Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270112049281/bi3050sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270112049281/bi3050Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270112049281/bi3050IIsup3.hkl |
CCDC references: 829163; 830824
For related literature, see: Aspinall (2007); Cosgriff et al. (1993); Halcrow (2009); Kobrsi et al. (2005, 2006); Mahata et al. (2009); Marques et al. (2002); Pfeiffer et al. (1999); Pi et al. (2008); Wei et al. (2010); Werrett et al. (2011); Yang et al. (2007, 2009); Yuasa et al. (2011); Zhang et al. (2007); Zheng et al. (2003).
All manipulations were carried out using standard Schlenk line or dry-box techniques under an atmosphere of nitrogen. The THF, hexane and deuterated benzene (C6D6) solvents were refluxed over sodium and distilled.
For the synthesis of (I), La[N(SiMe3)2]3 (1.0374 g, 1.673 mmol) in THF (10 ml) was added to a THF solution (20 ml) of Ph2PzH (1.1055 g, 5.019 mmol) at room temperature. The solution was stirred for 24 h and then evaporated to dryness under vacuum to afford a pale-yellow solid. The residue was extracted with a mixture of THF and hexane. Complex (I) was obtained from the filtered extract at 243 K as colourless crystals (yield 1.49 g, 82%). Analysis, calculated for C61H65LaN6O4: C 67.52, H 6.04, N 7.74%; found: C 67.46, H 6.13, N 7.61%. Spectroscopic analysis: 1H NMR (C6D6, 300 MHz, δ, p.p.m.): 8.15 (d, J = 7.6 Hz, 12H), 7.46 (s, 3H), 7.21–7.26 (m, 12H), 7.07–7.12 (m, 6H), 3.44 (m, 16H), 1.04 (m, 16H).
Complex (II) was obtained by protolysis of La[N(SiMe3)2]3 (0.6598 g, 1.064 mmol) with Ph2TzH (0.7063 g, 3.192 mmol), following a similar procedure to that for (I). After work-up, colourless crystals of (II) were obtained (yield 0.91 g, 84%). Analysis, calculated for C54H54LaN9O3: C 63.84, H 5.36, N 12.41%; found: C 63.75, H 5.43, N 12.34%. Spectroscopic analysis: 1H NMR (C6D6, 300 MHz, δ, p.p.m.): 8.62 (d, J = 6.4 Hz, 12H), 7.19–7.24 (m, 12H), 7.08–7.13 (m, 6H), 3.30 (m, 12H), 0.85 (m, 12H); 13C{H} NMR (C6D6, 75 MHz, δ, p.p.m.): 160.6, 132.7, 128.9, 128.7, 126.8, 69.8, 24.9.
All H atoms were placed geometrically and treated as riding atoms, with C—H = 0.95 (pyrazole and phenyl) or 0.99 Å (CH2), and with Uiso(H) = 1.2Ueq(C). Some of the coordinated THF ligands in both complexes show orientational disorder. Atom C51 of (I) is split over two sites (C51 and C51') with refined site occupancies of 0.899 (11) and 0.101 (11), respectively. In complex (II), two sets of positions are defined by atoms C44/C45/C46 and C44'/C45'/C46', with refined site occupancies of 0.347 (5) and 0.653 (5), respectively. Atom C49 of (II) is also split over two sites (C49 and C49'), with refined site occupancies of 0.48 (3) and 0.52 (3), respectively. The free THF molecule in (I) is refined as disordered over two positions, with site occupancies of 0.82 (3) and 0.19 (3). The geometries of the disordered groups were restrained and displacement parameters were either restrained to approximate isotropic behaviour or constrained to be equivalent for the atoms in the disordered parts. The crystal of (I) was refined as an inversion twin, with a refined twin ratio of 0.55 (1):0.45 (1).
For both compounds, data collection: CrystalClear (Rigaku, 2007); cell refinement: CrystalClear (Rigaku, 2007); data reduction: CrystalClear (Rigaku, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
Fig. 1. The molecular structure of (I), with the atom-numbering scheme.
Displacement ellipsoids are drawn at the 30% probability level. H atoms have
been omitted and only the major disorder component is shown for the solvent
THF molecule and disordered atom C51. Fig. 2. The molecular structure of (II), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted and only one disorder component is shown for disordered atoms C44, C45, C46 and C49. Fig. 3. The coordination geometry in (I) and (II). Dashed lines link atom La1 to the centres of the N—N bonds. Displacement ellipsoids are drawn at the 30% probability level. Fig. 4. The intramolecular C—H···N/O interactions (dashed lines) in (I). Fig. 5. The intramolecular C—H···N interactions (dashed lines) in (II). |
[La(C15H11N2)3(C4H8O)3]·C4H8O | F(000) = 2248 |
Mr = 1085.10 | Dx = 1.363 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 20820 reflections |
a = 14.146 (3) Å | θ = 2.6–29.1° |
b = 16.358 (3) Å | µ = 0.86 mm−1 |
c = 22.856 (5) Å | T = 173 K |
V = 5288.8 (18) Å3 | Prism, colourless |
Z = 4 | 0.20 × 0.20 × 0.20 mm |
Rigaku Saturn CCD area-detector diffractometer | 9592 independent reflections |
Radiation source: fine-focus sealed tube | 9280 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.031 |
ω scans | θmax = 25.4°, θmin = 3.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −14→17 |
Tmin = 0.811, Tmax = 1.000 | k = −17→19 |
22016 measured reflections | l = −23→27 |
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)] = 0.029 | H-atom parameters constrained |
wR(F2) = 0.054 | w = 1/[σ2(Fo2) + (0.0219P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max = 0.003 |
9592 reflections | Δρmax = 0.53 e Å−3 |
670 parameters | Δρmin = −0.34 e Å−3 |
76 restraints | Absolute structure: Flack (1983), with how many Friedel pairs? |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.450 (8) |
[La(C15H11N2)3(C4H8O)3]·C4H8O | V = 5288.8 (18) Å3 |
Mr = 1085.10 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 14.146 (3) Å | µ = 0.86 mm−1 |
b = 16.358 (3) Å | T = 173 K |
c = 22.856 (5) Å | 0.20 × 0.20 × 0.20 mm |
Rigaku Saturn CCD area-detector diffractometer | 9592 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 9280 reflections with I > 2σ(I) |
Tmin = 0.811, Tmax = 1.000 | Rint = 0.031 |
22016 measured reflections |
R[F2 > 2σ(F2)] = 0.029 | H-atom parameters constrained |
wR(F2) = 0.054 | Δρmax = 0.53 e Å−3 |
S = 1.03 | Δρmin = −0.34 e Å−3 |
9592 reflections | Absolute structure: Flack (1983), with how many Friedel pairs? |
670 parameters | Absolute structure parameter: 0.450 (8) |
76 restraints |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
C51 | 0.4821 (3) | 0.5595 (4) | 0.8603 (2) | 0.0457 (15) | 0.900 (12) |
H51A | 0.4477 | 0.5877 | 0.8284 | 0.055* | 0.900 (12) |
H51B | 0.4533 | 0.5051 | 0.8670 | 0.055* | 0.900 (12) |
C51' | 0.508 (3) | 0.5298 (11) | 0.886 (2) | 0.0457 (15) | 0.100 (12) |
H51C | 0.5278 | 0.4886 | 0.9154 | 0.055* | 0.100 (12) |
H51D | 0.4536 | 0.5081 | 0.8637 | 0.055* | 0.100 (12) |
O4 | 0.7878 (5) | 0.9162 (6) | 0.5183 (4) | 0.0403 (13) | 0.82 (3) |
C58 | 0.7538 (8) | 0.8655 (7) | 0.4719 (5) | 0.0460 (19) | 0.82 (3) |
H58A | 0.7187 | 0.8180 | 0.4876 | 0.055* | 0.82 (3) |
H58B | 0.8067 | 0.8455 | 0.4474 | 0.055* | 0.82 (3) |
C59 | 0.6893 (9) | 0.9205 (7) | 0.4370 (3) | 0.049 (2) | 0.82 (3) |
H59A | 0.6424 | 0.8883 | 0.4145 | 0.058* | 0.82 (3) |
H59B | 0.7256 | 0.9555 | 0.4097 | 0.058* | 0.82 (3) |
C60 | 0.6418 (6) | 0.9709 (8) | 0.4844 (3) | 0.061 (2) | 0.82 (3) |
H60A | 0.5795 | 0.9476 | 0.4949 | 0.073* | 0.82 (3) |
H60B | 0.6329 | 1.0282 | 0.4714 | 0.073* | 0.82 (3) |
C61 | 0.7098 (7) | 0.9665 (7) | 0.5358 (4) | 0.0378 (15) | 0.82 (3) |
H61A | 0.7323 | 1.0219 | 0.5463 | 0.045* | 0.82 (3) |
H61B | 0.6779 | 0.9424 | 0.5703 | 0.045* | 0.82 (3) |
O4' | 0.774 (2) | 0.915 (3) | 0.5306 (13) | 0.0403 (13) | 0.18 (3) |
C58' | 0.774 (4) | 0.868 (4) | 0.476 (2) | 0.0460 (19) | 0.18 (3) |
H58C | 0.7608 | 0.8092 | 0.4845 | 0.055* | 0.18 (3) |
H58D | 0.8368 | 0.8715 | 0.4571 | 0.055* | 0.18 (3) |
C59' | 0.699 (4) | 0.904 (4) | 0.4382 (15) | 0.049 (2) | 0.18 (3) |
H59C | 0.6684 | 0.8617 | 0.4135 | 0.058* | 0.18 (3) |
H59D | 0.7246 | 0.9475 | 0.4127 | 0.058* | 0.18 (3) |
C60' | 0.629 (2) | 0.939 (3) | 0.4823 (17) | 0.061 (2) | 0.18 (3) |
H60C | 0.5935 | 0.9857 | 0.4656 | 0.073* | 0.18 (3) |
H60D | 0.5829 | 0.8967 | 0.4952 | 0.073* | 0.18 (3) |
C61' | 0.690 (3) | 0.966 (4) | 0.532 (2) | 0.0378 (15) | 0.18 (3) |
H61C | 0.7077 | 1.0238 | 0.5271 | 0.045* | 0.18 (3) |
H61D | 0.6565 | 0.9591 | 0.5694 | 0.045* | 0.18 (3) |
La1 | 0.785393 (12) | 0.697118 (9) | 0.830200 (6) | 0.01865 (5) | |
O1 | 0.76950 (16) | 0.56576 (11) | 0.76309 (8) | 0.0276 (5) | |
O2 | 0.62490 (14) | 0.63184 (12) | 0.86200 (9) | 0.0290 (5) | |
O3 | 0.92245 (14) | 0.79929 (12) | 0.84184 (8) | 0.0314 (5) | |
N1 | 0.80336 (16) | 0.75407 (13) | 0.72821 (9) | 0.0222 (6) | |
