1)° | T = 100 K |
| γ = 63.523 (1)° | Block, colorless |
| V = 2461.54 (19) Å3 | 0.43 × 0.17 × 0.14 mm |
Data collection
| Bruker APEXII CCD diffractometer | 13082 independent reflections |
| Radiation source: fine-focus sealed tube | 10174 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.065 |
| ω scans | θmax = 29.0°, θmin = 1.9° |
| Absorption correction: multi-scan (SADABS; Bruker, 2008) | h = −18→18 |
| Tmin = 0.713, Tmax = 0.848 | k = −19→19 |
| 30779 measured reflections | l = −19→19 |
Refinement
| 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)] = 0.049 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.111 | H-atom parameters constrained |
| S = 1.01 | w = 1/[σ2(Fo2) + (0.0491P)2] where P = (Fo2 + 2Fc2)/3 |
| 13082 reflections | (Δ/σ)max = 0.001 |
| 596 parameters | Δρmax = 1.25 e Å−3 |
| 2 restraints | Δρmin = −1.36 e Å−3 |
Special details
| Experimental. moisture and air sensitive |
| 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. 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 > 2sigma(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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
| x | y | z | Uiso*/Ueq | Occ. (<1) | |
| La1 | −0.03227 (2) | 0.49487 (2) | 0.37122 (2) | 0.01306 (6) | |
| Al1 | −0.12529 (11) | 0.40803 (10) | 0.21948 (9) | 0.0286 (3) | |
| O1 | −0.0005 (2) | 0.3834 (3) | 0.2697 (2) | 0.0386 (7) | |
| C1 | 0.0953 (4) | 0.3005 (4) | 0.2479 (4) | 0.0524 (14) | |
| H1A | 0.088611 | 0.290505 | 0.185791 | 0.079* | |
| H1B | 0.109110 | 0.232657 | 0.297403 | 0.079* | |
| H1C | 0.155252 | 0.320192 | 0.245107 | 0.079* | |
| C2 | −0.2300 (4) | 0.5359 (3) | 0.2694 (3) | 0.0336 (10) | |
| H2A | −0.300473 | 0.565883 | 0.239855 | 0.050* | |
| H2B | −0.203033 | 0.591960 | 0.253632 | 0.050* | |
| H2C | −0.237368 | 0.512220 | 0.338947 | 0.050* | |
| C3 | −0.1116 (4) | 0.4476 (4) | 0.0776 (3) | 0.0460 (12) | |
| H3A | −0.097311 | 0.384953 | 0.053500 | 0.069* | |
| H3B | −0.051864 | 0.468840 | 0.059015 | 0.069* | |
| H3C | −0.178880 | 0.508554 | 0.050371 | 0.069* | |
| C4 | −0.1619 (4) | 0.2840 (4) | 0.2695 (3) | 0.0406 (11) | |
| H4A | −0.110910 | 0.223099 | 0.243557 | 0.061* | |
| H4B | −0.235322 | 0.304856 | 0.250611 | 0.061* | |
| H4C | −0.157613 | 0.261936 | 0.339463 | 0.061* | |
| O2 | −0.1140 (2) | 0.3706 (2) | 0.46652 (19) | 0.0320 (7) | |
| O3 | −0.0402 (2) | 0.4255 (2) | 0.54830 (18) | 0.0232 (6) | |
| C5 | −0.0957 (3) | 0.3754 (3) | 0.5459 (3) | 0.0214 (8) | |
| C6 | −0.1398 (3) | 0.3264 (3) | 0.6418 (3) | 0.0220 (8) | |
| C7 | −0.0810 (3) | 0.3348 (3) | 0.7189 (3) | 0.0234 (8) | |
| C8 | 0.0289 (3) | 0.2683 (3) | 0.7329 (3) | 0.0271 (8) | |
| H8 | 0.064082 | 0.213330 | 0.699308 | 0.033* | |
| C9 | 0.0885 (4) | 0.2798 (3) | 0.7944 (3) | 0.0307 (9) | |
| H9 | 0.163386 | 0.233326 | 0.802589 | 0.037* | |
| C10 | 0.0381 (4) | 0.3596 (4) | 0.8438 (3) | 0.0340 (10) | |
| H10 | 0.077959 | 0.367317 | 0.886831 | 0.041* | |
| C11 | −0.0703 (4) | 0.4277 (4) | 0.8303 (3) | 0.0325 (10) | |
| H11 | −0.104716 | 0.482567 | 0.864064 | 0.039* | |
| C12 | −0.1300 (3) | 0.4167 (3) | 0.7672 (3) | 0.0279 (9) | |
| H12 | −0.204174 | 0.465268 | 0.757361 | 0.033* | |
| C13 | −0.2633 (3) | 0.3918 (3) | 0.6482 (3) | 0.0233 (8) | |
| C14 | −0.3158 (3) | 0.3660 (4) | 0.7337 (3) | 0.0342 (10) | |
| H14 | −0.275619 | 0.309338 | 0.785860 | 0.041* | |
| C15 | −0.4279 (4) | 0.4235 (4) | 0.7427 (3) | 0.0391 (11) | |
| H15 | −0.463027 | 0.406832 | 0.801646 | 0.047* | |
| C16 | −0.4875 (4) | 0.5041 (4) | 0.6668 (4) | 0.0387 (11) | |
| H16 | −0.563524 | 0.542101 | 0.673235 | 0.046* | |
| C17 | −0.4364 (3) | 0.5292 (3) | 0.5818 (3) | 0.0340 (10) | |
| H17 | −0.477381 | 0.584819 | 0.529442 | 0.041* | |
| C18 | −0.3253 (3) | 0.4737 (3) | 0.5721 (3) | 0.0284 (9) | |
| H18 | −0.291035 | 0.491608 | 0.513002 | 0.034* | |
| C19 | −0.1186 (3) | 0.2076 (3) | 0.6507 (3) | 0.0249 (8) | |
| C20 | −0.0899 (4) | 0.1297 (3) | 0.7379 (3) | 0.0328 (10) | |
| H20 | −0.078929 | 0.148647 | 0.791600 | 0.039* | |
| C21 | −0.0772 (4) | 0.0247 (4) | 0.7475 (4) | 0.0424 (11) | |
| H21 | −0.059311 | −0.026807 | 0.807948 | 0.051* | |
| C22 | −0.0904 (4) | −0.0056 (4) | 0.6695 (4) | 0.0415 (12) | |
| H22 | −0.078727 | −0.078289 | 0.675550 | 0.050* | |
| C23 | −0.1208 (3) | 0.0713 (3) | 0.5833 (3) | 0.0340 (10) | |
| H23 | −0.131851 | 0.051784 | 0.530019 | 0.041* | |
| C24 | −0.1355 (3) | 0.1779 (3) | 0.5732 (3) | 0.0276 (9) | |
| H24 | −0.157055 | 0.230159 | 0.513513 | 0.033* | |
| O4 | −0.1812 (2) | 0.6313 (2) | 0.43281 (18) | 0.0240 (6) | |
| O5 | −0.1427 (2) | 0.6352 (2) | 0.57488 (19) | 0.0263 (6) | |
| C25 | −0.2039 (3) | 0.6717 (3) | 0.5035 (3) | 0.0227 (8) | |
