Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807053640/bv2078sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807053640/bv2078Isup2.hkl |
CCDC reference: 672584
Key indicators
- Single-crystal X-ray study
- T = 100 K
- Mean (C-C) = 0.012 Å
- R factor = 0.048
- wR factor = 0.109
- Data-to-parameter ratio = 18.4
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT413_ALERT_2_B Short Inter XH3 .. XHn H1" .. H18 .. 2.03 Ang.
Alert level C PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density .... 2.44 PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 3.43 Ratio PLAT222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) ... 3.97 Ratio PLAT342_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 12
Alert level G REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 26.37 From the CIF: _reflns_number_total 6249 Count of symmetry unique reflns 3340 Completeness (_total/calc) 187.10% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 2909 Fraction of Friedel pairs measured 0.871 Are heavy atom types Z>Si present yes PLAT033_ALERT_2_G Flack Parameter Value Deviates 2 * su from zero. 0.05 PLAT794_ALERT_5_G Check Predicted Bond Valency for La (3) 0.96 PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 1
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 4 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 4 ALERT type 2 Indicator that the structure model may be wrong or deficient 3 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
checkCIF publication errors
Alert level A PUBL022_ALERT_1_A There is a mismatched ~ on line 156 The title compound, [La(C~8~H~9)~3~(C~9~H~21~N~3~)], incorporating a If you require a ~ then it should be escaped with a \, i.e. \~ Otherwise there must be a matching closing ~, e.g. C~2~H~4~
1 ALERT level A = Data missing that is essential or data in wrong format 0 ALERT level G = General alerts. Data that may be required is missing
All preparations were performed under an inert nitrogen atmosphere, using standard Schlenk and glovebox techniques. Solid La(CH2Ph-4-Me)3[(THF)3] (134.0 mg, 200.0 µmol) was reacted with a solution of [Me3—TACN] (34.0 mg, 200 µmol) in THF (2 ml). The formed red solution was left to stand over night at -30 °C, after which time yellow-orange crystals of the title compound deposit (90 mg, 72%)·1H NMR (500 MHz, THF-d8, 20°C): δ 6.66 (t, 3JHH = 8.1 Hz, 6 H, m-Ar), 6.14 (d, 3JHH = 8.1 Hz, 6 H, o-Ar), 2.70 (m, 6 H, NCH2), 2.60 (m, 6 H, NCH2), 2.37 (s, 9H, NMe), 2.10 (s, 9 H, Me), 1.29 (s, 6 H, LaCH2). 13C NMR (125.7 MHz, THF-d8, 20°C): δ 150.7 (Ar Cipso), 131.8 (d, 1JCH = 153.3 Hz, Ar CH), 125.9 (Ar CMe), 123.6 (d, 1JCH = 152.0 Hz, Ar CH), 68.7 (t, 1JCH = 125.0 Hz, LaCH2), 56.6 (t, 1JCH = 134.8 Hz, NCH2), 48.2 (q, 1JCH = 134.8 Hz, NMe), 21.8 (q, 1JCH = 125.2 Hz, ArMe). Anal. Calcd for C33H48N3La: C 63.35; H 7.73; N 6.72. Found: C, 63.20; H, 7.68; N, 6.45.
The structure was solved by Patterson methods and extension of the model was accomplished by direct methods applied to difference structure factors using the program DIRDIF. The positional and anisotropic displacement parameters for the non-hydrogen atoms were refined. The hydrogen atoms were generated by geometrical considerations, constrained to idealized geometries, and allowed to ride on their carrier atoms with an isotropic displacement parameter related to the equivalent displacement parameter of their carrier atoms. The methyl-groups were refined as rigid groups, which were allowed to rotate freely.
Data collection: SMART (Bruker, 2006); cell refinement: SAINT-Plus (Bruker, 2006); data reduction: SAINT-Plus (Bruker, 2006); program(s) used to solve structure: DIRDIF99 (Beurskens et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: PLATON (Spek, 2003).