N2 | 0.70749 (18) | 0.75172 (13) | 0.73548 (9) | 0.0214 (5) | |
N3 | 0.70585 (17) | 0.81251 (13) | 0.88287 (9) | 0.0218 (5) | |
N4 | 0.75078 (16) | 0.76888 (13) | 0.92572 (9) | 0.0226 (6) | |
N5 | 0.86087 (17) | 0.58898 (14) | 0.89163 (10) | 0.0225 (5) | |
N6 | 0.92837 (17) | 0.60699 (14) | 0.85064 (10) | 0.0204 (6) | |
C1 | 0.9965 (2) | 0.79272 (18) | 0.68646 (12) | 0.0277 (7) | |
H1 | 0.9872 | 0.7971 | 0.7275 | 0.033* | |
C2 | 1.0870 (2) | 0.79866 (18) | 0.66337 (13) | 0.0308 (7) | |
H2 | 1.1391 | 0.8077 | 0.6888 | 0.037* | |
C3 | 1.1023 (2) | 0.7916 (2) | 0.60413 (13) | 0.0317 (7) | |
H3 | 1.1645 | 0.7961 | 0.5887 | 0.038* | |
C4 | 1.0265 (2) | 0.77800 (18) | 0.56721 (13) | 0.0321 (8) | |
H4 | 1.0369 | 0.7721 | 0.5264 | 0.039* | |
C5 | 0.9358 (2) | 0.77299 (17) | 0.58939 (13) | 0.0274 (7) | |
H5 | 0.8841 | 0.7645 | 0.5636 | 0.033* | |
C6 | 0.9194 (2) | 0.78037 (16) | 0.64970 (12) | 0.0232 (7) | |
C7 | 0.82176 (19) | 0.77513 (15) | 0.67219 (13) | 0.0201 (6) | |
C8 | 0.73724 (19) | 0.78759 (16) | 0.64280 (11) | 0.0222 (7) | |
H8 | 0.7291 | 0.8032 | 0.6031 | 0.027* | |
C9 | 0.6669 (2) | 0.77233 (16) | 0.68384 (11) | 0.0218 (7) | |
C10 | 0.5641 (2) | 0.77465 (15) | 0.67565 (13) | 0.0223 (6) | |
C11 | 0.5247 (2) | 0.8027 (2) | 0.62339 (13) | 0.0333 (7) | |
H11 | 0.5654 | 0.8217 | 0.5932 | 0.040* | |
C12 | 0.4281 (2) | 0.8035 (3) | 0.61433 (15) | 0.0448 (9) | |
H12 | 0.4031 | 0.8237 | 0.5786 | 0.054* | |
C13 | 0.3684 (2) | 0.7752 (2) | 0.65695 (15) | 0.0435 (9) | |
H13 | 0.3021 | 0.7749 | 0.6506 | 0.052* | |
C14 | 0.4052 (2) | 0.7469 (2) | 0.70936 (14) | 0.0369 (8) | |
H14 | 0.3636 | 0.7271 | 0.7388 | 0.044* | |
C15 | 0.5015 (2) | 0.74710 (18) | 0.71936 (13) | 0.0287 (7) | |
H15 | 0.5256 | 0.7286 | 0.7558 | 0.034* | |
C16 | 0.5753 (2) | 0.91037 (17) | 0.81623 (12) | 0.0224 (7) | |
H16 | 0.5949 | 0.8597 | 0.8000 | 0.027* | |
C17 | 0.5239 (2) | 0.96445 (18) | 0.78249 (14) | 0.0313 (8) | |
H17 | 0.5076 | 0.9506 | 0.7434 | 0.038* | |
C18 | 0.4960 (2) | 1.03875 (19) | 0.80557 (14) | 0.0339 (8) | |
H18 | 0.4611 | 1.0762 | 0.7823 | 0.041* | |
C19 | 0.5193 (3) | 1.05850 (19) | 0.86273 (15) | 0.0357 (9) | |
H19 | 0.5008 | 1.1097 | 0.8786 | 0.043* | |
C20 | 0.5692 (2) | 1.00383 (18) | 0.89661 (13) | 0.0292 (7) | |
H20 | 0.5836 | 1.0173 | 0.9360 | 0.035* | |
C21 | 0.5989 (2) | 0.92927 (17) | 0.87392 (12) | 0.0220 (7) | |
C22 | 0.6536 (2) | 0.87119 (16) | 0.90934 (12) | 0.0215 (6) | |
C23 | 0.6644 (2) | 0.86571 (17) | 0.96946 (12) | 0.0237 (7) | |
H23 | 0.6360 | 0.8994 | 0.9984 | 0.028* | |
C24 | 0.7258 (2) | 0.80041 (17) | 0.97836 (10) | 0.0217 (6) | |
C25 | 0.7645 (2) | 0.76662 (16) | 1.03296 (11) | 0.0222 (7) | |
C26 | 0.7370 (2) | 0.79762 (19) | 1.08712 (11) | 0.0277 (7) | |
H26 | 0.6910 | 0.8398 | 1.0890 | 0.033* | |
C27 | 0.7762 (2) | 0.76741 (18) | 1.13811 (12) | 0.0332 (7) | |
H27 | 0.7571 | 0.7893 | 1.1748 | 0.040* | |
C28 | 0.8431 (2) | 0.7055 (2) | 1.13635 (12) | 0.0337 (7) | |
H28 | 0.8704 | 0.6853 | 1.1715 | 0.040* | |
C29 | 0.8697 (2) | 0.67349 (18) | 1.08276 (13) | 0.0319 (8) | |
H29 | 0.9145 | 0.6303 | 1.0811 | 0.038* | |
C30 | 0.8315 (2) | 0.70402 (19) | 1.03171 (12) | 0.0294 (7) | |
H30 | 0.8512 | 0.6821 | 0.9952 | 0.035* | |
C31 | 0.7372 (2) | 0.5109 (2) | 0.97492 (14) | 0.0354 (9) | |
H31 | 0.7121 | 0.5522 | 0.9501 | 0.042* | |
C32 | 0.6780 (2) | 0.4714 (2) | 1.01429 (14) | 0.0402 (9) | |
H32 | 0.6132 | 0.4862 | 1.0166 | 0.048* | |
C33 | 0.7129 (3) | 0.41100 (19) | 1.04996 (13) | 0.0378 (8) | |
H33 | 0.6718 | 0.3825 | 1.0757 | 0.045* | |
C34 | 0.8074 (3) | 0.3919 (2) | 1.04828 (14) | 0.0404 (9) | |
H34 | 0.8320 | 0.3511 | 1.0736 | 0.048* | |
C35 | 0.8671 (3) | 0.43231 (18) | 1.00952 (13) | 0.0336 (8) | |
H35 | 0.9326 | 0.4194 | 1.0093 | 0.040* | |
C36 | 0.8330 (2) | 0.49096 (17) | 0.97126 (12) | 0.0220 (7) | |
C37 | 0.8930 (2) | 0.52735 (16) | 0.92581 (12) | 0.0221 (7) | |
C38 | 0.9827 (2) | 0.50520 (17) | 0.90712 (12) | 0.0235 (7) | |
H38 | 1.0224 | 0.4643 | 0.9234 | 0.028* | |
C39 | 1.0026 (2) | 0.55600 (17) | 0.85902 (13) | 0.0231 (7) | |
C40 | 1.0836 (2) | 0.55542 (16) | 0.81899 (12) | 0.0231 (7) | |
C41 | 1.1576 (2) | 0.49997 (16) | 0.82650 (14) | 0.0271 (7) | |
H41 | 1.1564 | 0.4635 | 0.8588 | 0.032* | |
C42 | 1.2322 (2) | 0.49735 (19) | 0.78776 (14) | 0.0333 (8) | |
H42 | 1.2819 | 0.4592 | 0.7936 | 0.040* | |
C43 | 1.2353 (2) | 0.55001 (18) | 0.74034 (13) | 0.0328 (8) | |
H43 | 1.2868 | 0.5483 | 0.7137 | 0.039* | |
C44 | 1.1625 (2) | 0.6048 (2) | 0.73240 (14) | 0.0335 (8) | |
H44 | 1.1638 | 0.6410 | 0.6999 | 0.040* | |
C45 | 1.0876 (2) | 0.60778 (19) | 0.77117 (13) | 0.0293 (7) | |
H45 | 1.0382 | 0.6462 | 0.7651 | 0.035* | |
C46 | 0.8014 (3) | 0.48449 (17) | 0.77923 (13) | 0.0360 (9) | |
H46A | 0.7813 | 0.4706 | 0.8195 | 0.043* | |
H46B | 0.8711 | 0.4803 | 0.7767 | 0.043* | |
C47 | 0.7547 (3) | 0.42933 (19) | 0.73541 (13) | 0.0402 (9) | |
H47A | 0.6913 | 0.4123 | 0.7491 | 0.048* | |
H47B | 0.7935 | 0.3800 | 0.7283 | 0.048* | |
C48 | 0.7472 (2) | 0.48106 (17) | 0.68051 (12) | 0.0333 (8) | |
H48A | 0.6820 | 0.4802 | 0.6649 | 0.040* | |
H48B | 0.7910 | 0.4610 | 0.6499 | 0.040* | |
C49 | 0.7744 (3) | 0.56677 (17) | 0.70008 (12) | 0.0342 (8) | |
H49A | 0.8392 | 0.5804 | 0.6869 | 0.041* | |
H49B | 0.7300 | 0.6076 | 0.6838 | 0.041* | |
C50 | 0.5876 (2) | 0.5524 (2) | 0.84674 (15) | 0.0413 (9) | |
H50A | 0.6174 | 0.5089 | 0.8706 | 0.050* | |
H50B | 0.5982 | 0.5403 | 0.8048 | 0.050* | |
C52 | 0.4830 (3) | 0.6096 (2) | 0.91524 (15) | 0.0445 (9) | |
H52A | 0.5016 | 0.5766 | 0.9496 | 0.053* | |
H52B | 0.4208 | 0.6353 | 0.9227 | 0.053* | |
C53 | 0.5569 (2) | 0.6722 (2) | 0.90024 (17) | 0.0475 (10) | |
H53A | 0.5277 | 0.7194 | 0.8800 | 0.057* | |
H53B | 0.5884 | 0.6921 | 0.9362 | 0.057* | |
C54 | 0.9082 (2) | 0.88662 (17) | 0.83397 (16) | 0.0386 (7) | |
H54A | 0.8557 | 0.9065 | 0.8589 | 0.046* | |
H54B | 0.8937 | 0.8995 | 0.7926 | 0.046* | |
C55 | 1.0010 (3) | 0.9248 (2) | 0.85231 (16) | 0.0508 (9) | |
H55A | 0.9917 | 0.9809 | 0.8674 | 0.061* | |
H55B | 1.0465 | 0.9262 | 0.8194 | 0.061* | |
C56 | 1.0343 (3) | 0.8677 (2) | 0.90017 (18) | 0.0580 (10) | |
H56A | 1.1042 | 0.8673 | 0.9025 | 0.070* | |
H56B | 1.0084 | 0.8845 | 0.9386 | 0.070* | |
C57 | 0.9984 (3) | 0.7874 (2) | 0.88324 (15) | 0.0497 (8) | |
H57A | 1.0496 | 0.7547 | 0.8652 | 0.060* | |
H57B | 0.9750 | 0.7578 | 0.9181 | 0.060* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C51 | 0.033 (2) | 0.061 (3) | 0.042 (3) | −0.020 (2) | 0.007 (2) | −0.006 (3) |
C51' | 0.033 (2) | 0.061 (3) | 0.042 (3) | −0.020 (2) | 0.007 (2) | −0.006 (3) |
O4 | 0.040 (3) | 0.0516 (14) | 0.029 (3) | 0.010 (2) | 0.007 (2) | −0.002 (3) |
C58 | 0.059 (5) | 0.041 (2) | 0.038 (3) | −0.003 (3) | 0.003 (3) | −0.002 (2) |
C59 | 0.064 (4) | 0.049 (6) | 0.0322 (19) | −0.001 (3) | −0.005 (2) | −0.003 (2) |
C60 | 0.050 (3) | 0.078 (5) | 0.054 (3) | 0.013 (4) | −0.006 (3) | −0.020 (4) |
C61 | 0.039 (4) | 0.0407 (18) | 0.034 (2) | −0.001 (4) | 0.002 (3) | 0.0014 (17) |
O4' | 0.040 (3) | 0.0516 (14) | 0.029 (3) | 0.010 (2) | 0.007 (2) | −0.002 (3) |
C58' | 0.059 (5) | 0.041 (2) | 0.038 (3) | −0.003 (3) | 0.003 (3) | −0.002 (2) |
C59' | 0.064 (4) | 0.049 (6) | 0.0322 (19) | −0.001 (3) | −0.005 (2) | −0.003 (2) |
C60' | 0.050 (3) | 0.078 (5) | 0.054 (3) | 0.013 (4) | −0.006 (3) | −0.020 (4) |
C61' | 0.039 (4) | 0.0407 (18) | 0.034 (2) | −0.001 (4) | 0.002 (3) | 0.0014 (17) |
La1 | 0.01842 (8) | 0.02096 (7) | 0.01658 (7) | 0.00280 (8) | −0.00025 (7) | 0.00084 (7) |
O1 | 0.0359 (14) | 0.0258 (10) | 0.0210 (10) | 0.0044 (10) | −0.0012 (10) | −0.0007 (8) |
O2 | 0.0210 (12) | 0.0304 (11) | 0.0357 (12) | −0.0032 (10) | 0.0035 (10) | −0.0045 (10) |
O3 | 0.0271 (11) | 0.0266 (8) | 0.0406 (12) | −0.0022 (10) | −0.0063 (9) | −0.0008 (11) |
N1 | 0.0197 (15) | 0.0242 (12) | 0.0227 (12) | 0.0008 (11) | −0.0007 (11) | 0.0004 (10) |
N2 | 0.0179 (13) | 0.0234 (12) | 0.0228 (12) | −0.0007 (12) | −0.0006 (12) | 0.0019 (10) |
N3 | 0.0205 (13) | 0.0252 (12) | 0.0198 (11) | 0.0019 (13) | 0.0001 (10) | 0.0004 (10) |
N4 | 0.0241 (14) | 0.0247 (12) | 0.0190 (12) | 0.0043 (10) | −0.0027 (10) | 0.0002 (10) |
N5 | 0.0227 (14) | 0.0236 (13) | 0.0211 (12) | 0.0008 (11) | 0.0004 (11) | 0.0021 (11) |
N6 | 0.0183 (13) | 0.0232 (12) | 0.0196 (12) | 0.0015 (11) | −0.0006 (10) | 0.0034 (11) |
C1 | 0.0275 (17) | 0.0285 (16) | 0.0271 (16) | −0.0011 (15) | −0.0019 (13) | 0.0007 (14) |