| C26 | −0.3096 (3) | 0.7777 (3) | 0.5032 (3) | 0.0227 (8) | |
| C27 | −0.2810 (3) | 0.8697 (3) | 0.4371 (3) | 0.0231 (8) | |
| C28 | −0.1853 (3) | 0.8743 (3) | 0.4508 (3) | 0.0301 (9) | |
| H28 | −0.137299 | 0.820458 | 0.499793 | 0.036* | |
| C29 | −0.1600 (3) | 0.9568 (3) | 0.3933 (3) | 0.0337 (10) | |
| H29 | −0.093985 | 0.957802 | 0.402696 | 0.040* | |
| C30 | −0.2283 (4) | 1.0370 (4) | 0.3232 (3) | 0.0368 (10) | |
| H30 | −0.210354 | 1.093329 | 0.284112 | 0.044* | |
| C31 | −0.3234 (4) | 1.0339 (4) | 0.3106 (3) | 0.0382 (11) | |
| H31 | −0.371889 | 1.089322 | 0.262629 | 0.046* | |
| C32 | −0.3499 (3) | 0.9516 (3) | 0.3667 (3) | 0.0304 (9) | |
| H32 | −0.416150 | 0.951342 | 0.356674 | 0.037* | |
| C33 | −0.3352 (3) | 0.7907 (3) | 0.6049 (3) | 0.0257 (8) | |
| C34 | −0.3485 (3) | 0.8825 (3) | 0.6307 (3) | 0.0314 (9) | |
| H34 | −0.339816 | 0.940681 | 0.584050 | 0.038* | |
| C35 | −0.3746 (4) | 0.8894 (4) | 0.7256 (4) | 0.0437 (12) | |
| H35 | −0.383374 | 0.952358 | 0.742752 | 0.052* | |
| C36 | −0.3876 (4) | 0.8057 (4) | 0.7943 (3) | 0.0447 (12) | |
| H36 | −0.404321 | 0.810532 | 0.858570 | 0.054* | |
| C37 | −0.3762 (3) | 0.7144 (4) | 0.7688 (3) | 0.0382 (11) | |
| H37 | −0.386189 | 0.656965 | 0.815430 | 0.046* | |
| C38 | −0.3502 (3) | 0.7074 (4) | 0.6750 (3) | 0.0311 (9) | |
| H38 | −0.342435 | 0.644566 | 0.658109 | 0.037* | |
| C39 | −0.4077 (3) | 0.7783 (3) | 0.4627 (3) | 0.0229 (8) | |
| C40 | −0.4009 (3) | 0.7506 (3) | 0.3772 (3) | 0.0257 (8) | |
| H40 | −0.334014 | 0.729044 | 0.343230 | 0.031* | |
| C41 | −0.4902 (3) | 0.7541 (3) | 0.3408 (3) | 0.0300 (9) | |
| H41 | −0.482883 | 0.732093 | 0.283689 | 0.036* | |
| C42 | −0.5896 (3) | 0.7893 (3) | 0.3865 (3) | 0.0316 (9) | |
| H42 | −0.650696 | 0.792166 | 0.361079 | 0.038* | |
| C43 | −0.5981 (3) | 0.8199 (4) | 0.4696 (3) | 0.0334 (10) | |
| H43 | −0.666067 | 0.844944 | 0.501464 | 0.040* | |
| C44 | −0.5089 (3) | 0.8148 (3) | 0.5072 (3) | 0.0287 (9) | |
| H44 | −0.516858 | 0.836590 | 0.564489 | 0.034* | |
| C45 | 0.3342 (4) | −0.0048 (5) | 1.0374 (4) | 0.0480 (13) | |
| C46 | 0.3902 (4) | −0.0087 (5) | 0.9511 (4) | 0.0585 (15) | |
| H46 | 0.427274 | −0.076125 | 0.934371 | 0.070* | |
| C47 | 0.3928 (5) | 0.0844 (6) | 0.8891 (5) | 0.074 (2) | |
| H47 | 0.430937 | 0.080655 | 0.829926 | 0.088* | |
| C48 | 0.3409 (6) | 0.1817 (6) | 0.9125 (5) | 0.075 (2) | |
| H48 | 0.344572 | 0.245235 | 0.870865 | 0.090* | |
| C49 | 0.2825 (5) | 0.1870 (5) | 0.9978 (5) | 0.0677 (19) | |
| H49 | 0.244438 | 0.254804 | 1.013625 | 0.081* | |
| C50 | 0.2794 (4) | 0.0939 (5) | 1.0599 (4) | 0.0563 (15) | |
| H50 | 0.239503 | 0.098150 | 1.118164 | 0.068* | |
| C51 | 0.3334 (5) | −0.1067 (5) | 1.1063 (4) | 0.0719 (19) | |
| H51A | 0.398951 | −0.169935 | 1.096588 | 0.108* | |
| H51B | 0.269827 | −0.115018 | 1.094882 | 0.108* | |
| H51C | 0.330958 | −0.101436 | 1.172030 | 0.108* | |
| C52 | 1.0278 (10) | −0.0489 (11) | −0.0048 (11) | 0.153 (5) | 0.5 |
| C53 | 1.0634 (11) | 0.0326 (16) | −0.0286 (11) | 0.153 (5) | 0.5 |
| H53 | 1.131932 | 0.020149 | −0.058622 | 0.184* | 0.5 |
| C54 | 0.9986 (15) | 0.1324 (13) | −0.0086 (9) | 0.153 (5) | 0.5 |
| H54 | 1.022959 | 0.188084 | −0.024851 | 0.184* | 0.5 |
| C55 | 0.8983 (14) | 0.1506 (8) | 0.0354 (9) | 0.153 (5) | 0.5 |
| H55 | 0.854108 | 0.218810 | 0.049064 | 0.184* | 0.5 |
| C56 | 0.8628 (8) | 0.0691 (11) | 0.0592 (7) | 0.088 (5) | 0.5 |
| H56 | 0.794229 | 0.081601 | 0.089209 | 0.106* | 0.5 |
| C57 | 0.9275 (10) | −0.0306 (9) | 0.0391 (8) | 0.066 (4) | 0.5 |
| H57 | 0.903200 | −0.086335 | 0.055439 | 0.079* | 0.5 |
| C58 | 1.1043 (16) | −0.1507 (13) | −0.0328 (18) | 0.167 (13) | 0.5 |
| H58A | 1.147324 | −0.132880 | −0.088484 | 0.251* | 0.5 |
| H58B | 1.063330 | −0.184832 | −0.048928 | 0.251* | 0.5 |
| H58C | 1.152284 | −0.201064 | 0.020591 | 0.251* | 0.5 |
| C59 | 0.4395 (9) | 0.4875 (10) | −0.0082 (9) | 0.088 (6) | 0.5 |
| C60 | 0.3781 (7) | 0.5983 (10) | −0.0446 (7) | 0.153 (5) | 0.5 |
| H60 | 0.308346 | 0.623626 | −0.069200 | 0.184* | 0.5 |
| C61 | 0.4186 (10) | 0.6720 (8) | −0.0449 (8) | 0.079 (4) | 0.5 |
| H61 | 0.376605 | 0.747699 | −0.069740 | 0.095* | 0.5 |
| C62 | 0.5206 (11) | 0.6349 (10) | −0.0089 (8) | 0.153 (5) | 0.5 |
| H62 | 0.548327 | 0.685295 | −0.009072 | 0.184* | 0.5 |
| C63 | 0.5821 (8) | 0.5242 (11) | 0.0275 (8) | 0.134 (11) | 0.5 |
| H63 | 0.651790 | 0.498818 | 0.052136 | 0.161* | 0.5 |
| C64 | 0.5415 (9) | 0.4504 (8) | 0.0278 (8) | 0.104 (7) | 0.5 |
| H64 | 0.583532 | 0.374743 | 0.052676 | 0.125* | 0.5 |
| C65 | 0.421 (2) | 0.4005 (15) | −0.0297 (12) | 0.153 (5) | 0.5 |
| H65A | 0.409788 | 0.418014 | −0.098456 | 0.230* | 0.5 |