C2 | 0.0215 (15) | 0.0321 (15) | 0.0389 (17) | 0.0002 (14) | −0.0010 (14) | −0.0016 (19) |
C3 | 0.0217 (17) | 0.0334 (18) | 0.0400 (18) | 0.0015 (15) | 0.0077 (14) | 0.0034 (16) |
C4 | 0.0335 (19) | 0.0354 (18) | 0.0274 (17) | 0.0024 (15) | 0.0056 (15) | 0.0000 (15) |
C5 | 0.0245 (18) | 0.0300 (17) | 0.0276 (16) | −0.0017 (14) | −0.0004 (14) | 0.0021 (14) |
C6 | 0.0263 (17) | 0.0177 (15) | 0.0254 (15) | 0.0009 (12) | 0.0002 (13) | 0.0015 (12) |
C7 | 0.0250 (15) | 0.0172 (13) | 0.0181 (13) | −0.0014 (11) | 0.0001 (14) | 0.0029 (13) |
C8 | 0.0238 (17) | 0.0248 (16) | 0.0179 (13) | −0.0011 (13) | −0.0015 (12) | 0.0020 (13) |
C9 | 0.0255 (17) | 0.0175 (13) | 0.0223 (16) | 0.0015 (12) | −0.0035 (13) | 0.0005 (12) |
C10 | 0.0248 (16) | 0.0181 (13) | 0.0239 (15) | 0.0000 (12) | −0.0007 (14) | −0.0046 (13) |
C11 | 0.0239 (17) | 0.0397 (17) | 0.0362 (17) | 0.0000 (18) | −0.0042 (14) | 0.0048 (19) |
C12 | 0.034 (2) | 0.058 (2) | 0.0422 (19) | 0.003 (2) | −0.0127 (17) | 0.005 (2) |
C13 | 0.0192 (18) | 0.062 (2) | 0.050 (2) | 0.0043 (16) | −0.0030 (16) | −0.0173 (19) |
C14 | 0.0258 (19) | 0.050 (2) | 0.0343 (19) | −0.0052 (17) | 0.0053 (16) | −0.0153 (17) |
C15 | 0.0280 (19) | 0.0299 (16) | 0.0283 (17) | −0.0025 (15) | 0.0009 (14) | −0.0086 (14) |
C16 | 0.0220 (16) | 0.0191 (14) | 0.0261 (16) | 0.0007 (13) | −0.0007 (13) | 0.0027 (13) |
C17 | 0.0291 (19) | 0.0320 (17) | 0.0327 (18) | −0.0006 (15) | −0.0063 (15) | 0.0029 (15) |
C18 | 0.034 (2) | 0.0295 (17) | 0.0382 (19) | 0.0036 (16) | −0.0047 (16) | 0.0117 (16) |
C19 | 0.040 (2) | 0.0238 (17) | 0.043 (2) | 0.0080 (16) | 0.0028 (18) | 0.0032 (16) |
C20 | 0.0322 (19) | 0.0281 (17) | 0.0273 (16) | 0.0045 (15) | 0.0030 (15) | −0.0051 (14) |
C21 | 0.0161 (16) | 0.0246 (16) | 0.0255 (16) | −0.0005 (13) | 0.0045 (13) | 0.0012 (13) |
C22 | 0.0214 (16) | 0.0180 (14) | 0.0250 (15) | 0.0013 (13) | −0.0015 (13) | −0.0023 (13) |
C23 | 0.0238 (17) | 0.0253 (15) | 0.0220 (15) | 0.0019 (13) | −0.0019 (13) | −0.0042 (13) |
C24 | 0.0211 (15) | 0.0235 (13) | 0.0205 (13) | 0.0014 (16) | 0.0005 (12) | −0.0037 (13) |
C25 | 0.0259 (18) | 0.0200 (14) | 0.0205 (14) | −0.0022 (13) | −0.0028 (13) | −0.0019 (12) |
C26 | 0.0278 (17) | 0.0333 (16) | 0.0221 (14) | −0.0003 (15) | 0.0012 (12) | −0.0029 (15) |
C27 | 0.036 (2) | 0.0422 (17) | 0.0209 (14) | −0.0041 (17) | −0.0001 (16) | −0.0042 (14) |
C28 | 0.042 (2) | 0.0367 (18) | 0.0227 (15) | −0.0043 (18) | −0.0083 (14) | 0.0062 (16) |
C29 | 0.036 (2) | 0.0297 (18) | 0.0301 (17) | 0.0007 (14) | −0.0077 (15) | 0.0029 (14) |
C30 | 0.0370 (18) | 0.0305 (16) | 0.0207 (14) | 0.0006 (16) | −0.0018 (13) | −0.0025 (15) |
C31 | 0.033 (2) | 0.0396 (19) | 0.0333 (18) | −0.0023 (16) | 0.0027 (16) | 0.0104 (16) |
C32 | 0.034 (2) | 0.051 (2) | 0.0357 (19) | −0.0033 (17) | 0.0047 (16) | 0.0052 (18) |
C33 | 0.048 (2) | 0.0393 (18) | 0.0260 (16) | −0.015 (2) | 0.0080 (19) | −0.0014 (15) |
C34 | 0.061 (3) | 0.0327 (18) | 0.0279 (17) | 0.0013 (18) | 0.0041 (17) | 0.0099 (15) |
C35 | 0.040 (2) | 0.0357 (18) | 0.0251 (17) | 0.0104 (16) | 0.0016 (16) | 0.0069 (15) |
C36 | 0.0257 (18) | 0.0224 (15) | 0.0181 (15) | −0.0007 (13) | 0.0001 (13) | −0.0044 (13) |
C37 | 0.0249 (17) | 0.0189 (14) | 0.0226 (15) | 0.0008 (13) | −0.0031 (13) | −0.0002 (13) |
C38 | 0.0256 (17) | 0.0237 (15) | 0.0212 (15) | 0.0044 (13) | −0.0010 (13) | 0.0029 (13) |
C39 | 0.0243 (18) | 0.0220 (15) | 0.0231 (16) | 0.0036 (13) | −0.0063 (14) | −0.0009 (13) |
C40 | 0.0199 (16) | 0.0214 (14) | 0.0279 (17) | 0.0017 (12) | −0.0007 (13) | −0.0036 (13) |
C41 | 0.0275 (17) | 0.0250 (14) | 0.0287 (16) | 0.0047 (13) | −0.0033 (16) | 0.0025 (15) |
C42 | 0.025 (2) | 0.0324 (16) | 0.0427 (19) | 0.0076 (15) | 0.0000 (16) | 0.0003 (15) |
C43 | 0.028 (2) | 0.0356 (18) | 0.0345 (18) | 0.0021 (15) | 0.0070 (15) | −0.0083 (15) |
C44 | 0.032 (2) | 0.0359 (18) | 0.0324 (18) | 0.0035 (16) | 0.0039 (16) | 0.0056 (15) |
C45 | 0.0271 (18) | 0.0316 (17) | 0.0291 (17) | 0.0096 (15) | 0.0035 (14) | 0.0060 (15) |
C46 | 0.053 (3) | 0.0236 (15) | 0.0315 (17) | 0.0112 (17) | −0.0095 (17) | −0.0009 (14) |
C47 | 0.053 (3) | 0.0329 (18) | 0.0341 (18) | −0.0016 (16) | −0.0087 (16) | −0.0014 (15) |
C48 | 0.041 (2) | 0.0318 (16) | 0.0267 (17) | 0.0027 (14) | −0.0013 (14) | −0.0069 (14) |
C49 | 0.049 (2) | 0.0326 (16) | 0.0210 (15) | −0.0006 (17) | −0.0022 (17) | 0.0002 (13) |
C50 | 0.044 (2) | 0.045 (2) | 0.035 (2) | −0.0159 (18) | 0.0084 (17) | −0.0147 (17) |
C52 | 0.034 (2) | 0.043 (2) | 0.057 (2) | −0.0055 (17) | 0.0098 (19) | −0.0009 (19) |
C53 | 0.028 (2) | 0.047 (2) | 0.068 (3) | −0.0027 (16) | 0.0152 (18) | −0.0120 (19) |
C54 | 0.0399 (10) | 0.0325 (8) | 0.0434 (11) | 0.0022 (8) | 0.0011 (9) | 0.0025 (9) |
C55 | 0.0489 (11) | 0.0494 (12) | 0.0542 (13) | −0.0050 (9) | −0.0013 (9) | −0.0004 (9) |
C56 | 0.0588 (13) | 0.0554 (11) | 0.0597 (13) | −0.0036 (9) | −0.0051 (10) | −0.0033 (9) |
C57 | 0.0470 (11) | 0.0512 (11) | 0.0508 (11) | 0.0008 (9) | −0.0162 (8) | 0.0018 (9) |
C51—C52 | 1.500 (5) | C15—H15 | 0.9500 |
C51—C50 | 1.529 (5) | C16—C17 | 1.381 (4) |
C51—H51A | 0.9900 | C16—C21 | 1.395 (4) |
C51—H51B | 0.9900 | C16—H16 | 0.9500 |
C51'—C50 | 1.492 (10) | C17—C18 | 1.382 (4) |
C51'—C52 | 1.505 (10) | C17—H17 | 0.9500 |
C51'—H51C | 0.9900 | C18—C19 | 1.385 (4) |
C51'—H51D | 0.9900 | C18—H18 | 0.9500 |
O4—C58 | 1.430 (7) | C19—C20 | 1.378 (4) |
O4—C61 | 1.434 (6) | C19—H19 | 0.9500 |
C58—C59 | 1.509 (8) | C20—C21 | 1.390 (4) |
C58—H58A | 0.9900 | C20—H20 | 0.9500 |
C58—H58B | 0.9900 | C21—C22 | 1.469 (4) |
C59—C60 | 1.519 (6) | C22—C23 | 1.386 (4) |
C59—H59A | 0.9900 | C23—C24 | 1.391 (4) |
C59—H59B | 0.9900 | C23—H23 | 0.9500 |
C60—C61 | 1.521 (7) | C24—C25 | 1.470 (4) |
C60—H60A | 0.9900 | C25—C26 | 1.393 (4) |
C60—H60B | 0.9900 | C25—C30 | 1.396 (4) |
C61—H61A | 0.9900 | C26—C27 | 1.382 (4) |
C61—H61B | 0.9900 | C26—H26 | 0.9500 |
O4'—C61' | 1.450 (18) | C27—C28 | 1.387 (4) |
O4'—C58' | 1.457 (18) | C27—H27 | 0.9500 |
C58'—C59' | 1.507 (19) | C28—C29 | 1.384 (4) |
C58'—H58C | 0.9900 | C28—H28 | 0.9500 |
C58'—H58D | 0.9900 | C29—C30 | 1.379 (4) |
C59'—C60' | 1.52 (2) | C29—H29 | 0.9500 |
C59'—H59C | 0.9900 | C30—H30 | 0.9500 |
C59'—H59D | 0.9900 | C31—C32 | 1.388 (4) |
C60'—C61' | 1.491 (19) | C31—C36 | 1.397 (4) |
C60'—H60C | 0.9900 | C31—H31 | 0.9500 |
C60'—H60D | 0.9900 | C32—C33 | 1.373 (4) |
C61'—H61C | 0.9900 | C32—H32 | 0.9500 |
C61'—H61D | 0.9900 | C33—C34 | 1.372 (5) |
La1—N1 | 2.523 (2) | C33—H33 | 0.9500 |
La1—N2 | 2.588 (2) | C34—C35 | 1.391 (4) |
La1—N3 | 2.506 (2) | C34—H34 | 0.9500 |
La1—N4 | 2.527 (2) | C35—C36 | 1.385 (4) |
La1—N5 | 2.498 (2) | C35—H35 | 0.9500 |
La1—N6 | 2.546 (2) | C36—C37 | 1.468 (4) |
La1—O1 | 2.6496 (19) | C37—C38 | 1.386 (4) |
La1—O2 | 2.612 (2) | C38—C39 | 1.407 (4) |
La1—O3 | 2.573 (2) | C38—H38 | 0.9500 |
O1—C49 | 1.442 (3) | C39—C40 | 1.467 (4) |
O1—C46 | 1.451 (3) | C40—C45 | 1.390 (4) |
O2—C50 | 1.445 (3) | C40—C41 | 1.395 (4) |
O2—C53 | 1.458 (4) | C41—C42 | 1.379 (4) |
O3—C57 | 1.445 (4) | C41—H41 | 0.9500 |
O3—C54 | 1.454 (3) | C42—C43 | 1.385 (4) |
N1—C7 | 1.351 (3) | C42—H42 | 0.9500 |
N1—N2 | 1.367 (3) | C43—C44 | 1.378 (4) |
N2—C9 | 1.355 (3) | C43—H43 | 0.9500 |
N3—C22 | 1.354 (3) | C44—C45 | 1.381 (4) |
N3—N4 | 1.368 (3) | C44—H44 | 0.9500 |
N4—C24 | 1.356 (3) | C45—H45 | 0.9500 |
N5—C37 | 1.354 (3) | C46—C47 | 1.501 (4) |
N5—N6 | 1.370 (3) | C46—H46A | 0.9900 |
N6—C39 | 1.355 (4) | C46—H46B | 0.9900 |
C1—C2 | 1.388 (4) | C47—C48 | 1.517 (4) |
C1—C6 | 1.392 (4) | C47—H47A | 0.9900 |
C1—H1 | 0.9500 | C47—H47B | 0.9900 |
C2—C3 | 1.376 (4) | C48—C49 | 1.521 (4) |
C2—H2 | 0.9500 | C48—H48A | 0.9900 |
C3—C4 | 1.383 (4) | C48—H48B | 0.9900 |
C3—H3 | 0.9500 | C49—H49A | 0.9900 |
C4—C5 | 1.382 (4) | C49—H49B | 0.9900 |
C4—H4 | 0.9500 | C50—H50A | 0.9900 |
C5—C6 | 1.403 (4) | C50—H50B | 0.9900 |
C5—H5 | 0.9500 | C52—C53 | 1.503 (4) |
C6—C7 | 1.476 (4) | C52—H52A | 0.9900 |
C7—C8 | 1.386 (4) | C52—H52B | 0.9900 |
C8—C9 | 1.390 (4) | C53—H53A | 0.9900 |
C8—H8 | 0.9500 | C53—H53B | 0.9900 |
C9—C10 | 1.467 (4) | C54—C55 | 1.513 (5) |
C10—C11 | 1.396 (4) | C54—H54A | 0.9900 |
C10—C15 | 1.409 (4) | C54—H54B | 0.9900 |
C11—C12 | 1.382 (4) | C55—C56 | 1.513 (5) |
C11—H11 | 0.9500 | C55—H55A | 0.9900 |
C12—C13 | 1.370 (4) | C55—H55B | 0.9900 |
C12—H12 | 0.9500 | C56—C57 | 1.460 (5) |
C13—C14 | 1.385 (4) | C56—H56A | 0.9900 |