| H65B | 0.357617 | 0.395283 | 0.005788 | 0.230* | 0.5 |
| H65C | 0.484644 | 0.330811 | −0.010675 | 0.230* | 0.5 |
Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| La1 | 0.01304 (9) | 0.01478 (10) | 0.01329 (9) | −0.00636 (7) | −0.00039 (6) | −0.00557 (7) |
| Al1 | 0.0374 (7) | 0.0314 (7) | 0.0258 (6) | −0.0203 (6) | 0.0014 (5) | −0.0117 (5) |
| O1 | 0.0376 (18) | 0.049 (2) | 0.0400 (18) | −0.0229 (16) | 0.0015 (14) | −0.0198 (15) |
| C1 | 0.052 (3) | 0.047 (3) | 0.067 (4) | −0.018 (3) | −0.012 (3) | −0.025 (3) |
| C2 | 0.047 (3) | 0.027 (2) | 0.029 (2) | −0.018 (2) | 0.0001 (19) | −0.0075 (18) |
| C3 | 0.060 (3) | 0.065 (3) | 0.030 (2) | −0.038 (3) | −0.004 (2) | −0.016 (2) |
| C4 | 0.047 (3) | 0.041 (3) | 0.047 (3) | −0.028 (2) | −0.005 (2) | −0.014 (2) |
| O2 | 0.0475 (18) | 0.0466 (18) | 0.0183 (14) | −0.0334 (16) | −0.0007 (13) | −0.0097 (13) |
| O3 | 0.0256 (14) | 0.0203 (13) | 0.0257 (14) | −0.0117 (11) | −0.0054 (11) | −0.0034 (11) |
| C5 | 0.0194 (18) | 0.0199 (18) | 0.025 (2) | −0.0081 (15) | 0.0007 (15) | −0.0069 (15) |
| C6 | 0.0241 (19) | 0.0241 (19) | 0.0222 (19) | −0.0139 (16) | 0.0003 (15) | −0.0067 (15) |
| C7 | 0.029 (2) | 0.027 (2) | 0.0189 (18) | −0.0185 (17) | −0.0003 (15) | −0.0031 (15) |
| C8 | 0.032 (2) | 0.030 (2) | 0.024 (2) | −0.0181 (18) | −0.0006 (16) | −0.0053 (16) |
| C9 | 0.037 (2) | 0.034 (2) | 0.027 (2) | −0.023 (2) | −0.0081 (18) | 0.0000 (17) |
| C10 | 0.050 (3) | 0.042 (3) | 0.022 (2) | −0.032 (2) | −0.0093 (19) | −0.0013 (18) |
| C11 | 0.049 (3) | 0.040 (3) | 0.019 (2) | −0.027 (2) | 0.0043 (18) | −0.0113 (18) |
| C12 | 0.036 (2) | 0.031 (2) | 0.023 (2) | −0.0203 (19) | 0.0058 (17) | −0.0101 (17) |
| C13 | 0.026 (2) | 0.027 (2) | 0.025 (2) | −0.0165 (17) | 0.0047 (16) | −0.0115 (16) |
| C14 | 0.031 (2) | 0.033 (2) | 0.035 (2) | −0.0144 (19) | 0.0036 (19) | −0.0057 (19) |
| C15 | 0.036 (2) | 0.043 (3) | 0.041 (3) | −0.022 (2) | 0.014 (2) | −0.012 (2) |
| C16 | 0.027 (2) | 0.036 (3) | 0.056 (3) | −0.014 (2) | 0.003 (2) | −0.016 (2) |
| C17 | 0.031 (2) | 0.029 (2) | 0.044 (3) | −0.0140 (19) | −0.004 (2) | −0.0091 (19) |
| C18 | 0.029 (2) | 0.032 (2) | 0.027 (2) | −0.0155 (18) | 0.0020 (17) | −0.0097 (17) |
| C19 | 0.0196 (19) | 0.027 (2) | 0.031 (2) | −0.0126 (16) | 0.0006 (16) | −0.0089 (16) |
| C20 | 0.039 (2) | 0.030 (2) | 0.034 (2) | −0.021 (2) | −0.0053 (19) | −0.0018 (18) |
| C21 | 0.048 (3) | 0.032 (3) | 0.050 (3) | −0.024 (2) | −0.008 (2) | 0.001 (2) |
| C22 | 0.035 (3) | 0.024 (2) | 0.067 (3) | −0.014 (2) | −0.005 (2) | −0.008 (2) |
| C23 | 0.025 (2) | 0.030 (2) | 0.055 (3) | −0.0130 (18) | 0.000 (2) | −0.021 (2) |
| C24 | 0.022 (2) | 0.026 (2) | 0.038 (2) | −0.0117 (17) | −0.0013 (17) | −0.0103 (17) |
| O4 | 0.0219 (13) | 0.0260 (14) | 0.0255 (14) | −0.0085 (11) | −0.0015 (11) | −0.0110 (11) |
| O5 | 0.0196 (13) | 0.0295 (15) | 0.0269 (15) | −0.0044 (11) | −0.0029 (11) | −0.0120 (12) |
| C25 | 0.0205 (19) | 0.0220 (19) | 0.028 (2) | −0.0091 (15) | 0.0005 (15) | −0.0101 (16) |
| C26 | 0.0171 (18) | 0.0212 (19) | 0.031 (2) | −0.0064 (15) | −0.0023 (15) | −0.0105 (16) |
| C27 | 0.0201 (18) | 0.0227 (19) | 0.030 (2) | −0.0083 (15) | −0.0005 (15) | −0.0125 (16) |
| C28 | 0.022 (2) | 0.028 (2) | 0.043 (3) | −0.0088 (17) | −0.0016 (18) | −0.0158 (19) |
| C29 | 0.024 (2) | 0.034 (2) | 0.053 (3) | −0.0145 (19) | 0.0061 (19) | −0.024 (2) |
| C30 | 0.040 (3) | 0.031 (2) | 0.047 (3) | −0.022 (2) | 0.010 (2) | −0.015 (2) |
| C31 | 0.040 (3) | 0.030 (2) | 0.046 (3) | −0.017 (2) | −0.007 (2) | −0.004 (2) |
| C32 | 0.028 (2) | 0.027 (2) | 0.039 (2) | −0.0135 (18) | −0.0037 (18) | −0.0078 (18) |
| C33 | 0.0177 (18) | 0.033 (2) | 0.026 (2) | −0.0042 (16) | −0.0031 (15) | −0.0161 (17) |
| C34 | 0.022 (2) | 0.033 (2) | 0.038 (2) | −0.0033 (17) | −0.0048 (17) | −0.0196 (19) |
| C35 | 0.035 (3) | 0.046 (3) | 0.046 (3) | −0.003 (2) | −0.007 (2) | −0.028 (2) |
| C36 | 0.035 (3) | 0.065 (3) | 0.031 (3) | −0.010 (2) | 0.002 (2) | −0.027 (2) |
| C37 | 0.032 (2) | 0.050 (3) | 0.026 (2) | −0.011 (2) | −0.0008 (18) | −0.011 (2) |
| C38 | 0.027 (2) | 0.038 (2) | 0.027 (2) | −0.0113 (19) | 0.0001 (17) | −0.0112 (18) |
| C39 | 0.0200 (18) | 0.0205 (19) | 0.027 (2) | −0.0074 (15) | −0.0043 (15) | −0.0049 (15) |
| C40 | 0.0205 (19) | 0.029 (2) | 0.027 (2) | −0.0090 (16) | −0.0006 (16) | −0.0084 (17) |
| C41 | 0.028 (2) | 0.033 (2) | 0.030 (2) | −0.0114 (18) | −0.0058 (17) | −0.0111 (18) |
| C42 | 0.024 (2) | 0.038 (2) | 0.038 (2) | −0.0156 (19) | −0.0055 (18) | −0.0116 (19) |
| C43 | 0.019 (2) | 0.038 (2) | 0.044 (3) | −0.0092 (18) | 0.0008 (18) | −0.017 (2) |
| C44 | 0.023 (2) | 0.030 (2) | 0.032 (2) | −0.0074 (17) | −0.0003 (17) | −0.0139 (18) |
| C45 | 0.035 (3) | 0.063 (4) | 0.046 (3) | −0.023 (3) | −0.008 (2) | −0.006 (3) |
| C46 | 0.043 (3) | 0.071 (4) | 0.052 (3) | −0.019 (3) | 0.004 (3) | −0.012 (3) |
| C47 | 0.058 (4) | 0.099 (6) | 0.054 (4) | −0.043 (4) | −0.009 (3) | 0.014 (4) |
| C48 | 0.081 (5) | 0.069 (5) | 0.081 (5) | −0.047 (4) | −0.048 (4) | 0.019 (4) |
| C49 | 0.069 (4) | 0.054 (4) | 0.081 (5) | −0.015 (3) | −0.043 (4) | −0.018 (3) |
| C50 | 0.048 (3) | 0.074 (4) | 0.050 (3) | −0.021 (3) | −0.014 (3) | −0.022 (3) |
| C51 | 0.071 (4) | 0.081 (5) | 0.064 (4) | −0.046 (4) | −0.012 (3) | 0.010 (3) |
| C52 | 0.237 (14) | 0.187 (12) | 0.044 (5) | −0.111 (12) | −0.030 (6) | 0.006 (6) |
| C53 | 0.237 (14) | 0.187 (12) | 0.044 (5) | −0.111 (12) | −0.030 (6) | 0.006 (6) |
| C54 | 0.237 (14) | 0.187 (12) | 0.044 (5) | −0.111 (12) | −0.030 (6) | 0.006 (6) |
| C55 | 0.237 (14) | 0.187 (12) | 0.044 (5) | −0.111 (12) | −0.030 (6) | 0.006 (6) |
| C56 | 0.077 (10) | 0.133 (15) | 0.049 (8) | −0.037 (11) | −0.010 (7) | −0.023 (10) |
| C57 | 0.085 (9) | 0.077 (9) | 0.061 (8) | −0.075 (8) | −0.048 (7) | 0.034 (6) |
| C58 | 0.19 (2) | 0.063 (12) | 0.20 (2) | 0.052 (12) | −0.125 (19) | −0.094 (15) |
| C59 | 0.090 (12) | 0.167 (18) | 0.083 (12) | −0.115 (14) | 0.040 (9) | −0.058 (12) |
| C60 | 0.237 (14) | 0.187 (12) | 0.044 (5) | −0.111 (12) | −0.030 (6) | 0.006 (6) |
| C61 | 0.072 (9) | 0.066 (9) | 0.099 (11) | −0.038 (8) | 0.035 (8) | −0.023 (8) |
| C62 | 0.237 (14) | 0.187 (12) | 0.044 (5) | −0.111 (12) | −0.030 (6) | 0.006 (6) |
| C63 | 0.112 (15) | 0.29 (3) | 0.127 (16) | −0.16 (2) | 0.072 (12) | −0.15 (2) |
| C64 | 0.095 (13) | 0.22 (3) | 0.046 (9) | −0.107 (16) | 0.015 (7) | −0.042 (12) |
| C65 | 0.237 (14) | 0.187 (12) | 0.044 (5) | −0.111 (12) | −0.030 (6) | 0.006 (6) |
Geometric parameters (Å, º)
| La1—O1 | 2.336 (3) | C27—C32 | 1.383 (5) |
| La1—O2 | 2.501 (3) | C27—C28 | 1.400 (5) |
| La1—O3 | 2.494 (3) | C28—C29 | 1.383 (6) |
| La1—O3i | 2.403 (2) | C28—H28 | 0.9500 |
| La1—O4 | 2.396 (3) | C29—C30 | 1.370 (6) |
| La1—O5i | 2.367 (3) | C29—H29 | 0.9500 |
| La1—C2 | 3.042 (4) | C30—C31 | 1.376 (6) |
| La1—C5 | 2.892 (4) | C30—H30 | 0.9500 |
| La1—C7i | 3.318 (4) | C31—C32 | 1.385 (6) |
| La1—C8i | 3.287 (4) | C31—H31 | 0.9500 |
| La1—C9i | 3.246 (4) | C32—H32 | 0.9500 |
| La1—C10i | 3.212 (4) | C33—C34 | 1.388 (5) |
| La1—C11i | 3.201 (4) | C33—C38 | 1.398 (6) |
| La1—C12i | 3.239 (4) | C34—C35 | 1.403 (6) |
| Al1—O1 | 1.819 (3) | C34—H34 | 0.9500 |
| Al1—C2 | 2.014 (4) | C35—C36 | 1.380 (7) |
| Al1—C3 | 1.990 (5) | C35—H35 | 0.9500 |
| Al1—C4 | 1.961 (4) | C36—C37 | 1.387 (7) |
| La1—Al1 | 3.4481 (12) | C36—H36 | 0.9500 |
| La1—La1i | 4.0432 (4) | C37—C38 | 1.388 (6) |
| O1—C1 | 1.398 (6) | C37—H37 | 0.9500 |
| C1—H1A | 0.9800 | C38—H38 | 0.9500 |
| C1—H1B | 0.9800 | C39—C40 | 1.394 (5) |
| C1—H1C | 0.9800 | C39—C44 | 1.396 (5) |
| C2—H2A | 0.9800 | C40—C41 | 1.388 (5) |
| C2—H2B | 0.9800 | C40—H40 | 0.9500 |
| C2—H2C | 0.9800 | C41—C42 | 1.382 (6) |
| C3—H3A | 0.9800 | C41—H41 | 0.9500 |
| C3—H3B | 0.9800 | C42—C43 | 1.378 (6) |
| C3—H3C | 0.9800 | C42—H42 | 0.9500 |
| C4—H4A | 0.9800 | C43—C44 | 1.385 (6) |
| C4—H4B | 0.9800 | C43—H43 | 0.9500 |
| C4—H4C | 0.9800 | C44—H44 | 0.9500 |
| O2—C5 | 1.247 (4) | C45—C50 | 1.378 (8) |
| O3—C5 | 1.269 (4) | C45—C46 | 1.387 (7) |
| C5—C6 | 1.548 (5) | C45—C51 | 1.509 (7) |
| C6—C7 | 1.538 (5) | C46—C47 | 1.383 (8) |
| C6—C13 | 1.544 (5) | C46—H46 | 0.9500 |
| C6—C19 | 1.548 (5) | C47—C48 | 1.365 (9) |
| C7—C8 | 1.394 (5) | C47—H47 | 0.9500 |
| C7—C12 | 1.397 (5) | C48—C49 | 1.389 (9) |
| C8—C9 | 1.389 (5) | C48—H48 | 0.9500 |
| C8—H8 | 0.9500 | C49—C50 | 1.385 (9) |
| C9—C10 | 1.385 (6) | C49—H49 | 0.9500 |
| C9—H9 | 0.9500 | C50—H50 | 0.9500 |
| C10—C11 | 1.379 (6) | C51—H51A | 0.9800 |
| C10—H10 | 0.9500 | C51—H51B | 0.9800 |
| C11—C12 | 1.403 (5) | C51—H51C | 0.9800 |
| C11—H11 | 0.9500 | C52—C53 | 1.3900 |
| C12—H12 | 0.9500 | C52—C57 | 1.3900 |
| C13—C14 | 1.394 (5) | C52—C58 | 1.496 (8) |
| C13—C18 | 1.397 (5) | C53—C54 | 1.3900 |
| C14—C15 | 1.402 (6) | C53—H53 | 0.9500 |
| C14—H14 | 0.9500 | C54—C55 | 1.3900 |
| C15—C16 | 1.378 (6) | C54—H54 | 0.9500 |
| C15—H15 | 0.9500 | C55—C56 | 1.3900 |
| C16—C17 | 1.376 (6) | C55—H55 | 0.9500 |
| C16—H16 | 0.9500 | C56—C57 | 1.3900 |
| C17—C18 | 1.389 (6) | C56—H56 | 0.9500 |
| C17—H17 | 0.9500 | C57—H57 | 0.9500 |
| C18—H18 | 0.9500 | C58—H58A | 0.9800 |
| C19—C20 | 1.393 (6) | C58—H58B | 0.9800 |
| C19—C24 | 1.397 (5) | C58—H58C | 0.9800 |
| C20—C21 | 1.388 (6) | C59—C60 | 1.3900 |
| C20—H20 | 0.9500 | C59—C64 | 1.3900 |
| C21—C22 | 1.389 (7) | C59—C65 | 1.489 (9) |
| C21—H21 | 0.9500 | C60—C61 | 1.3900 |