C13—H13 | 0.9500 | C56—H56B | 0.9900 |
C14—C15 | 1.382 (4) | C57—H57A | 0.9900 |
C14—H14 | 0.9500 | C57—H57B | 0.9900 |
C52—C51—C50 | 101.7 (3) | C15—C14—H14 | 119.6 |
C52—C51—H51A | 111.4 | C13—C14—H14 | 119.6 |
C50—C51—H51A | 111.4 | C14—C15—C10 | 120.2 (3) |
C52—C51—H51B | 111.4 | C14—C15—H15 | 119.9 |
C50—C51—H51B | 111.4 | C10—C15—H15 | 119.9 |
H51A—C51—H51B | 109.3 | C17—C16—C21 | 120.8 (3) |
C50—C51'—C52 | 103.2 (8) | C17—C16—H16 | 119.6 |
C50—C51'—H51C | 111.1 | C21—C16—H16 | 119.6 |
C52—C51'—H51C | 111.1 | C16—C17—C18 | 120.0 (3) |
C50—C51'—H51D | 111.1 | C16—C17—H17 | 120.0 |
C52—C51'—H51D | 111.1 | C18—C17—H17 | 120.0 |
H51C—C51'—H51D | 109.1 | C17—C18—C19 | 119.8 (3) |
C58—O4—C61 | 106.3 (5) | C17—C18—H18 | 120.1 |
O4—C58—C59 | 104.5 (6) | C19—C18—H18 | 120.1 |
O4—C58—H58A | 110.8 | C20—C19—C18 | 120.0 (3) |
C59—C58—H58A | 110.8 | C20—C19—H19 | 120.0 |
O4—C58—H58B | 110.8 | C18—C19—H19 | 120.0 |
C59—C58—H58B | 110.8 | C19—C20—C21 | 121.0 (3) |
H58A—C58—H58B | 108.9 | C19—C20—H20 | 119.5 |
C58—C59—C60 | 102.3 (4) | C21—C20—H20 | 119.5 |
C58—C59—H59A | 111.3 | C20—C21—C16 | 118.4 (3) |
C60—C59—H59A | 111.3 | C20—C21—C22 | 121.4 (3) |
C58—C59—H59B | 111.3 | C16—C21—C22 | 120.2 (3) |
C60—C59—H59B | 111.3 | N3—C22—C23 | 109.7 (2) |
H59A—C59—H59B | 109.2 | N3—C22—C21 | 120.0 (2) |
C59—C60—C61 | 104.2 (4) | C23—C22—C21 | 130.3 (3) |
C59—C60—H60A | 110.9 | C22—C23—C24 | 105.3 (2) |
C61—C60—H60A | 110.9 | C22—C23—H23 | 127.4 |
C59—C60—H60B | 110.9 | C24—C23—H23 | 127.4 |
C61—C60—H60B | 110.9 | N4—C24—C23 | 109.0 (2) |
H60A—C60—H60B | 108.9 | N4—C24—C25 | 120.9 (2) |
O4—C61—C60 | 107.4 (4) | C23—C24—C25 | 130.1 (2) |
O4—C61—H61A | 110.2 | C26—C25—C30 | 118.3 (3) |
C60—C61—H61A | 110.2 | C26—C25—C24 | 120.9 (2) |
O4—C61—H61B | 110.2 | C30—C25—C24 | 120.7 (2) |
C60—C61—H61B | 110.2 | C27—C26—C25 | 120.5 (3) |
H61A—C61—H61B | 108.5 | C27—C26—H26 | 119.8 |
C61'—O4'—C58' | 108.9 (11) | C25—C26—H26 | 119.8 |
O4'—C58'—C59' | 106.3 (13) | C26—C27—C28 | 120.7 (3) |
O4'—C58'—H58C | 110.5 | C26—C27—H27 | 119.7 |
C59'—C58'—H58C | 110.5 | C28—C27—H27 | 119.7 |
O4'—C58'—H58D | 110.5 | C29—C28—C27 | 119.2 (3) |
C59'—C58'—H58D | 110.5 | C29—C28—H28 | 120.4 |
H58C—C58'—H58D | 108.7 | C27—C28—H28 | 120.4 |
C58'—C59'—C60' | 103.1 (15) | C30—C29—C28 | 120.3 (3) |
C58'—C59'—H59C | 111.1 | C30—C29—H29 | 119.8 |
C60'—C59'—H59C | 111.1 | C28—C29—H29 | 119.8 |
C58'—C59'—H59D | 111.1 | C29—C30—C25 | 121.0 (3) |
C60'—C59'—H59D | 111.1 | C29—C30—H30 | 119.5 |
H59C—C59'—H59D | 109.1 | C25—C30—H30 | 119.5 |
C61'—C60'—C59' | 103.5 (15) | C32—C31—C36 | 121.0 (3) |
C61'—C60'—H60C | 111.1 | C32—C31—H31 | 119.5 |
C59'—C60'—H60C | 111.1 | C36—C31—H31 | 119.5 |
C61'—C60'—H60D | 111.1 | C33—C32—C31 | 120.2 (3) |
C59'—C60'—H60D | 111.1 | C33—C32—H32 | 119.9 |
H60C—C60'—H60D | 109.0 | C31—C32—H32 | 119.9 |
O4'—C61'—C60' | 107.1 (13) | C34—C33—C32 | 119.8 (3) |
O4'—C61'—H61C | 110.3 | C34—C33—H33 | 120.1 |
C60'—C61'—H61C | 110.3 | C32—C33—H33 | 120.1 |
O4'—C61'—H61D | 110.3 | C33—C34—C35 | 120.1 (3) |
C60'—C61'—H61D | 110.3 | C33—C34—H34 | 120.0 |
H61C—C61'—H61D | 108.5 | C35—C34—H34 | 120.0 |
N5—La1—N3 | 117.09 (7) | C36—C35—C34 | 121.3 (3) |
N5—La1—N1 | 137.53 (7) | C36—C35—H35 | 119.4 |
N3—La1—N1 | 102.18 (7) | C34—C35—H35 | 119.4 |
N5—La1—N4 | 85.76 (7) | C35—C36—C31 | 117.6 (3) |
N3—La1—N4 | 31.55 (6) | C35—C36—C37 | 121.7 (3) |
N1—La1—N4 | 130.26 (7) | C31—C36—C37 | 120.6 (3) |
N5—La1—N6 | 31.49 (7) | N5—C37—C38 | 108.9 (2) |
N3—La1—N6 | 134.81 (7) | N5—C37—C36 | 121.0 (3) |
N1—La1—N6 | 107.66 (7) | C38—C37—C36 | 129.9 (3) |
N4—La1—N6 | 105.33 (7) | C37—C38—C39 | 105.6 (3) |
N5—La1—O3 | 94.57 (7) | C37—C38—H38 | 127.2 |
N3—La1—O3 | 78.43 (7) | C39—C38—H38 | 127.2 |
N1—La1—O3 | 77.28 (7) | N6—C39—C38 | 108.6 (3) |
N4—La1—O3 | 75.82 (7) | N6—C39—C40 | 121.4 (2) |
N6—La1—O3 | 76.03 (7) | C38—C39—C40 | 129.8 (3) |
N5—La1—N2 | 153.70 (7) | C45—C40—C41 | 117.8 (3) |
N3—La1—N2 | 87.17 (7) | C45—C40—C39 | 121.2 (3) |
N1—La1—N2 | 30.99 (7) | C41—C40—C39 | 120.9 (3) |
N4—La1—N2 | 118.68 (7) | C42—C41—C40 | 121.0 (3) |
N6—La1—N2 | 133.75 (7) | C42—C41—H41 | 119.5 |
O3—La1—N2 | 100.55 (7) | C40—C41—H41 | 119.5 |
N5—La1—O2 | 85.73 (7) | C41—C42—C43 | 120.5 (3) |
N3—La1—O2 | 77.53 (7) | C41—C42—H42 | 119.8 |
N1—La1—O2 | 119.71 (7) | C43—C42—H42 | 119.8 |
N4—La1—O2 | 77.35 (7) | C44—C43—C42 | 119.0 (3) |
N6—La1—O2 | 113.74 (7) | C44—C43—H43 | 120.5 |
O3—La1—O2 | 153.06 (6) | C42—C43—H43 | 120.5 |
N2—La1—O2 | 90.22 (7) | C43—C44—C45 | 120.7 (3) |
N5—La1—O1 | 77.73 (7) | C43—C44—H44 | 119.6 |
N3—La1—O1 | 148.32 (7) | C45—C44—H44 | 119.6 |
N1—La1—O1 | 76.89 (6) | C44—C45—C40 | 121.0 (3) |
N4—La1—O1 | 149.38 (7) | C44—C45—H45 | 119.5 |
N6—La1—O1 | 72.78 (7) | C40—C45—H45 | 119.5 |
O3—La1—O1 | 130.57 (7) | O1—C46—C47 | 104.1 (2) |
N2—La1—O1 | 76.08 (6) | O1—C46—H46A | 110.9 |
O2—La1—O1 | 75.87 (6) | C47—C46—H46A | 110.9 |
C49—O1—C46 | 104.4 (2) | O1—C46—H46B | 110.9 |
C49—O1—La1 | 124.39 (15) | C47—C46—H46B | 110.9 |
C46—O1—La1 | 124.70 (15) | H46A—C46—H46B | 108.9 |
C50—O2—C53 | 108.1 (2) | C46—C47—C48 | 104.3 (2) |
C50—O2—La1 | 128.13 (18) | C46—C47—H47A | 110.9 |
C53—O2—La1 | 123.73 (17) | C48—C47—H47A | 110.9 |
C57—O3—C54 | 108.4 (2) | C46—C47—H47B | 110.9 |
C57—O3—La1 | 122.74 (18) | C48—C47—H47B | 110.9 |
C54—O3—La1 | 121.39 (17) | H47A—C47—H47B | 108.9 |
C7—N1—N2 | 108.3 (2) | C47—C48—C49 | 104.7 (2) |
C7—N1—La1 | 171.48 (18) | C47—C48—H48A | 110.8 |
N2—N1—La1 | 77.13 (13) | C49—C48—H48A | 110.8 |
C9—N2—N1 | 107.9 (2) | C47—C48—H48B | 110.8 |
C9—N2—La1 | 174.13 (17) | C49—C48—H48B | 110.8 |
N1—N2—La1 | 71.88 (13) | H48A—C48—H48B | 108.9 |
C22—N3—N4 | 107.7 (2) | O1—C49—C48 | 105.7 (2) |
C22—N3—La1 | 173.6 (2) | O1—C49—H49A | 110.6 |
N4—N3—La1 | 75.07 (13) | C48—C49—H49A | 110.6 |
C24—N4—N3 | 108.4 (2) | O1—C49—H49B | 110.6 |
C24—N4—La1 | 173.70 (19) | C48—C49—H49B | 110.6 |
N3—N4—La1 | 73.37 (13) | H49A—C49—H49B | 108.7 |
C37—N5—N6 | 108.7 (2) | O2—C50—C51' | 110.6 (7) |
C37—N5—La1 | 174.3 (2) | O2—C50—C51 | 103.8 (3) |
N6—N5—La1 | 76.19 (14) | O2—C50—H50A | 111.0 |
C39—N6—N5 | 108.1 (2) | C51—C50—H50A | 111.0 |
C39—N6—La1 | 176.61 (19) | O2—C50—H50B | 111.0 |
N5—N6—La1 | 72.32 (14) | C51'—C50—H50B | 130.6 |
C2—C1—C6 | 120.3 (3) | C51—C50—H50B | 111.0 |
C2—C1—H1 | 119.9 | H50A—C50—H50B | 109.0 |
C6—C1—H1 | 119.9 | C51—C52—C53 | 100.8 (3) |
C3—C2—C1 | 120.9 (3) | C53—C52—C51' | 109.2 (6) |
C3—C2—H2 | 119.5 | C51—C52—H52A | 111.6 |
C1—C2—H2 | 119.5 | C53—C52—H52A | 111.6 |
C2—C3—C4 | 119.4 (3) | C51—C52—H52B | 111.6 |
C2—C3—H3 | 120.3 | C53—C52—H52B | 111.6 |
C4—C3—H3 | 120.3 | C51'—C52—H52B | 130.6 |
C3—C4—C5 | 120.4 (3) | H52A—C52—H52B | 109.4 |
C3—C4—H4 | 119.8 | O2—C53—C52 | 106.7 (3) |
C5—C4—H4 | 119.8 | O2—C53—H53A | 110.4 |
C4—C5—C6 | 120.6 (3) | C52—C53—H53A | 110.4 |
C4—C5—H5 | 119.7 | O2—C53—H53B | 110.4 |
C6—C5—H5 | 119.7 | C52—C53—H53B | 110.4 |
C1—C6—C5 | 118.4 (3) | H53A—C53—H53B | 108.6 |
C1—C6—C7 | 122.1 (3) | O3—C54—C55 | 104.5 (3) |
C5—C6—C7 | 119.5 (3) | O3—C54—H54A | 110.9 |
N1—C7—C8 | 109.3 (2) | C55—C54—H54A | 110.9 |
N1—C7—C6 | 121.7 (2) | O3—C54—H54B | 110.9 |
C8—C7—C6 | 129.0 (3) | C55—C54—H54B | 110.9 |
C7—C8—C9 | 105.3 (2) | H54A—C54—H54B | 108.9 |
C7—C8—H8 | 127.4 | C54—C55—C56 | 102.5 (3) |
C9—C8—H8 | 127.4 | C54—C55—H55A | 111.3 |
N2—C9—C8 | 109.2 (3) | C56—C55—H55A | 111.3 |
N2—C9—C10 | 122.5 (3) | C54—C55—H55B | 111.3 |
C8—C9—C10 | 128.2 (3) | C56—C55—H55B | 111.3 |
C11—C10—C15 | 117.4 (3) | H55A—C55—H55B | 109.2 |
C11—C10—C9 | 120.9 (3) | C57—C56—C55 | 104.8 (3) |
C15—C10—C9 | 121.6 (3) | C57—C56—H56A | 110.8 |
C12—C11—C10 | 121.8 (3) | C55—C56—H56A | 110.8 |
C12—C11—H11 | 119.1 | C57—C56—H56B | 110.8 |
C10—C11—H11 | 119.1 | C55—C56—H56B | 110.8 |
C13—C12—C11 | 120.0 (3) | H56A—C56—H56B | 108.9 |
C13—C12—H12 | 120.0 | O3—C57—C56 | 108.1 (3) |
C11—C12—H12 | 120.0 | O3—C57—H57A | 110.1 |
C12—C13—C14 | 119.8 (3) | C56—C57—H57A | 110.1 |
C12—C13—H13 | 120.1 | O3—C57—H57B | 110.1 |
C14—C13—H13 | 120.1 | C56—C57—H57B | 110.1 |
C15—C14—C13 | 120.8 (3) | H57A—C57—H57B | 108.4 |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1···O3 | 0.95 | 2.77 | 3.704 (4) | 168 |
C16—H16···N2 | 0.95 | 2.79 | 3.690 (4) | 157 |
C30—H30···N5 | 0.95 | 2.81 | 3.734 (4) | 163 |
C31—H31···O2 | 0.95 | 2.70 | 3.617 (5) | 163 |
[La(C14H10N3)3(C4H8O)3] | F(000) = 2088 |