| C22—C23 | 1.379 (6) | C60—H60 | 0.9500 |
| C22—H22 | 0.9500 | C61—C62 | 1.3900 |
| C23—C24 | 1.400 (5) | C61—H61 | 0.9500 |
| C23—H23 | 0.9500 | C62—C63 | 1.3900 |
| C24—H24 | 0.9500 | C62—H62 | 0.9500 |
| O4—C25 | 1.260 (4) | C63—C64 | 1.3900 |
| O5—C25 | 1.271 (4) | C63—H63 | 0.9500 |
| C25—C26 | 1.563 (5) | C64—H64 | 0.9500 |
| C26—C33 | 1.522 (5) | C65—H65A | 0.9800 |
| C26—C39 | 1.550 (5) | C65—H65B | 0.9800 |
| C26—C27 | 1.557 (5) | C65—H65C | 0.9800 |
| O1—La1—O5i | 82.41 (10) | C10—C9—H9 | 120.2 |
| O1—La1—O4 | 139.15 (10) | C8—C9—H9 | 120.2 |
| O5i—La1—O4 | 135.39 (9) | C11—C10—C9 | 119.8 (4) |
| O1—La1—O3i | 147.59 (10) | C11—C10—H10 | 120.1 |
| O5i—La1—O3i | 71.61 (9) | C9—C10—H10 | 120.1 |
| O4—La1—O3i | 72.32 (9) | C10—C11—C12 | 120.6 (4) |
| O1—La1—O3 | 121.24 (10) | C10—C11—H11 | 119.7 |
| O5i—La1—O3 | 71.46 (9) | C12—C11—H11 | 119.7 |
| O4—La1—O3 | 71.58 (9) | C7—C12—C11 | 120.3 (4) |
| O3i—La1—O3 | 68.70 (10) | C7—C12—H12 | 119.8 |
| O1—La1—O2 | 78.88 (10) | C11—C12—H12 | 119.8 |
| O5i—La1—O2 | 91.47 (10) | C14—C13—C18 | 118.4 (4) |
| O4—La1—O2 | 84.39 (9) | C14—C13—C6 | 118.1 (4) |
| O3i—La1—O2 | 119.83 (8) | C18—C13—C6 | 123.5 (3) |
| O3—La1—O2 | 51.29 (8) | C13—C14—C15 | 120.0 (4) |
| O1—La1—C5 | 101.05 (11) | C13—C14—H14 | 120.0 |
| O5i—La1—C5 | 82.20 (10) | C15—C14—H14 | 120.0 |
| O4—La1—C5 | 75.29 (10) | C16—C15—C14 | 120.6 (4) |
| O3i—La1—C5 | 94.40 (9) | C16—C15—H15 | 119.7 |
| O3—La1—C5 | 25.94 (9) | C14—C15—H15 | 119.7 |
| O2—La1—C5 | 25.44 (9) | C17—C16—C15 | 119.7 (4) |
| O1—La1—C2 | 64.73 (11) | C17—C16—H16 | 120.1 |
| O5i—La1—C2 | 144.59 (10) | C15—C16—H16 | 120.1 |
| O4—La1—C2 | 74.60 (10) | C16—C17—C18 | 120.3 (4) |
| O3i—La1—C2 | 143.78 (10) | C16—C17—H17 | 119.9 |
| O3—La1—C2 | 113.77 (10) | C18—C17—H17 | 119.9 |
| O2—La1—C2 | 70.40 (10) | C17—C18—C13 | 120.9 (4) |
| C5—La1—C2 | 91.12 (11) | C17—C18—H18 | 119.5 |
| O1—La1—C11i | 67.47 (11) | C13—C18—H18 | 119.5 |
| O5i—La1—C11i | 89.35 (11) | C20—C19—C24 | 118.4 (4) |
| O4—La1—C11i | 117.69 (10) | C20—C19—C6 | 120.8 (3) |
| O3i—La1—C11i | 92.66 (9) | C24—C19—C6 | 120.7 (4) |
| O3—La1—C11i | 156.40 (10) | C21—C20—C19 | 120.9 (4) |
| O2—La1—C11i | 145.92 (9) | C21—C20—H20 | 119.5 |
| C5—La1—C11i | 166.69 (10) | C19—C20—H20 | 119.5 |
| C2—La1—C11i | 89.83 (11) | C20—C21—C22 | 120.6 (4) |
| O1—La1—C10i | 73.06 (11) | C20—C21—H21 | 119.7 |
| O5i—La1—C10i | 114.19 (11) | C22—C21—H21 | 119.7 |
| O4—La1—C10i | 97.09 (11) | C23—C22—C21 | 119.0 (4) |
| O3i—La1—C10i | 99.91 (9) | C23—C22—H22 | 120.5 |
| O3—La1—C10i | 165.67 (10) | C21—C22—H22 | 120.5 |
| O2—La1—C10i | 138.28 (9) | C22—C23—C24 | 120.9 (4) |
| C5—La1—C10i | 160.95 (11) | C22—C23—H23 | 119.6 |
| C2—La1—C10i | 69.92 (11) | C24—C23—H23 | 119.6 |
| C11i—La1—C10i | 24.84 (11) | C19—C24—C23 | 120.2 (4) |
| O1—La1—C12i | 86.54 (10) | C19—C24—H24 | 119.9 |
| O5i—La1—C12i | 75.20 (10) | C23—C24—H24 | 119.9 |
| O4—La1—C12i | 114.12 (10) | C25—O4—La1 | 139.1 (2) |
| O3i—La1—C12i | 68.61 (9) | C25—O5—La1i | 141.2 (2) |
| O3—La1—C12i | 132.01 (9) | O4—C25—O5 | 124.1 (3) |
| O2—La1—C12i | 161.48 (10) | O4—C25—C26 | 119.6 (3) |
| C5—La1—C12i | 155.02 (11) | O5—C25—C26 | 116.2 (3) |
| C2—La1—C12i | 113.49 (11) | C33—C26—C39 | 109.6 (3) |
| C11i—La1—C12i | 25.16 (10) | C33—C26—C27 | 111.5 (3) |
| C10i—La1—C12i | 44.00 (11) | C39—C26—C27 | 109.9 (3) |
| O1—La1—C9i | 96.80 (11) | C33—C26—C25 | 109.0 (3) |
| O5i—La1—C9i | 125.80 (10) | C39—C26—C25 | 113.0 (3) |
| O4—La1—C9i | 74.39 (10) | C27—C26—C25 | 103.8 (3) |
| O3i—La1—C9i | 83.65 (9) | C32—C27—C28 | 117.8 (4) |
| O3—La1—C9i | 141.16 (9) | C32—C27—C26 | 122.1 (3) |
| O2—La1—C9i | 141.89 (10) | C28—C27—C26 | 120.0 (3) |
| C5—La1—C9i | 148.71 (11) | C29—C28—C27 | 120.4 (4) |
| C2—La1—C9i | 73.57 (10) | C29—C28—H28 | 119.8 |
| C11i—La1—C9i | 43.54 (11) | C27—C28—H28 | 119.8 |
| C10i—La1—C9i | 24.77 (11) | C30—C29—C28 | 121.3 (4) |
| C12i—La1—C9i | 50.79 (11) | C30—C29—H29 | 119.3 |
| O1—La1—C8i | 115.26 (11) | C28—C29—H29 | 119.3 |
| O5i—La1—C8i | 109.86 (10) | C29—C30—C31 | 118.4 (4) |
| O4—La1—C8i | 71.71 (10) | C29—C30—H30 | 120.8 |
| O3i—La1—C8i | 59.29 (9) | C31—C30—H30 | 120.8 |
| O3—La1—C8i | 122.88 (9) | C30—C31—C32 | 121.2 (4) |
| O2—La1—C8i | 155.27 (10) | C30—C31—H31 | 119.4 |
| C5—La1—C8i | 142.66 (10) | C32—C31—H31 | 119.4 |
| C2—La1—C8i | 96.47 (10) | C27—C32—C31 | 120.8 (4) |
| C11i—La1—C8i | 50.24 (11) | C27—C32—H32 | 119.6 |
| C10i—La1—C8i | 43.27 (10) | C31—C32—H32 | 119.6 |
| C12i—La1—C8i | 42.94 (10) | C34—C33—C38 | 118.4 (4) |
| C9i—La1—C8i | 24.55 (9) | C34—C33—C26 | 123.6 (4) |
| O1—La1—C7i | 110.09 (10) | C38—C33—C26 | 118.0 (3) |