Mr = 1015.97 | Dx = 1.385 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 21602 reflections |
a = 11.531 (2) Å | θ = 1.8–29.0° |
b = 18.688 (4) Å | µ = 0.93 mm−1 |
c = 23.827 (7) Å | T = 173 K |
β = 108.38 (3)° | Prism, colourless |
V = 4873 (2) Å3 | 0.20 × 0.20 × 0.20 mm |
Z = 4 |
Rigaku Saturn CCD area-detector diffractometer | 8861 independent reflections |
Radiation source: fine-focus sealed tube | 8240 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.020 |
ω scans | θmax = 25.4°, θmin = 3.1° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −13→13 |
Tmin = 0.836, Tmax = 0.836 | k = −22→18 |
25724 measured reflections | l = −28→24 |
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)] = 0.026 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.063 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.031P)2 + 2.4124P] where P = (Fo2 + 2Fc2)/3 |
8861 reflections | (Δ/σ)max = 0.001 |
636 parameters | Δρmax = 0.86 e Å−3 |
124 restraints | Δρmin = −0.49 e Å−3 |
[La(C14H10N3)3(C4H8O)3] | V = 4873 (2) Å3 |
Mr = 1015.97 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.531 (2) Å | µ = 0.93 mm−1 |
b = 18.688 (4) Å | T = 173 K |
c = 23.827 (7) Å | 0.20 × 0.20 × 0.20 mm |
β = 108.38 (3)° |
Rigaku Saturn CCD area-detector diffractometer | 8861 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 8240 reflections with I > 2σ(I) |
Tmin = 0.836, Tmax = 0.836 | Rint = 0.020 |
25724 measured reflections |
R[F2 > 2σ(F2)] = 0.026 | 124 restraints |
wR(F2) = 0.063 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.86 e Å−3 |
8861 reflections | Δρmin = −0.49 e Å−3 |
636 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
La1 | 0.796348 (11) | 0.078435 (7) | 0.288811 (5) | 0.01892 (5) | |
N1 | 0.70232 (17) | −0.00896 (10) | 0.34168 (8) | 0.0240 (4) | |
N2 | 0.57341 (17) | −0.02964 (10) | 0.39309 (8) | 0.0275 (4) | |
N3 | 0.64725 (17) | 0.05507 (10) | 0.34712 (8) | 0.0236 (4) | |
N4 | 0.60869 (17) | 0.07355 (9) | 0.19992 (8) | 0.0230 (4) | |
N5 | 0.52881 (17) | 0.08045 (10) | 0.10150 (8) | 0.0249 (4) | |
N6 | 0.69835 (16) | 0.09932 (10) | 0.17828 (8) | 0.0227 (4) | |
N7 | 0.95033 (16) | −0.02676 (10) | 0.30164 (8) | 0.0234 (4) | |
N8 | 1.00673 (16) | −0.11199 (10) | 0.24884 (8) | 0.0237 (4) | |
N9 | 0.86725 (16) | −0.02728 (10) | 0.24545 (8) | 0.0230 (4) | |
O1 | 0.92452 (16) | 0.11968 (10) | 0.39398 (7) | 0.0390 (4) | |
O2 | 0.71655 (15) | 0.21128 (8) | 0.28564 (7) | 0.0316 (4) | |
O3 | 0.98764 (14) | 0.13811 (8) | 0.27547 (7) | 0.0266 (3) | |
C1 | 0.6554 (2) | −0.05768 (12) | 0.36971 (9) | 0.0240 (5) | |
C2 | 0.6897 (2) | −0.13375 (12) | 0.37495 (9) | 0.0266 (5) | |
C3 | 0.7921 (2) | −0.15818 (13) | 0.36175 (10) | 0.0316 (5) | |
H3 | 0.8405 | −0.1255 | 0.3482 | 0.038* | |
C4 | 0.8238 (3) | −0.22993 (14) | 0.36824 (11) | 0.0397 (6) | |
H4 | 0.8951 | −0.2460 | 0.3602 | 0.048* | |
C5 | 0.7520 (3) | −0.27830 (14) | 0.38633 (11) | 0.0421 (7) | |
H5A | 0.7730 | −0.3276 | 0.3899 | 0.050* | |
C6 | 0.6497 (3) | −0.25470 (14) | 0.39913 (11) | 0.0392 (6) | |
H6 | 0.6000 | −0.2879 | 0.4113 | 0.047* | |
C7 | 0.6191 (2) | −0.18249 (13) | 0.39423 (10) | 0.0334 (6) | |
H7 | 0.5498 | −0.1664 | 0.4041 | 0.040* | |
C8 | 0.5715 (2) | 0.04007 (12) | 0.37777 (9) | 0.0231 (5) | |
C9 | 0.4966 (2) | 0.09343 (13) | 0.39563 (10) | 0.0256 (5) | |
C10 | 0.4298 (2) | 0.07334 (14) | 0.43257 (11) | 0.0312 (6) | |
H10 | 0.4291 | 0.0246 | 0.4439 | 0.037* | |
C11 | 0.3647 (2) | 0.12339 (15) | 0.45300 (12) | 0.0384 (6) | |
H11 | 0.3200 | 0.1090 | 0.4784 | 0.046* | |
C12 | 0.3643 (2) | 0.19391 (16) | 0.43665 (12) | 0.0408 (6) | |
H12 | 0.3201 | 0.2283 | 0.4510 | 0.049* | |
C13 | 0.4288 (2) | 0.21462 (14) | 0.39913 (13) | 0.0411 (6) | |
H13 | 0.4277 | 0.2632 | 0.3873 | 0.049* | |
C14 | 0.4945 (2) | 0.16476 (14) | 0.37897 (11) | 0.0347 (6) | |
H14 | 0.5388 | 0.1794 | 0.3534 | 0.042* | |
C15 | 0.5104 (2) | 0.06294 (11) | 0.15269 (10) | 0.0227 (5) | |
C16 | 0.3954 (2) | 0.03386 (12) | 0.15796 (10) | 0.0263 (5) | |
C17 | 0.3836 (2) | 0.02153 (13) | 0.21361 (11) | 0.0307 (5) | |
H17 | 0.4501 | 0.0314 | 0.2482 | 0.037* | |
C18 | 0.2754 (2) | −0.00509 (14) | 0.21873 (13) | 0.0385 (6) | |
H18 | 0.2684 | −0.0140 | 0.2568 | 0.046* | |
C19 | 0.1776 (2) | −0.01880 (14) | 0.16880 (14) | 0.0430 (7) | |
H19 | 0.1027 | −0.0359 | 0.1725 | 0.052* | |
C20 | 0.1888 (2) | −0.00763 (14) | 0.11363 (13) | 0.0412 (7) | |
H20 | 0.1217 | −0.0176 | 0.0793 | 0.049* | |
C21 | 0.2975 (2) | 0.01810 (13) | 0.10762 (11) | 0.0322 (5) | |
H21 | 0.3050 | 0.0249 | 0.0694 | 0.039* | |
C22 | 0.6466 (2) | 0.10141 (12) | 0.11954 (10) | 0.0244 (5) | |
C23 | 0.7157 (2) | 0.12114 (12) | 0.07936 (10) | 0.0280 (5) | |
C24 | 0.6546 (2) | 0.14608 (14) | 0.02269 (11) | 0.0386 (6) | |
H24 | 0.5684 | 0.1516 | 0.0102 | 0.046* | |
C25 | 0.7198 (3) | 0.16281 (17) | −0.01552 (13) | 0.0508 (7) | |
H25 | 0.6780 | 0.1802 | −0.0541 | 0.061* | |
C26 | 0.8443 (3) | 0.15443 (17) | 0.00211 (14) | 0.0537 (8) | |
H26 | 0.8882 | 0.1655 | −0.0245 | 0.064* | |
C27 | 0.9062 (3) | 0.13004 (17) | 0.05829 (13) | 0.0501 (7) | |
H27 | 0.9924 | 0.1245 | 0.0703 | 0.060* | |
C28 | 0.8422 (2) | 0.11371 (15) | 0.09706 (12) | 0.0393 (6) | |
H28 | 0.8848 | 0.0974 | 0.1359 | 0.047* | |
C29 | 1.0310 (2) | −0.07802 (11) | 0.30154 (10) | 0.0219 (5) | |
C30 | 1.1327 (2) | −0.09750 (12) | 0.35437 (10) | 0.0245 (5) | |
C31 | 1.1652 (2) | −0.05491 (14) | 0.40482 (10) | 0.0315 (5) | |
H31 | 1.1234 | −0.0112 | 0.4050 | 0.038* | |
C32 | 1.2586 (2) | −0.07617 (14) | 0.45488 (11) | 0.0360 (6) | |
H32 | 1.2811 | −0.0465 | 0.4890 | 0.043* | |
C33 | 1.3186 (2) | −0.13981 (15) | 0.45550 (12) | 0.0412 (7) | |
H33 | 1.3802 | −0.1550 | 0.4904 | 0.049* | |
C34 | 1.2889 (3) | −0.18157 (15) | 0.40509 (13) | 0.0488 (8) | |
H34 | 1.3314 | −0.2251 | 0.4050 | 0.059* | |
C35 | 1.1975 (2) | −0.16014 (14) | 0.35465 (12) | 0.0405 (6) | |
H35 | 1.1790 | −0.1886 | 0.3199 | 0.049* | |
C36 | 0.9041 (2) | −0.07852 (11) | 0.21579 (10) | 0.0219 (5) | |
C37 | 0.8388 (2) | −0.09391 (12) | 0.15308 (10) | 0.0236 (5) | |
C38 | 0.8956 (2) | −0.13039 (13) | 0.11790 (10) | 0.0306 (5) | |
H38 | 0.9765 | −0.1479 | 0.1348 | 0.037* | |
C39 | 0.8347 (3) | −0.14126 (14) | 0.05845 (11) | 0.0382 (6) | |
H39 | 0.8742 | −0.1660 | 0.0348 | 0.046* | |
C40 | 0.7164 (3) | −0.11622 (14) | 0.03320 (11) | 0.0404 (7) | |
H40 | 0.6748 | −0.1237 | −0.0076 | 0.048* | |
C41 | 0.6598 (3) | −0.08038 (13) | 0.06786 (12) | 0.0411 (7) | |
H41 | 0.5790 | −0.0629 | 0.0507 | 0.049* | |
C42 | 0.7196 (2) | −0.06965 (12) | 0.12725 (11) | 0.0319 (6) | |
H42 | 0.6790 | −0.0455 | 0.1508 | 0.038* | |
C43 | 1.0338 (2) | 0.16221 (16) | 0.41354 (11) | 0.0413 (7) | |
H43A | 1.0157 | 0.2136 | 0.4053 | 0.050* | |
H43B | 1.0945 | 0.1467 | 0.3944 | 0.050* | |
C44' | 1.0569 (5) | 0.1748 (3) | 0.4791 (2) | 0.0359 (12) | 0.653 (5) |
H44A | 0.9995 | 0.2101 | 0.4866 | 0.043* | 0.653 (5) |
H44B | 1.1422 | 0.1896 | 0.4998 | 0.043* | 0.653 (5) |
C45' | 1.0306 (5) | 0.0979 (3) | 0.49546 (17) | 0.0505 (13) | 0.653 (5) |
H45A | 1.1004 | 0.0657 | 0.4983 | 0.061* | 0.653 (5) |
H45B | 1.0123 | 0.0970 | 0.5334 | 0.061* | 0.653 (5) |
C46' | 0.9196 (6) | 0.0772 (3) | 0.44422 (17) | 0.0646 (16) | 0.653 (5) |
H46A | 0.9217 | 0.0255 | 0.4354 | 0.077* | 0.653 (5) |
H46B | 0.8437 | 0.0875 | 0.4537 | 0.077* | 0.653 (5) |
C44 | 1.0795 (10) | 0.1472 (6) | 0.4806 (5) | 0.0359 (12) | 0.347 (5) |
H44C | 1.1148 | 0.0986 | 0.4890 | 0.043* | 0.347 (5) |
H44D | 1.1415 | 0.1828 | 0.5018 | 0.043* | 0.347 (5) |
C45 | 0.9669 (8) | 0.1539 (6) | 0.4969 (3) | 0.053 (2) | 0.347 (5) |
H45C | 0.9443 | 0.2045 | 0.4999 | 0.063* | 0.347 (5) |
H45D | 0.9739 | 0.1289 | 0.5345 | 0.063* | 0.347 (5) |
C46 | 0.8764 (7) | 0.1161 (5) | 0.4436 (2) | 0.0362 (18) | 0.347 (5) |
H46C | 0.8661 | 0.0655 | 0.4535 | 0.043* | 0.347 (5) |
H46D | 0.7956 | 0.1399 | 0.4330 | 0.043* | 0.347 (5) |
C47 | 0.7446 (2) | 0.26343 (15) | 0.33268 (13) | 0.0469 (7) | |
H47A | 0.8226 | 0.2879 | 0.3359 | 0.056* | |
H47B | 0.7523 | 0.2399 | 0.3709 | 0.056* | |
C48 | 0.6417 (3) | 0.31621 (13) | 0.31765 (11) | 0.0367 (6) | |
H48A | 0.6651 | 0.3627 | 0.3380 | 0.044* | |
H48B | 0.5674 | 0.2973 | 0.3248 | 0.044* | |
C49 | 0.6296 (19) | 0.3197 (5) | 0.2519 (4) | 0.052 (3) | 0.48 (2) |
H49A | 0.7036 | 0.3402 | 0.2454 | 0.062* | 0.48 (2) |
H49B | 0.5569 | 0.3475 | 0.2291 | 0.062* | 0.48 (2) |
C49' | 0.5763 (13) | 0.3126 (6) | 0.2506 (4) | 0.046 (2) | 0.52 (2) |