| O5i—La1—C7i | 85.71 (10) | C33—C34—C35 | 120.1 (4) |
| O4—La1—C7i | 90.93 (9) | C33—C34—H34 | 119.9 |
| O3i—La1—C7i | 50.27 (9) | C35—C34—H34 | 119.9 |
| O3—La1—C7i | 118.89 (8) | C36—C35—C34 | 120.7 (4) |
| O2—La1—C7i | 170.08 (9) | C36—C35—H35 | 119.6 |
| C5—La1—C7i | 144.67 (10) | C34—C35—H35 | 119.6 |
| C2—La1—C7i | 116.78 (10) | C35—C36—C37 | 119.5 (4) |
| C11i—La1—C7i | 43.70 (10) | C35—C36—H36 | 120.2 |
| C10i—La1—C7i | 50.94 (10) | C37—C36—H36 | 120.2 |
| C12i—La1—C7i | 24.56 (9) | C36—C37—C38 | 119.8 (5) |
| C9i—La1—C7i | 43.50 (10) | C36—C37—H37 | 120.1 |
| C8i—La1—C7i | 24.35 (9) | C38—C37—H37 | 120.1 |
| O1—La1—Al1 | 29.38 (8) | C37—C38—C33 | 121.3 (4) |
| O5i—La1—Al1 | 110.37 (7) | C37—C38—H38 | 119.3 |
| O4—La1—Al1 | 109.78 (6) | C33—C38—H38 | 119.3 |
| O3i—La1—Al1 | 169.94 (6) | C40—C39—C44 | 117.2 (3) |
| O3—La1—Al1 | 121.36 (6) | C40—C39—C26 | 121.8 (3) |
| O2—La1—Al1 | 70.20 (6) | C44—C39—C26 | 120.8 (3) |
| C5—La1—Al1 | 95.64 (8) | C41—C40—C39 | 121.1 (4) |
| C2—La1—Al1 | 35.46 (8) | C41—C40—H40 | 119.5 |
| C11i—La1—Al1 | 77.62 (7) | C39—C40—H40 | 119.5 |
| C10i—La1—Al1 | 70.17 (7) | C42—C41—C40 | 120.9 (4) |
| C12i—La1—Al1 | 102.03 (7) | C42—C41—H41 | 119.6 |
| C9i—La1—Al1 | 87.46 (7) | C40—C41—H41 | 119.6 |
| C8i—La1—Al1 | 111.50 (7) | C43—C42—C41 | 118.6 (4) |
| C7i—La1—Al1 | 119.68 (7) | C43—C42—H42 | 120.7 |
| O1—La1—La1i | 145.25 (8) | C41—C42—H42 | 120.7 |
| O5i—La1—La1i | 67.44 (6) | C42—C43—C44 | 120.8 (4) |
| O4—La1—La1i | 67.95 (6) | C42—C43—H43 | 119.6 |
| O3i—La1—La1i | 35.07 (6) | C44—C43—H43 | 119.6 |
| O3—La1—La1i | 33.63 (6) | C43—C44—C39 | 121.4 (4) |
| O2—La1—La1i | 84.84 (6) | C43—C44—H44 | 119.3 |
| C5—La1—La1i | 59.40 (7) | C39—C44—H44 | 119.3 |
| C2—La1—La1i | 136.72 (8) | C50—C45—C46 | 118.9 (6) |
| C11i—La1—La1i | 126.35 (7) | C50—C45—C51 | 120.2 (6) |
| C10i—La1—La1i | 134.41 (7) | C46—C45—C51 | 120.9 (6) |
| C12i—La1—La1i | 101.30 (7) | C47—C46—C45 | 120.8 (6) |
| C9i—La1—La1i | 114.49 (7) | C47—C46—H46 | 119.6 |
| C8i—La1—La1i | 91.79 (7) | C45—C46—H46 | 119.6 |
| C7i—La1—La1i | 85.30 (6) | C48—C47—C46 | 120.3 (7) |
| Al1—La1—La1i | 154.99 (2) | C48—C47—H47 | 119.8 |
| O1—Al1—C4 | 111.77 (18) | C46—C47—H47 | 119.8 |
| O1—Al1—C3 | 108.32 (18) | C47—C48—C49 | 119.4 (6) |
| C4—Al1—C3 | 113.2 (2) | C47—C48—H48 | 120.3 |
| O1—Al1—C2 | 100.03 (17) | C49—C48—H48 | 120.3 |
| C4—Al1—C2 | 110.7 (2) | C50—C49—C48 | 120.4 (6) |
| C3—Al1—C2 | 112.0 (2) | C50—C49—H49 | 119.8 |
| O1—Al1—La1 | 39.05 (10) | C48—C49—H49 | 119.8 |
| C4—Al1—La1 | 120.09 (15) | C45—C50—C49 | 120.2 (6) |
| C3—Al1—La1 | 124.87 (14) | C45—C50—H50 | 119.9 |
| C2—Al1—La1 | 61.19 (13) | C49—C50—H50 | 119.9 |
| C1—O1—Al1 | 118.0 (3) | C45—C51—H51A | 109.5 |
| C1—O1—La1 | 130.3 (3) | C45—C51—H51B | 109.5 |
| Al1—O1—La1 | 111.57 (15) | H51A—C51—H51B | 109.5 |
| O1—C1—H1A | 109.5 | C45—C51—H51C | 109.5 |
| O1—C1—H1B | 109.5 | H51A—C51—H51C | 109.5 |
| H1A—C1—H1B | 109.5 | H51B—C51—H51C | 109.5 |
| O1—C1—H1C | 109.5 | C53—C52—C57 | 120.0 |
| H1A—C1—H1C | 109.5 | C53—C52—C58 | 114.2 (15) |
| H1B—C1—H1C | 109.5 | C57—C52—C58 | 125.7 (15) |
| Al1—C2—La1 | 83.34 (15) | C54—C53—C52 | 120.0 |
| Al1—C2—H2A | 109.5 | C54—C53—H53 | 120.0 |
| La1—C2—H2A | 166.5 | C52—C53—H53 | 120.0 |
| Al1—C2—H2B | 109.5 | C55—C54—C53 | 120.0 |
| La1—C2—H2B | 60.7 | C55—C54—H54 | 120.0 |
| H2A—C2—H2B | 109.5 | C53—C54—H54 | 120.0 |
| Al1—C2—H2C | 109.5 | C54—C55—C56 | 120.0 |
| La1—C2—H2C | 68.5 | C54—C55—H55 | 120.0 |
| H2A—C2—H2C | 109.5 | C56—C55—H55 | 120.0 |
| H2B—C2—H2C | 109.5 | C55—C56—C57 | 120.0 |
| Al1—C3—H3A | 109.5 | C55—C56—H56 | 120.0 |
| Al1—C3—H3B | 109.5 | C57—C56—H56 | 120.0 |
| H3A—C3—H3B | 109.5 | C56—C57—C52 | 120.0 |
| Al1—C3—H3C | 109.5 | C56—C57—H57 | 120.0 |
| H3A—C3—H3C | 109.5 | C52—C57—H57 | 120.0 |
| H3B—C3—H3C | 109.5 | C52—C58—H58A | 109.5 |
| Al1—C4—H4A | 109.5 | C52—C58—H58B | 109.5 |
| Al1—C4—H4B | 109.5 | H58A—C58—H58B | 109.5 |
| H4A—C4—H4B | 109.5 | C52—C58—H58C | 109.5 |
| Al1—C4—H4C | 109.5 | H58A—C58—H58C | 109.5 |
| H4A—C4—H4C | 109.5 | H58B—C58—H58C | 109.5 |
| H4B—C4—H4C | 109.5 | C60—C59—C64 | 120.0 |
| C5—O2—La1 | 95.0 (2) | C60—C59—C65 | 124.4 (10) |
| C5—O3—La1i | 152.7 (2) | C64—C59—C65 | 113.0 (12) |
| C5—O3—La1 | 94.8 (2) | C61—C60—C59 | 120.0 |
| La1i—O3—La1 | 111.30 (9) | C61—C60—H60 | 120.0 |
| O2—C5—O3 | 118.4 (3) | C59—C60—H60 | 120.0 |
| O2—C5—C6 | 123.7 (3) | C60—C61—C62 | 120.0 |
| O3—C5—C6 | 117.8 (3) | C60—C61—H61 | 120.0 |
| O2—C5—La1 | 59.51 (19) | C62—C61—H61 | 120.0 |
| O3—C5—La1 | 59.24 (19) | C63—C62—C61 | 120.0 |
| C6—C5—La1 | 172.3 (2) | C63—C62—H62 | 120.0 |
| C7—C6—C13 | 111.8 (3) | C61—C62—H62 | 120.0 |
| C7—C6—C5 | 104.6 (3) | C62—C63—C64 | 120.0 |
| C13—C6—C5 | 110.0 (3) | C62—C63—H63 | 120.0 |
| C7—C6—C19 | 112.2 (3) | C64—C63—H63 | 120.0 |
| C13—C6—C19 | 106.7 (3) | C63—C64—C59 | 120.0 |
| C5—C6—C19 | 111.6 (3) | C63—C64—H64 | 120.0 |
| C8—C7—C12 | 117.8 (4) | C59—C64—H64 | 120.0 |
| C8—C7—C6 | 119.4 (3) | C59—C65—H65A | 109.5 |
| C12—C7—C6 | 122.2 (4) | C59—C65—H65B | 109.5 |
| C9—C8—C7 | 122.0 (4) | H65A—C65—H65B | 109.5 |
| C9—C8—H8 | 119.0 | C59—C65—H65C | 109.5 |
| C7—C8—H8 | 119.0 | H65A—C65—H65C | 109.5 |
| C10—C9—C8 | 119.5 (4) | H65B—C65—H65C | 109.5 |
| C4—Al1—O1—C1 | 65.1 (4) | O5—C25—C26—C39 | −142.5 (3) |
| C3—Al1—O1—C1 | −60.3 (4) | O4—C25—C26—C27 | −77.6 (4) |
| C2—Al1—O1—C1 | −177.7 (4) | O5—C25—C26—C27 | 98.5 (4) |
| La1—Al1—O1—C1 | 176.5 (4) | C33—C26—C27—C32 | −108.6 (4) |
| C4—Al1—O1—La1 | −111.4 (2) | C39—C26—C27—C32 | 13.0 (5) |
| C3—Al1—O1—La1 | 123.2 (2) | C25—C26—C27—C32 | 134.2 (4) |
| C2—Al1—O1—La1 | 5.8 (2) | C33—C26—C27—C28 | 68.4 (4) |
| La1—O2—C5—O3 | −6.3 (4) | C39—C26—C27—C28 | −170.0 (3) |
| La1—O2—C5—C6 | 171.8 (3) | C25—C26—C27—C28 | −48.8 (4) |
| La1i—O3—C5—O2 | 169.6 (3) | C32—C27—C28—C29 | −1.8 (6) |
| La1—O3—C5—O2 | 6.4 (4) | C26—C27—C28—C29 | −179.0 (4) |
| La1i—O3—C5—C6 | −8.6 (7) | C27—C28—C29—C30 | 1.3 (6) |
| La1—O3—C5—C6 | −171.9 (3) | C28—C29—C30—C31 | −0.1 (7) |
| La1i—O3—C5—La1 | 163.3 (5) | C29—C30—C31—C32 | −0.5 (7) |
| O2—C5—C6—C7 | 170.6 (4) | C28—C27—C32—C31 | 1.2 (6) |
| O3—C5—C6—C7 | −11.2 (4) | C26—C27—C32—C31 | 178.3 (4) |
| O2—C5—C6—C13 | −69.2 (5) | C30—C31—C32—C27 | −0.1 (7) |
| O3—C5—C6—C13 | 109.0 (4) | C39—C26—C33—C34 | −112.0 (4) |
| O2—C5—C6—C19 | 49.1 (5) | C27—C26—C33—C34 | 9.8 (5) |
| O3—C5—C6—C19 | −132.8 (3) | C25—C26—C33—C34 | 123.8 (4) |
| C13—C6—C7—C8 | 170.5 (3) | C39—C26—C33—C38 | 65.4 (4) |
| C5—C6—C7—C8 | −70.4 (4) | C27—C26—C33—C38 | −172.8 (3) |
| C19—C6—C7—C8 | 50.7 (5) | C25—C26—C33—C38 | −58.7 (4) |
| C13—C6—C7—C12 | −18.2 (5) | C38—C33—C34—C35 | 1.0 (6) |
| C5—C6—C7—C12 | 100.9 (4) | C26—C33—C34—C35 | 178.4 (4) |
| C19—C6—C7—C12 | −138.0 (4) | C33—C34—C35—C36 | −0.1 (7) |
| C12—C7—C8—C9 | 1.7 (6) | C34—C35—C36—C37 | −0.9 (7) |
| C6—C7—C8—C9 | 173.3 (3) | C35—C36—C37—C38 | 1.0 (7) |
| C7—C8—C9—C10 | 0.0 (6) | C36—C37—C38—C33 | −0.1 (6) |
| C8—C9—C10—C11 | −1.0 (6) | C34—C33—C38—C37 | −0.9 (6) |
| C9—C10—C11—C12 | 0.2 (6) | C26—C33—C38—C37 | −178.5 (4) |
| C8—C7—C12—C11 | −2.4 (6) | C33—C26—C39—C40 | −169.7 (4) |
| C6—C7—C12—C11 | −173.8 (3) | C27—C26—C39—C40 | 67.6 (4) |
| C10—C11—C12—C7 | 1.5 (6) | C25—C26—C39—C40 | −47.9 (5) |
| C7—C6—C13—C14 | −58.2 (4) | C33—C26—C39—C44 | 15.3 (5) |
| C5—C6—C13—C14 | −173.9 (3) | C27—C26—C39—C44 | −107.4 (4) |
| C19—C6—C13—C14 | 64.8 (4) | C25—C26—C39—C44 | 137.1 (4) |
| C7—C6—C13—C18 | 123.4 (4) | C44—C39—C40—C41 | −3.2 (6) |
| C5—C6—C13—C18 | 7.6 (5) | C26—C39—C40—C41 | −178.4 (4) |
| C19—C6—C13—C18 | −113.7 (4) | C39—C40—C41—C42 | 2.6 (6) |
| C18—C13—C14—C15 | −1.6 (6) | C40—C41—C42—C43 | −0.6 (6) |
| C6—C13—C14—C15 | 179.8 (4) | C41—C42—C43—C44 | −0.6 (7) |
| C13—C14—C15—C16 | 1.6 (7) | C42—C43—C44—C39 | −0.2 (7) |
| C14—C15—C16—C17 | −0.8 (7) | C40—C39—C44—C43 | 2.1 (6) |
| C15—C16—C17—C18 | 0.1 (7) | C26—C39—C44—C43 | 177.3 (4) |
| C16—C17—C18—C13 | −0.2 (6) | C50—C45—C46—C47 | 1.0 (8) |
| C14—C13—C18—C17 | 1.0 (6) | C51—C45—C46—C47 | −178.5 (5) |
| C6—C13—C18—C17 | 179.4 (3) | C45—C46—C47—C48 | 0.6 (9) |
| C7—C6—C19—C20 | 24.5 (5) | C46—C47—C48—C49 | −2.0 (9) |
| C13—C6—C19—C20 | −98.2 (4) | C47—C48—C49—C50 | 1.8 (9) |
| C5—C6—C19—C20 | 141.6 (4) | C46—C45—C50—C49 | −1.2 (8) |
| C7—C6—C19—C24 | −160.1 (3) | C51—C45—C50—C49 | 178.3 (5) |
| C13—C6—C19—C24 | 77.2 (4) | C48—C49—C50—C45 | −0.2 (8) |
| C5—C6—C19—C24 | −43.1 (5) | C57—C52—C53—C54 | 0.0 |
| C24—C19—C20—C21 | 0.7 (6) | C58—C52—C53—C54 | 178.4 (16) |
| C6—C19—C20—C21 | 176.1 (4) | C52—C53—C54—C55 | 0.0 |
| C19—C20—C21—C22 | 1.5 (7) | C53—C54—C55—C56 | 0.0 |
| C20—C21—C22—C23 | −2.7 (7) | C54—C55—C56—C57 | 0.0 |
| C21—C22—C23—C24 | 1.6 (7) | C55—C56—C57—C52 | 0.0 |
| C20—C19—C24—C23 | −1.7 (6) | C53—C52—C57—C56 | 0.0 |
| C6—C19—C24—C23 | −177.2 (3) | C58—C52—C57—C56 | −178.3 (18) |
| C22—C23—C24—C19 | 0.5 (6) | C64—C59—C60—C61 | 0.0 |
| La1—O4—C25—O5 | −7.1 (6) | C65—C59—C60—C61 | −160.7 (16) |
| La1—O4—C25—C26 | 168.7 (2) | C59—C60—C61—C62 | 0.0 |
| La1i—O5—C25—O4 | 6.7 (7) | C60—C61—C62—C63 | 0.0 |
| La1i—O5—C25—C26 | −169.3 (3) | C61—C62—C63—C64 | 0.0 |
| O4—C25—C26—C33 | 163.5 (3) | C62—C63—C64—C59 | 0.0 |
| O5—C25—C26—C33 | −20.4 (5) | C60—C59—C64—C63 | 0.0 |
| O4—C25—C26—C39 | 41.4 (5) | C65—C59—C64—C63 | 162.8 (13) |
Symmetry code: (i) −x, −y+1, −z+1.