H49C | 0.4865 | 0.3160 | 0.2412 | 0.056* | 0.52 (2) |
H49D | 0.6050 | 0.3506 | 0.2293 | 0.056* | 0.52 (2) |
C50 | 0.6152 (3) | 0.23866 (16) | 0.23647 (13) | 0.0514 (7) | |
H50A | 0.5354 | 0.2197 | 0.2371 | 0.062* | |
H50B | 0.6262 | 0.2283 | 0.1977 | 0.062* | |
C51 | 0.9964 (2) | 0.21138 (13) | 0.25803 (11) | 0.0331 (6) | |
H51A | 0.9575 | 0.2442 | 0.2794 | 0.040* | |
H51B | 0.9565 | 0.2175 | 0.2150 | 0.040* | |
C52 | 1.1319 (2) | 0.22574 (14) | 0.27454 (13) | 0.0395 (6) | |
H52A | 1.1673 | 0.2375 | 0.3170 | 0.047* | |
H52B | 1.1495 | 0.2651 | 0.2506 | 0.047* | |
C53 | 1.1796 (2) | 0.15482 (14) | 0.26013 (14) | 0.0434 (7) | |
H53A | 1.1723 | 0.1519 | 0.2177 | 0.052* | |
H53B | 1.2662 | 0.1477 | 0.2840 | 0.052* | |
C54 | 1.0990 (2) | 0.10073 (14) | 0.27584 (13) | 0.0362 (6) | |
H54A | 1.0795 | 0.0613 | 0.2466 | 0.043* | |
H54B | 1.1404 | 0.0804 | 0.3155 | 0.043* |
U11 | U22 | U33 | U12 | U13 | U23 | |
La1 | 0.01885 (8) | 0.02081 (8) | 0.01656 (7) | −0.00078 (5) | 0.00484 (5) | 0.00016 (5) |
N1 | 0.0266 (10) | 0.0219 (10) | 0.0235 (9) | −0.0004 (8) | 0.0078 (8) | 0.0007 (8) |
N2 | 0.0303 (11) | 0.0277 (11) | 0.0260 (10) | −0.0038 (9) | 0.0109 (9) | 0.0019 (8) |
N3 | 0.0253 (10) | 0.0227 (9) | 0.0229 (9) | 0.0005 (8) | 0.0078 (8) | 0.0003 (8) |
N4 | 0.0218 (10) | 0.0232 (10) | 0.0236 (10) | −0.0010 (8) | 0.0067 (8) | 0.0000 (8) |
N5 | 0.0242 (10) | 0.0257 (10) | 0.0223 (10) | 0.0014 (8) | 0.0036 (8) | 0.0002 (8) |
N6 | 0.0221 (10) | 0.0235 (10) | 0.0224 (10) | −0.0011 (8) | 0.0068 (8) | 0.0006 (8) |
N7 | 0.0223 (9) | 0.0254 (10) | 0.0209 (9) | −0.0004 (8) | 0.0047 (8) | 0.0012 (8) |
N8 | 0.0220 (9) | 0.0233 (10) | 0.0232 (9) | 0.0004 (8) | 0.0036 (8) | −0.0004 (8) |
N9 | 0.0216 (9) | 0.0247 (10) | 0.0206 (9) | −0.0003 (8) | 0.0036 (8) | −0.0008 (8) |
O1 | 0.0373 (10) | 0.0565 (12) | 0.0206 (8) | −0.0195 (9) | 0.0054 (8) | −0.0031 (8) |
O2 | 0.0405 (9) | 0.0257 (9) | 0.0279 (8) | −0.0007 (7) | 0.0095 (7) | −0.0044 (7) |
O3 | 0.0242 (8) | 0.0253 (8) | 0.0318 (9) | 0.0005 (7) | 0.0108 (7) | 0.0023 (7) |
C1 | 0.0252 (12) | 0.0266 (12) | 0.0181 (11) | −0.0036 (10) | 0.0038 (9) | 0.0011 (9) |
C2 | 0.0355 (13) | 0.0243 (12) | 0.0169 (11) | −0.0055 (10) | 0.0040 (10) | 0.0005 (9) |
C3 | 0.0424 (14) | 0.0274 (13) | 0.0256 (12) | −0.0012 (11) | 0.0113 (11) | 0.0003 (10) |
C4 | 0.0524 (17) | 0.0307 (14) | 0.0361 (14) | 0.0067 (13) | 0.0141 (13) | −0.0015 (11) |
C5 | 0.0609 (19) | 0.0230 (13) | 0.0361 (14) | 0.0014 (13) | 0.0065 (13) | 0.0005 (11) |
C6 | 0.0498 (16) | 0.0298 (14) | 0.0311 (13) | −0.0130 (13) | 0.0030 (12) | 0.0068 (11) |
C7 | 0.0380 (14) | 0.0313 (13) | 0.0272 (13) | −0.0057 (11) | 0.0050 (11) | 0.0047 (10) |
C8 | 0.0225 (11) | 0.0277 (12) | 0.0185 (10) | −0.0032 (10) | 0.0056 (9) | 0.0004 (9) |
C9 | 0.0198 (11) | 0.0325 (13) | 0.0223 (11) | −0.0013 (10) | 0.0034 (9) | −0.0008 (10) |
C10 | 0.0264 (13) | 0.0376 (14) | 0.0309 (13) | −0.0019 (11) | 0.0109 (11) | 0.0000 (11) |
C11 | 0.0295 (13) | 0.0499 (17) | 0.0406 (15) | 0.0019 (12) | 0.0180 (12) | −0.0026 (13) |
C12 | 0.0285 (13) | 0.0484 (17) | 0.0463 (16) | 0.0055 (12) | 0.0129 (12) | −0.0094 (13) |
C13 | 0.0379 (15) | 0.0304 (14) | 0.0557 (17) | 0.0043 (12) | 0.0158 (13) | 0.0009 (13) |
C14 | 0.0330 (13) | 0.0359 (14) | 0.0382 (14) | 0.0017 (11) | 0.0152 (12) | 0.0039 (11) |
C15 | 0.0217 (11) | 0.0199 (11) | 0.0243 (11) | 0.0025 (9) | 0.0039 (9) | −0.0014 (9) |
C16 | 0.0226 (11) | 0.0217 (11) | 0.0329 (12) | 0.0025 (9) | 0.0064 (10) | −0.0021 (10) |
C17 | 0.0267 (12) | 0.0309 (13) | 0.0357 (13) | −0.0013 (11) | 0.0115 (11) | −0.0074 (11) |
C18 | 0.0382 (15) | 0.0355 (14) | 0.0501 (16) | −0.0036 (12) | 0.0255 (13) | −0.0100 (12) |
C19 | 0.0308 (14) | 0.0369 (15) | 0.069 (2) | −0.0076 (12) | 0.0263 (14) | −0.0139 (14) |
C20 | 0.0238 (13) | 0.0383 (15) | 0.0550 (17) | −0.0042 (11) | 0.0029 (12) | −0.0104 (13) |
C21 | 0.0268 (12) | 0.0318 (13) | 0.0348 (13) | −0.0021 (11) | 0.0052 (11) | −0.0015 (11) |
C22 | 0.0267 (12) | 0.0215 (11) | 0.0217 (11) | 0.0033 (10) | 0.0030 (10) | −0.0018 (9) |
C23 | 0.0338 (13) | 0.0267 (12) | 0.0245 (10) | −0.0055 (10) | 0.0108 (9) | −0.0054 (9) |
C24 | 0.0403 (10) | 0.0420 (10) | 0.0321 (8) | −0.0026 (8) | 0.0091 (7) | 0.0012 (8) |
C25 | 0.0549 (11) | 0.0569 (11) | 0.0432 (10) | −0.0052 (9) | 0.0191 (8) | 0.0034 (8) |
C26 | 0.0570 (11) | 0.0583 (12) | 0.0511 (11) | −0.0061 (9) | 0.0247 (9) | −0.0005 (9) |
C27 | 0.0475 (11) | 0.0546 (11) | 0.0518 (11) | −0.0039 (9) | 0.0207 (9) | −0.0009 (9) |
C28 | 0.0383 (10) | 0.0421 (10) | 0.0385 (10) | −0.0018 (8) | 0.0135 (8) | 0.0008 (8) |
C29 | 0.0204 (11) | 0.0212 (11) | 0.0228 (11) | −0.0039 (9) | 0.0052 (9) | 0.0027 (9) |
C30 | 0.0216 (11) | 0.0241 (11) | 0.0257 (12) | −0.0046 (9) | 0.0043 (10) | 0.0044 (9) |
C31 | 0.0316 (13) | 0.0362 (14) | 0.0253 (12) | 0.0016 (11) | 0.0068 (11) | 0.0012 (11) |
C32 | 0.0334 (14) | 0.0486 (16) | 0.0225 (12) | −0.0058 (12) | 0.0039 (11) | 0.0002 (11) |
C33 | 0.0336 (14) | 0.0442 (16) | 0.0341 (14) | −0.0041 (12) | −0.0061 (12) | 0.0122 (12) |
C34 | 0.0406 (16) | 0.0320 (15) | 0.0548 (18) | 0.0047 (12) | −0.0123 (14) | 0.0025 (13) |
C35 | 0.0370 (14) | 0.0293 (14) | 0.0405 (15) | 0.0015 (12) | −0.0089 (12) | −0.0048 (11) |
C36 | 0.0212 (11) | 0.0186 (11) | 0.0247 (11) | −0.0022 (9) | 0.0055 (10) | 0.0018 (9) |
C37 | 0.0259 (12) | 0.0200 (11) | 0.0218 (11) | −0.0033 (9) | 0.0033 (10) | −0.0002 (9) |
C38 | 0.0310 (13) | 0.0289 (13) | 0.0306 (13) | −0.0010 (11) | 0.0076 (11) | −0.0026 (10) |
C39 | 0.0529 (17) | 0.0348 (14) | 0.0288 (13) | −0.0060 (13) | 0.0154 (12) | −0.0068 (11) |
C40 | 0.0540 (17) | 0.0293 (14) | 0.0261 (13) | −0.0054 (13) | −0.0041 (12) | −0.0019 (11) |
C41 | 0.0385 (15) | 0.0294 (14) | 0.0387 (15) | 0.0027 (11) | −0.0115 (13) | −0.0043 (11) |
C42 | 0.0291 (13) | 0.0246 (12) | 0.0349 (13) | 0.0019 (10) | −0.0002 (11) | −0.0064 (10) |
C43 | 0.0337 (14) | 0.0590 (18) | 0.0272 (13) | −0.0168 (13) | 0.0040 (11) | −0.0056 (12) |
C44' | 0.031 (3) | 0.042 (4) | 0.0316 (16) | 0.003 (2) | 0.0047 (17) | −0.015 (3) |
C45' | 0.054 (3) | 0.072 (3) | 0.0193 (19) | −0.028 (2) | 0.0027 (18) | 0.0005 (19) |
C46' | 0.069 (3) | 0.083 (3) | 0.033 (2) | −0.037 (3) | 0.004 (2) | 0.010 (2) |
C44 | 0.031 (3) | 0.042 (4) | 0.0316 (16) | 0.003 (2) | 0.0047 (17) | −0.015 (3) |
C45 | 0.050 (4) | 0.075 (5) | 0.030 (3) | −0.020 (4) | 0.008 (3) | −0.006 (3) |
C46 | 0.037 (3) | 0.050 (4) | 0.019 (3) | −0.019 (3) | 0.005 (2) | 0.002 (3) |
C47 | 0.0381 (15) | 0.0462 (17) | 0.0507 (17) | 0.0002 (13) | 0.0059 (13) | −0.0243 (14) |
C48 | 0.0511 (16) | 0.0249 (13) | 0.0332 (14) | 0.0007 (12) | 0.0121 (12) | −0.0029 (11) |
C49 | 0.078 (7) | 0.033 (4) | 0.033 (3) | 0.022 (4) | 0.003 (4) | 0.003 (3) |
C49' | 0.054 (5) | 0.042 (4) | 0.036 (3) | 0.016 (4) | 0.003 (4) | −0.005 (3) |
C50 | 0.0581 (10) | 0.0456 (10) | 0.0438 (10) | 0.0115 (9) | 0.0064 (8) | −0.0001 (8) |
C51 | 0.0357 (13) | 0.0282 (13) | 0.0381 (14) | 0.0035 (11) | 0.0154 (12) | 0.0076 (11) |
C52 | 0.0404 (15) | 0.0301 (14) | 0.0560 (17) | −0.0042 (12) | 0.0264 (14) | −0.0008 (12) |
C53 | 0.0379 (15) | 0.0334 (14) | 0.0683 (19) | −0.0009 (12) | 0.0301 (15) | 0.0019 (13) |
C54 | 0.0298 (13) | 0.0323 (14) | 0.0517 (16) | 0.0050 (11) | 0.0201 (12) | 0.0028 (12) |
La1—N1 | 2.5083 (18) | C26—H26 | 0.9500 |
La1—N3 | 2.5658 (19) | C27—C28 | 1.386 (4) |
La1—N4 | 2.507 (2) | C27—H27 | 0.9500 |
La1—N6 | 2.547 (2) | C28—H28 | 0.9500 |
La1—N7 | 2.6016 (19) | C29—C30 | 1.471 (3) |
La1—N9 | 2.4843 (18) | C30—C35 | 1.388 (3) |
La1—O1 | 2.5926 (18) | C30—C31 | 1.391 (3) |
La1—O2 | 2.6404 (17) | C31—C32 | 1.389 (3) |
La1—O3 | 2.5792 (15) | C31—H31 | 0.9500 |
N1—C1 | 1.340 (3) | C32—C33 | 1.374 (4) |
N1—N3 | 1.380 (3) | C32—H32 | 0.9500 |
N2—C1 | 1.345 (3) | C33—C34 | 1.382 (4) |
N2—C8 | 1.351 (3) | C33—H33 | 0.9500 |
N3—C8 | 1.333 (3) | C34—C35 | 1.384 (4) |
N4—C15 | 1.337 (3) | C34—H34 | 0.9500 |
N4—N6 | 1.379 (3) | C35—H35 | 0.9500 |
N5—C15 | 1.343 (3) | C36—C37 | 1.474 (3) |
N5—C22 | 1.347 (3) | C37—C42 | 1.393 (3) |
N6—C22 | 1.338 (3) | C37—C38 | 1.394 (3) |
N7—C29 | 1.335 (3) | C38—C39 | 1.383 (3) |
N7—N9 | 1.379 (2) | C38—H38 | 0.9500 |
N8—C36 | 1.351 (3) | C39—C40 | 1.387 (4) |
N8—C29 | 1.355 (3) | C39—H39 | 0.9500 |
N9—C36 | 1.336 (3) | C40—C41 | 1.377 (4) |
O1—C43 | 1.438 (3) | C40—H40 | 0.9500 |
O1—C46' | 1.452 (2) | C41—C42 | 1.379 (4) |
O1—C46 | 1.457 (2) | C41—H41 | 0.9500 |
O2—C47 | 1.443 (3) | C42—H42 | 0.9500 |
O2—C50 | 1.462 (3) | C43—C44' | 1.519 (6) |
O3—C51 | 1.444 (3) | C43—C44 | 1.541 (11) |
O3—C54 | 1.460 (3) | C43—H43A | 0.9900 |
C1—C2 | 1.470 (3) | C43—H43B | 0.9900 |
C2—C3 | 1.391 (3) | C44'—C45' | 1.544 (7) |
C2—C7 | 1.392 (3) | C44'—H44A | 0.9900 |
C3—C4 | 1.386 (3) | C44'—H44B | 0.9900 |
C3—H3 | 0.9500 | C45'—C46' | 1.514 (6) |
C4—C5 | 1.383 (4) | C45'—H45A | 0.9900 |
C4—H4 | 0.9500 | C45'—H45B | 0.9900 |
C5—C6 | 1.380 (4) | C46'—H46A | 0.9900 |
C5—H5A | 0.9500 | C46'—H46B | 0.9900 |
C6—C7 | 1.390 (4) | C44—C45 | 1.475 (12) |
C6—H6 | 0.9500 | C44—H44C | 0.9900 |
C7—H7 | 0.9500 | C44—H44D | 0.9900 |
C8—C9 | 1.467 (3) | C45—C46 | 1.539 (9) |
C9—C14 | 1.389 (3) | C45—H45C | 0.9900 |
C9—C10 | 1.391 (3) | C45—H45D | 0.9900 |
C10—C11 | 1.381 (4) | C46—H46C | 0.9900 |
C10—H10 | 0.9500 | C46—H46D | 0.9900 |
C11—C12 | 1.374 (4) | C47—C48 | 1.497 (4) |
C11—H11 | 0.9500 | C47—H47A | 0.9900 |
C12—C13 | 1.386 (4) | C47—H47B | 0.9900 |
C12—H12 | 0.9500 | C48—C49 | 1.530 (9) |
C13—C14 | 1.380 (4) | C48—C49' | 1.538 (9) |
C13—H13 | 0.9500 | C48—H48A | 0.9900 |
C14—H14 | 0.9500 | C48—H48B | 0.9900 |
C15—C16 | 1.475 (3) | C49—C50 | 1.556 (10) |
C16—C17 | 1.394 (3) | C49—H49A | 0.9900 |
C16—C21 | 1.395 (3) | C49—H49B | 0.9900 |
C17—C18 | 1.384 (3) | C49'—C50 | 1.523 (9) |
C17—H17 | 0.9500 | C49'—H49C | 0.9900 |
C18—C19 | 1.381 (4) | C49'—H49D | 0.9900 |
C18—H18 | 0.9500 | C50—H50A | 0.9900 |
C19—C20 | 1.377 (4) | C50—H50B | 0.9900 |
C19—H19 | 0.9500 | C51—C52 | 1.510 (3) |
C20—C21 | 1.392 (4) | C51—H51A | 0.9900 |
C20—H20 | 0.9500 | C51—H51B | 0.9900 |
C21—H21 | 0.9500 | C52—C53 | 1.515 (4) |
C22—C23 | 1.472 (3) | C52—H52A | 0.9900 |
C23—C28 | 1.392 (3) | C52—H52B | 0.9900 |
C23—C24 | 1.392 (3) | C53—C54 | 1.498 (4) |
C24—C25 | 1.386 (4) | C53—H53A | 0.9900 |
C24—H24 | 0.9500 | C53—H53B | 0.9900 |
C25—C26 | 1.372 (4) | C54—H54A | 0.9900 |
C25—H25 | 0.9500 | C54—H54B | 0.9900 |
C26—C27 | 1.381 (4) | ||
N9—La1—N4 | 85.94 (6) | C27—C28—C23 | 120.2 (3) |
N9—La1—N1 | 86.68 (6) | C27—C28—H28 | 119.9 |
N4—La1—N1 | 90.34 (6) | C23—C28—H28 | 119.9 |
N9—La1—N6 | 77.81 (6) | N7—C29—N8 | 113.43 (19) |
N4—La1—N6 | 31.66 (6) | N7—C29—C30 | 123.0 (2) |
N1—La1—N6 | 119.86 (6) | N8—C29—C30 | 123.6 (2) |
N9—La1—N3 | 117.03 (6) | C35—C30—C31 | 118.7 (2) |
N4—La1—N3 | 84.49 (6) | C35—C30—C29 | 119.7 (2) |
N1—La1—N3 | 31.53 (6) | C31—C30—C29 | 121.5 (2) |
N6—La1—N3 | 115.55 (6) | C32—C31—C30 | 120.2 (2) |
N9—La1—O3 | 83.47 (6) | C32—C31—H31 | 119.9 |
N4—La1—O3 | 117.09 (6) | C30—C31—H31 | 119.9 |
N1—La1—O3 | 149.92 (6) | C33—C32—C31 | 120.6 (2) |
N6—La1—O3 | 85.65 (6) | C33—C32—H32 | 119.7 |
N3—La1—O3 | 152.31 (5) | C31—C32—H32 | 119.7 |
N9—La1—O1 | 118.45 (6) | C32—C33—C34 | 119.6 (2) |
N4—La1—O1 | 154.74 (6) | C32—C33—H33 | 120.2 |
N1—La1—O1 | 85.02 (6) | C34—C33—H33 | 120.2 |
N6—La1—O1 | 152.32 (6) | C33—C34—C35 | 120.2 (3) |
N3—La1—O1 | 78.60 (6) | C33—C34—H34 | 119.9 |
O3—La1—O1 | 75.02 (5) | C35—C34—H34 | 119.9 |
N9—La1—N7 | 31.36 (6) | C34—C35—C30 | 120.6 (3) |
N4—La1—N7 | 116.55 (6) | C34—C35—H35 | 119.7 |
N1—La1—N7 | 80.56 (6) | C30—C35—H35 | 119.7 |
N6—La1—N7 | 107.53 (6) | N9—C36—N8 | 112.94 (19) |
N3—La1—N7 | 110.90 (6) | N9—C36—C37 | 121.99 (19) |
O3—La1—N7 | 76.27 (5) | N8—C36—C37 | 125.0 (2) |
O1—La1—N7 | 87.20 (6) | C42—C37—C38 | 118.6 (2) |
N9—La1—O2 | 153.29 (5) | C42—C37—C36 | 120.1 (2) |
N4—La1—O2 | 79.04 (5) | C38—C37—C36 | 121.2 (2) |
N1—La1—O2 | 115.13 (6) | C39—C38—C37 | 120.3 (2) |
N6—La1—O2 | 77.84 (5) | C39—C38—H38 | 119.8 |
N3—La1—O2 | 83.60 (5) | C37—C38—H38 | 119.8 |
O3—La1—O2 | 83.91 (5) | C38—C39—C40 | 120.4 (2) |
O1—La1—O2 | 80.53 (6) | C38—C39—H39 | 119.8 |
N7—La1—O2 | 158.84 (5) | C40—C39—H39 | 119.8 |
C1—N1—N3 | 105.79 (17) | C41—C40—C39 | 119.4 (2) |
C1—N1—La1 | 177.65 (16) | C41—C40—H40 | 120.3 |
N3—N1—La1 | 76.53 (11) | C39—C40—H40 | 120.3 |
C1—N2—C8 | 102.58 (18) | C40—C41—C42 | 120.5 (3) |
C8—N3—N1 | 105.64 (17) | C40—C41—H41 | 119.7 |
C8—N3—La1 | 177.56 (16) | C42—C41—H41 | 119.7 |
N1—N3—La1 | 71.94 (10) | C41—C42—C37 | 120.7 (2) |
C15—N4—N6 | 105.90 (17) | C41—C42—H42 | 119.7 |
C15—N4—La1 | 173.53 (15) | C37—C42—H42 | 119.7 |
N6—N4—La1 | 75.76 (11) | O1—C43—C44' | 105.7 (3) |
C15—N5—C22 | 102.33 (19) | O1—C43—C44 | 102.3 (5) |
C22—N6—N4 | 105.18 (18) | O1—C43—H43A | 111.3 |
C22—N6—La1 | 172.86 (15) | C44—C43—H43A | 111.3 |
N4—N6—La1 | 72.58 (11) | O1—C43—H43B | 111.3 |
C29—N7—N9 | 105.31 (17) | C44'—C43—H43B | 126.8 |
C29—N7—La1 | 172.54 (15) | C44—C43—H43B | 111.3 |
N9—N7—La1 | 69.62 (11) | H43A—C43—H43B | 109.2 |
C36—N8—C29 | 102.11 (18) | C43—C44'—C45' | 97.5 (3) |
C36—N9—N7 | 106.21 (17) | C43—C44'—H44A | 112.3 |
C36—N9—La1 | 172.25 (15) | C45'—C44'—H44A | 112.3 |
N7—N9—La1 | 79.02 (11) | C43—C44'—H44B | 112.3 |
C43—O1—C46' | 107.0 (2) | C45'—C44'—H44B | 112.3 |
C43—O1—C46 | 106.4 (3) | H44A—C44'—H44B | 109.9 |
C43—O1—La1 | 130.69 (13) | C46'—C45'—C44' | 102.6 (4) |
C46'—O1—La1 | 118.4 (2) | C46'—C45'—H45A | 111.2 |
C46—O1—La1 | 121.5 (3) | C44'—C45'—H45A | 111.2 |
C47—O2—C50 | 108.25 (19) | C46'—C45'—H45B | 111.2 |
C47—O2—La1 | 128.47 (15) | C44'—C45'—H45B | 111.2 |
C50—O2—La1 | 122.36 (14) | H45A—C45'—H45B | 109.2 |
C51—O3—C54 | 108.30 (17) | O1—C46'—C45' | 106.4 (3) |
C51—O3—La1 | 125.87 (13) | O1—C46'—H46A | 110.4 |
C54—O3—La1 | 125.28 (13) | C45'—C46'—H46A | 110.4 |
N1—C1—N2 | 112.9 (2) | O1—C46'—H46B | 110.4 |
N1—C1—C2 | 124.0 (2) | C45'—C46'—H46B | 110.4 |
N2—C1—C2 | 123.1 (2) | H46A—C46'—H46B | 108.6 |
C3—C2—C7 | 119.1 (2) | C45—C44—C43 | 102.5 (7) |
C3—C2—C1 | 121.5 (2) | C45—C44—H44C | 111.3 |
C7—C2—C1 | 119.4 (2) | C43—C44—H44C | 111.3 |
C4—C3—C2 | 120.3 (2) | C45—C44—H44D | 111.3 |
C4—C3—H3 | 119.8 | C43—C44—H44D | 111.3 |
C2—C3—H3 | 119.8 | H44C—C44—H44D | 109.2 |
C5—C4—C3 | 120.3 (3) | C44—C45—C46 | 99.6 (7) |
C5—C4—H4 | 119.9 | C44—C45—H45C | 111.8 |
C3—C4—H4 | 119.9 | C46—C45—H45C | 111.8 |
C6—C5—C4 | 119.8 (2) | C44—C45—H45D | 111.8 |
C6—C5—H5A | 120.1 | C46—C45—H45D | 111.8 |
C4—C5—H5A | 120.1 | H45C—C45—H45D | 109.6 |
C5—C6—C7 | 120.2 (2) | O1—C46—C45 | 108.4 (5) |
C5—C6—H6 | 119.9 | O1—C46—H46C | 110.0 |
C7—C6—H6 | 119.9 | C45—C46—H46C | 110.0 |
C6—C7—C2 | 120.3 (3) | O1—C46—H46D | 110.0 |
C6—C7—H7 | 119.9 | C45—C46—H46D | 110.0 |
C2—C7—H7 | 119.9 | H46C—C46—H46D | 108.4 |
N3—C8—N2 | 113.1 (2) | O2—C47—C48 | 107.0 (2) |
N3—C8—C9 | 124.3 (2) | O2—C47—H47A | 110.3 |
N2—C8—C9 | 122.6 (2) | C48—C47—H47A | 110.3 |
C14—C9—C10 | 118.5 (2) | O2—C47—H47B | 110.3 |
C14—C9—C8 | 121.9 (2) | C48—C47—H47B | 110.3 |
C10—C9—C8 | 119.6 (2) | H47A—C47—H47B | 108.6 |
C11—C10—C9 | 120.7 (2) | C47—C48—C49 | 94.7 (6) |
C11—C10—H10 | 119.6 | C47—C48—C49' | 108.2 (4) |
C9—C10—H10 | 119.6 | C47—C48—H48A | 112.8 |
C12—C11—C10 | 120.2 (2) | C49—C48—H48A | 112.8 |
C12—C11—H11 | 119.9 | C49'—C48—H48A | 121.1 |
C10—C11—H11 | 119.9 | C47—C48—H48B | 112.8 |
C11—C12—C13 | 119.8 (2) | C49—C48—H48B | 112.8 |
C11—C12—H12 | 120.1 | C49'—C48—H48B | 89.7 |
C13—C12—H12 | 120.1 | H48A—C48—H48B | 110.2 |
C14—C13—C12 | 120.1 (3) | C48—C49—C50 | 99.7 (6) |
C14—C13—H13 | 120.0 | C48—C49—H49A | 111.8 |
C12—C13—H13 | 120.0 | C50—C49—H49A | 111.8 |
C13—C14—C9 | 120.7 (2) | C48—C49—H49B | 111.8 |
C13—C14—H14 | 119.6 | C50—C49—H49B | 111.8 |
C9—C14—H14 | 119.6 | H49A—C49—H49B | 109.6 |
N4—C15—N5 | 113.2 (2) | C50—C49'—C48 | 100.8 (5) |
N4—C15—C16 | 122.0 (2) | C50—C49'—H49C | 111.6 |
N5—C15—C16 | 124.8 (2) | C48—C49'—H49C | 111.6 |
C17—C16—C21 | 119.2 (2) | C50—C49'—H49D | 111.6 |
C17—C16—C15 | 120.1 (2) | C48—C49'—H49D | 111.6 |
C21—C16—C15 | 120.7 (2) | H49C—C49'—H49D | 109.4 |
C18—C17—C16 | 120.3 (2) | O2—C50—C49' | 110.9 (4) |
C18—C17—H17 | 119.9 | O2—C50—C49 | 98.8 (6) |
C16—C17—H17 | 119.9 | O2—C50—H50A | 112.0 |
C19—C18—C17 | 120.3 (3) | C49'—C50—H50A | 88.9 |
C19—C18—H18 | 119.8 | C49—C50—H50A | 112.0 |
C17—C18—H18 | 119.8 | O2—C50—H50B | 112.0 |
C20—C19—C18 | 119.8 (2) | C49'—C50—H50B | 121.1 |
C20—C19—H19 | 120.1 | C49—C50—H50B | 112.0 |
C18—C19—H19 | 120.1 | H50A—C50—H50B | 109.7 |
C19—C20—C21 | 120.6 (2) | O3—C51—C52 | 104.73 (19) |
C19—C20—H20 | 119.7 | O3—C51—H51A | 110.8 |
C21—C20—H20 | 119.7 | C52—C51—H51A | 110.8 |
C20—C21—C16 | 119.7 (2) | O3—C51—H51B | 110.8 |
C20—C21—H21 | 120.2 | C52—C51—H51B | 110.8 |
C16—C21—H21 | 120.2 | H51A—C51—H51B | 108.9 |