Hydrogen-bond geometry (Å, º)
Cg1, Cg2, Cg3 and Cg4 are the centroids of the C33–C38, C39–C44, C52–C57 and C19–C24 rings, respectively.
| D—H···A | D—H | H···A | D···A | D—H···A |
| C1—H1C······Cg1i | 0.98 | 2.69 | 3.425 (6) | 132 |
| C17—H17······Cg2 | 0.95 | 2.71 | 3.485 (4) | 139 |
| C21—H21······Cg3ii | 0.95 | 2.93 | 3.677 (8) | 136 |
| C29—H29······Cg4 | 0.95 | 2.62 | 3.415 (4) | 142 |
| C32—H32······Cg2 | 0.95 | 2.95 | 3.654 (5) | 132 |
| C44—H44······Cg1 | 0.95 | 2.88 | 3.592 (5) | 132 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, −y, −z+1.
Funding Statement
This work was funded by the TIPS RAS State Plan and the Russian Science Foundation grant 17-13-01357.
References
- Anwander, R. (2002). In Applied Homogeneous Catalysis with Organometallic Compounds, edited by B. Cornils & W. A. Herrmann, pp. 974–1013. Weinheim: Wiley-VCH.
- Biagini, P., Lugli, G., Abis, L. & Millini, R. (1994). J. Organomet. Chem. 474, C16–C18.
- Bruker (2008). APEX2, SAINT and SADABS. Bruker AXS Inc.,Madison, Wisconsin, USA.
- Butcher, R. J., Clark, D. L., Grumbine, S. K., Vincent-Hollis, R. L., Scott, B. L. & Watkin, J. G. (1995). Inorg. Chem. 34, 5468–5476.
- Deacon, G. B., Feng, T., Forsyth, C. M., Gitlits, A., Hockless, D. C. R., Shen, Q., Skelton, B. W. & White, A. H. (2000). J. Chem. Soc. Dalton Trans. pp. 961–966.
- Evans, W. J., Boyle, T. J. & Ziller, J. W. (1993a). J. Am. Chem. Soc. 115, 5084–5092.
- Evans, W. J., Boyle, T. J. & Ziller, J. W. (1993b). J. Organomet. Chem. 462, 141–148.
- Evans, W. J., Greci, M. A. & Ziller, J. W. (1998). Inorg. Chem. 37, 5221–5226.
- Filatov, A. S., Gifford, S. N., Kumar, D. K. & Petrukhina, M. A. (2009). Acta Cryst. E65, m286–m287. [DOI] [PMC free article] [PubMed]
- Filatov, A. S., Rogachev, A. Yu. & Petrukhina, M. A. (2008). J. Mol. Struct. 890, 116–122.
- Fischbach, A., Herdtweck, E. & Anwander, R. (2006b). Inorg. Chim. Acta, 359, 4855–4864.
- Fischbach, A., Herdtweck, E., Anwander, R., Eickerling, G. & Scherer, W. (2003). Organometallics, 22, 499–509.
- Fischbach, A., Klimpel, M. G., Widenmeyer, M., Herdtweck, E., Scherer, W. & Anwander, R. (2004). Angew. Chem. Int. Ed. 43, 2234–2239. [DOI] [PubMed]
- Fischbach, A., Meermann, C., Eickerling, G., Scherer, W. & Anwander, R. (2006c). Macromolecules, 39, 6811–6816.
- Fischbach, A., Perdih, F., Herdtweck, E. & Anwander, R. (2006a). Organometallics, 25, 1626–1642.
- Friebe, L., Nuyken, O. & Obrecht, W. (2006). Adv. Polym. Sci. 204, 1–154.
- Gerber, L. C. H., Le Roux, E., Törnroos, K. W. & Anwander, R. (2008). Chem. Eur. J. 14, 9555–9564. [DOI] [PubMed]
- Giesbrecht, G. R., Gordon, J. C., Brady, J. T., Clark, D. L., Keogh, D. W., Michalczyk, R., Scott, B. L. & Watkin, J. G. (2002). Eur. J. Inorg. Chem. pp. 723–731.
- Giesbrecht, G. R., Gordon, J. C., Clark, D. L., Hay, P. J., Scott, B. L. & Tait, C. D. (2004). J. Am. Chem. Soc. 126, 6387–6401. [DOI] [PubMed]
- Gordon, J. C., Giesbrecht, G. R., Brady, J. T., Clark, D. L., Keogh, D. W., Scott, B. L. & Watkin, J. G. (2002). Organometallics, 21, 127–131.
- Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. [DOI] [PMC free article] [PubMed]
- Hamidi, S., Jende, L. N., Dietrich, H. M., Maichle-Mössmer, C., Törnroos, K. W., Deacon, G. B., Junk, P. C. & Anwander, R. (2013). Organometallics, 32, 1209–1223.
- Korobkov, I. & Gambarotta, S. (2009). Organometallics, 28, 4009–4019.
- Liu, S., Wei, P., Wang, Y., Santillan-Jimenez, E., Bakus, R. C. II & Atwood, D. A. (2005). Main Group Chem. 4, 3–10.
- Minyaev, M. E., Vinogradov, A. A., Roitershtein, D. M., Lyssenko, K. A., Ananyev, I. V. & Nifant’ev, I. E. (2016). Acta Cryst. C72, 578–584. [DOI] [PubMed]
- Occhipinti, G., Meermann, C., Dietrich, H. M., Litlabø, R., Auras, F., Törnroos, K. W., Maichle-Mössmer, C., Jensen, V. R. & Anwander, R. (2011). J. Am. Chem. Soc. 133, 6323–6337. [DOI] [PubMed]
- Roitershtein, D. M., Vinogradov, A. A., Lyssenko, K. A. & Nifant’ev, I. E. (2017). Inorg. Chem. Commun. 84, 225–228.
- Roitershtein, D. M., Vinogradov, A. A., Vinogradov, A. A., Lyssenko, K. A., Nelyubina, Y. V., Anan’ev, I. V., Nifant’ev, I. E., Yakovlev, V. A. & Kostitsyna, N. N. (2013). Organometallics, 32, 1272–-1286.
- Sharples, J. W., Zheng, Y.-Z., Tuna, F., McInnes, E. J. L. & Collison, D. (2011). Chem. Commun. 47, 7650–7652. [DOI] [PubMed]
- Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [DOI] [PubMed]
- Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8.
- Sommerfeldt, H.-M., Meermann, C., Törnroos, K. W. & Anwander, R. (2008). Inorg. Chem. 47, 4696–4705. [DOI] [PubMed]
- Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.
- Zimmermann, M., Frøystein, N. Å., Fischbach, A., Sirsch, P., Dietrich, H. M., Törnroos, K. W., Herdtweck, E. & Anwander, R. (2007). Chem. Eur. J. 13, 8784–8800. [DOI] [PubMed]
Associated Data
This section collects any data citations, data availability statements, or supplementary materials included in this article.
Supplementary Materials
Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989018015876/rz5247sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989018015876/rz5247Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989018015876/rz5247Isup3.cdx
CCDC reference: 1877930
Additional supporting information: crystallographic information; 3D view; checkCIF report