N6—C22—N5 | 113.4 (2) | C51—C52—C53 | 101.8 (2) |
N6—C22—C23 | 122.2 (2) | C51—C52—H52A | 111.4 |
N5—C22—C23 | 124.3 (2) | C53—C52—H52A | 111.4 |
C28—C23—C24 | 119.2 (2) | C51—C52—H52B | 111.4 |
C28—C23—C22 | 120.5 (2) | C53—C52—H52B | 111.4 |
C24—C23—C22 | 120.2 (2) | H52A—C52—H52B | 109.3 |
C25—C24—C23 | 120.0 (3) | C54—C53—C52 | 103.6 (2) |
C25—C24—H24 | 120.0 | C54—C53—H53A | 111.0 |
C23—C24—H24 | 120.0 | C52—C53—H53A | 111.0 |
C26—C25—C24 | 120.3 (3) | C54—C53—H53B | 111.0 |
C26—C25—H25 | 119.9 | C52—C53—H53B | 111.0 |
C24—C25—H25 | 119.9 | H53A—C53—H53B | 109.0 |
C25—C26—C27 | 120.4 (3) | O3—C54—C53 | 106.8 (2) |
C25—C26—H26 | 119.8 | O3—C54—H54A | 110.4 |
C27—C26—H26 | 119.8 | C53—C54—H54A | 110.4 |
C26—C27—C28 | 119.9 (3) | O3—C54—H54B | 110.4 |
C26—C27—H27 | 120.1 | C53—C54—H54B | 110.4 |
C28—C27—H27 | 120.1 | H54A—C54—H54B | 108.6 |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···N7 | 0.95 | 2.67 | 3.614 (3) | 173 |
C17—H17···N3 | 0.95 | 2.75 | 3.696 (3) | 178 |
C42—H42···N4 | 0.95 | 2.75 | 3.632 (3) | 154 |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | [La(C15H11N2)3(C4H8O)3]·C4H8O | [La(C14H10N3)3(C4H8O)3] |
Mr | 1085.10 | 1015.97 |
Crystal system, space group | Orthorhombic, P212121 | Monoclinic, P21/c |
Temperature (K) | 173 | 173 |
a, b, c (Å) | 14.146 (3), 16.358 (3), 22.856 (5) | 11.531 (2), 18.688 (4), 23.827 (7) |
α, β, γ (°) | 90, 90, 90 | 90, 108.38 (3), 90 |
V (Å3) | 5288.8 (18) | 4873 (2) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.86 | 0.93 |
Crystal size (mm) | 0.20 × 0.20 × 0.20 | 0.20 × 0.20 × 0.20 |
Data collection | ||
Diffractometer | Rigaku Saturn CCD area-detector diffractometer | Rigaku Saturn CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.811, 1.000 | 0.836, 0.836 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 22016, 9592, 9280 | 25724, 8861, 8240 |
Rint | 0.031 | 0.020 |
(sin θ/λ)max (Å−1) | 0.602 | 0.602 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.029, 0.054, 1.03 | 0.026, 0.063, 1.05 |
No. of reflections | 9592 | 8861 |
No. of parameters | 670 | 636 |
No. of restraints | 76 | 124 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.53, −0.34 | 0.86, −0.49 |
Absolute structure | Flack (1983), with how many Friedel pairs? | ? |
Absolute structure parameter | 0.450 (8) | ? |
Computer programs: CrystalClear (Rigaku, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009), SHELXTL (Sheldrick, 2008).
La1—N1 | 2.523 (2) | La1—N6 | 2.546 (2) |
La1—N2 | 2.588 (2) | La1—O1 | 2.6496 (19) |
La1—N3 | 2.506 (2) | La1—O2 | 2.612 (2) |
La1—N4 | 2.527 (2) | La1—O3 | 2.573 (2) |
La1—N5 | 2.498 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1···O3 | 0.95 | 2.77 | 3.704 (4) | 168.2 |
C16—H16···N2 | 0.95 | 2.79 | 3.690 (4) | 157.3 |
C30—H30···N5 | 0.95 | 2.81 | 3.734 (4) | 163.2 |
C31—H31···O2 | 0.95 | 2.70 | 3.617 (5) | 163.0 |
La1—N1 | 2.5083 (18) | La1—N9 | 2.4843 (18) |
La1—N3 | 2.5658 (19) | La1—O1 | 2.5926 (18) |
La1—N4 | 2.507 (2) | La1—O2 | 2.6404 (17) |
La1—N6 | 2.547 (2) | La1—O3 | 2.5792 (15) |
La1—N7 | 2.6016 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···N7 | 0.95 | 2.67 | 3.614 (3) | 172.8 |
C17—H17···N3 | 0.95 | 2.75 | 3.696 (3) | 177.6 |
C42—H42···N4 | 0.95 | 2.75 | 3.632 (3) | 154.3 |
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The structural chemistry of anionic five-membered nitrogen heterocyclic ligands, especially pyrazolate and 1,2,4-triazolate ligands, has received much of attention because of the structural diversity and variety of coordination modes of these compounds (Zheng et al., 2003; Kobrsi et al., 2005, 2006; Werrett et al., 2011). Pyrazolate ligands are among the most versatile of ligands, with 20 different coordination modes identified so far (Halcrow, 2009). 1,2,4-Triazolate ligands are frequently used to construct metal–organic frameworks (MOFs) with various transition metal ions (Yang et al., 2007, 2009; Mahata et al., 2009; Wei et al., 2010). However, to the best of our knowledge, there is only one reported example of a lanthanide complex containing 1,2,4-triazolate anions, namely the tetranuclear complex [Cp'2Yb(µ-η1:η2-Tz)]4.2THF (Tz = C2H2N3 and Cp' = CH3C5H4; Zhang et al., 2007). Monomeric lanthanide complexes are typically obtained in the presence of sterically demanding ligands. We report here the synthesis and crystal structures of two monomeric lanthanum complexes containing η2-3,5-diphenylpyrazolate (Ph2Pz) and η2-3,5-diphenyl-1,2,4-triazolate (Ph2Tz) ligands, namely tris(3,5-diphenylpyrazolato-κ2N,N')tris(tetrahydrofuran-κO)lanthanum(III) tetrahydrofuran monosolvate, (I), and tris(3,5-diphenyl-1,2,4-triazolato-κ2N1,N2)tris(tetrahydrofuran-κO)lanthanum(III), (II).
Complex (I) crystallizes as a monomeric complex with three η2-Ph2Pz ligands and three coordinated tetrahydrofuran (THF) molecules in the asymmetric unit (Fig. 1), together with one solvent molecule of THF, while (II) is monomeric with three η2-Ph2Tz ligands and three coordinated THF molecules, and no solvent (Fig. 2). The average La—N [2.531 (3) Å] and La—O [2.612 (2) Å] bond lengths in (I) do not differ significantly from those of (II) [La—N = 2.535 (2) Å and La—O = 2.603 (2) Å] (Tables 1 and 3). The coordination geometries about atom La1 in both (I) and (II) can be described as distorted octahedral if the centres of the N—N bonds are treated as monodentate donors (Pfeiffer et al., 1999). However, complex (I) has a mer-distorted octahedral geometry, while complex (II) has a fac-distorted geometry (Fig. 3). There are a few other lanthanide complexes reported so far with the formula [ML3X3] (M = lanthanide, X = THF and L = pyrazolate or pseudo-pyrazolate ligands), for instance [Nd(η2-Ph2Pz)3(THF)3].THF (Cosgriff et al., 1993) and [Sm(η2-N,N-3,5-Ph2dp)3(THF)3].THF (3,5-Ph2dp = 3,5-diphenyl-1,2,4-diazaphospholide; Pi et al., 2008); both of these are isostructural with (I). All of the complexes with a mer configuration are solvated with THF in the crystal structure, while (II), having a fac configuration, is not solvated.
Since bonding between lanthanide ions and ligands is highly electrostatic and nondirectional, the coordination geometries of lanthanide complexes are often very irregular, depending mainly on steric factors associated with the ligands (Marques et al., 2002; Aspinall, 2007). From this viewpoint, the structure of (II) might be expected to be similar to that of (I). It has been demonstrated recently that intramolecular noncovalent interactions also play important roles in the geometries of the metal centres of lanthanide complexes (Yuasa et al., 2011) and we suggest that the stability of complexes (I) and (II) could depend on intramolecular C—H···N/O interactions, in addition to steric factors. In both (I) and (II), C—H···N/O interactions are formed between the ligands (Tables 2 and 4). In (I), one of the η2-Ph2Pz ligands (containing atoms H16 and H30) forms C—H···N interactions with the triazole rings of the other two η2-Ph2Pz ligands, while the other two η2-Ph2Pz ligands form C—H···O interactions with the THF ligands (Fig. 4). One η2-Ph2Pz ligand forms a short C1—H1···O3 interaction and a much longer C15—H15···O2 contact (H···O = 3.22 Å), while another η2-Ph2Pz ligand forms a short C31—H31···O2 interaction and no apparent contact with atom O3. In (II), the fac coordination geometry permits each of the η2-Ph2Tz ligands to form one short C—H···N contact in a threefold cyclic arrangement (Fig. 5). All of the C—H···O contacts to the THF ligands in (II) are much longer (H···O > 3 Å).
Although C—H···N/O interactions are generally considered to be weak, they appear to have an impact on the La—N bond lengths. For all three η2-Ph2Tz ligands in (II), the two La—N bonds have significantly different lengths (Table 3), and the shorter length in each case is at the same end of the ligand as the C—H···N contact. In (I), a similar asymmetry in the La—N bond lengths is observed for the two η2-Ph2Pz ligands forming C—H···O contacts, while the ligand forming C—H···N contacts at both of its ends (H16 and H30) displays the most symmetrical La—N distances (La1—N3/N4; Table 1). It has previously been reported that weak C—H···N interactions produce asymmetric η2-bonding between five-membered heterocyclic ligands and Ba2+ or K+ ions (Kobrsi et al., 2005, 2006).