Fig. 1. Perspective ORTEP drawing of I. Displacement ellipsoids for non-H are represented at the 50% probability level. The H-atoms have been omitted to improve clarity. |
[La(C8H9)3(C9H21N3)] | The final unit cell was obtained from the xyz centroids of
5692 reflections after integration using the SAINTPLUS
software package (Bruker, 2006). Reduced cell calculations did not indicate any higher metric lattice symmetry and examination of the finalatomic coordinates of the structure did not yield extra symmetry elements [Le Page, Y. (1987). J. Appl. Cryst. 20, 264–269; Le Page, Y. (1988). J. Appl. Cryst. 21, 983–984; Spek, A. L. (1988). J. Appl. Cryst. 21, 578–579]. |
Mr = 625.67 | Dx = 1.323 Mg m−3 |
Orthorhombic, Pna21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2c -2n | Cell parameters from 5692 reflections |
a = 16.094 (2) Å | θ = 2.4–27.2° |
b = 13.472 (1) Å | µ = 1.38 mm−1 |
c = 14.488 (1) Å | T = 100 K |
V = 3141.3 (5) Å3 | Platelet, orange |
Z = 4 | 0.22 × 0.15 × 0.06 mm |
F(000) = 1296 |
Bruker SMART APEX CCD area-detector diffractometer | 6249 independent reflections |
Radiation source: fine focus sealed Siemens Mo tube | 4265 reflections with I > 2σ(I) |
Parallel mounted graphite monochromator | Rint = 0.093 |
Detector resolution: 66.06 pixels mm-1 | θmax = 26.4°, θmin = 2.5° |
ϕ and ω scans | h = −20→20 |
Absorption correction: multi-scan (SADABS; Bruker, 2006)) | k = −16→16 |
Tmin = 0.758, Tmax = 0.920 | l = −18→17 |
23512 measured reflections |
Refinement on F2 | Secondary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.048 | H-atom parameters constrained |
wR(F2) = 0.109 | w = 1/[σ2(Fo2) + (0.0532P)2 + 0.P] where P = (Fo2 + 2Fc2)/3 |
S = 0.97 | (Δ/σ)max = 0.001 |
6249 reflections | Δρmax = 1.47 e Å−3 |
340 parameters | Δρmin = −0.60 e Å−3 |
1 restraint | Absolute structure: Flack & Bernardinelli (1999, 2000), 2909 Friedel pairs |
Primary atom site location: heavy-atom method | Absolute structure parameter: 0.05 (2) |
[La(C8H9)3(C9H21N3)] | V = 3141.3 (5) Å3 |
Mr = 625.67 | Z = 4 |
Orthorhombic, Pna21 | Mo Kα radiation |
a = 16.094 (2) Å | µ = 1.38 mm−1 |
b = 13.472 (1) Å | T = 100 K |
c = 14.488 (1) Å | 0.22 × 0.15 × 0.06 mm |
Bruker SMART APEX CCD area-detector diffractometer | 6249 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2006)) | 4265 reflections with I > 2σ(I) |
Tmin = 0.758, Tmax = 0.920 | Rint = 0.093 |
23512 measured reflections |
R[F2 > 2σ(F2)] = 0.048 | H-atom parameters constrained |
wR(F2) = 0.109 | Δρmax = 1.47 e Å−3 |
S = 0.97 | Δρmin = −0.60 e Å−3 |
6249 reflections | Absolute structure: Flack & Bernardinelli (1999, 2000), 2909 Friedel pairs |
340 parameters | Absolute structure parameter: 0.05 (2) |
1 restraint |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles |
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 | ||
La | 0.42537 (2) | 0.58635 (2) | 0.50450 (4) | 0.0211 (1) | |
N1 | 0.5365 (4) | 0.6802 (5) | 0.3935 (5) | 0.026 (2) | |
N2 | 0.5294 (4) | 0.7266 (6) | 0.5891 (5) | 0.027 (3) | |
N3 | 0.5890 (4) | 0.5310 (5) | 0.5298 (4) | 0.025 (2) | |
C1 | 0.4963 (4) | 0.6822 (6) | 0.3013 (5) | 0.029 (3) | |
C2 | 0.5419 (5) | 0.7849 (6) | 0.4269 (6) | 0.024 (3) | |
C3 | 0.5758 (4) | 0.7908 (5) | 0.5244 (5) | 0.023 (3) | |
C4 | 0.4736 (4) | 0.7884 (6) | 0.6465 (5) | 0.034 (3) | |
C5 | 0.5867 (5) | 0.6692 (7) | 0.6479 (6) | 0.030 (3) | |
C6 | 0.6392 (5) | 0.5957 (6) | 0.5938 (6) | 0.027 (3) | |
C7 | 0.5891 (4) | 0.4283 (5) | 0.5652 (5) | 0.032 (3) | |
C8 | 0.6227 (5) | 0.5317 (6) | 0.4373 (6) | 0.028 (3) | |
C9 | 0.6199 (5) | 0.6331 (7) | 0.3894 (6) | 0.027 (3) | |
C10 | 0.3210 (4) | 0.7356 (5) | 0.4818 (5) | 0.030 (3) | |
C11 | 0.2747 (4) | 0.6733 (6) | 0.4198 (5) | 0.026 (3) | |
C12 | 0.2381 (4) | 0.5834 (5) | 0.4513 (5) | 0.023 (2) | |
C13 | 0.1999 (4) | 0.5183 (6) | 0.3904 (6) | 0.032 (3) | |
C14 | 0.1981 (6) | 0.5344 (8) | 0.2965 (7) | 0.032 (3) | |
C15 | 0.2339 (5) | 0.6229 (7) | 0.2639 (5) | 0.032 (3) | |
C16 | 0.2709 (4) | 0.6885 (6) | 0.3221 (5) | 0.031 (3) | |
C17 | 0.1569 (5) | 0.4621 (8) | 0.2326 (6) | 0.055 (4) | |
C18 | 0.4079 (4) | 0.5330 (7) | 0.6762 (6) | 0.039 (3) | |
C19 | 0.3228 (4) | 0.4991 (6) | 0.6723 (5) | 0.030 (3) | |
C20 | 0.2566 (5) | 0.5528 (7) | 0.7110 (5) | 0.033 (3) | |
C21 | 0.1759 (6) | 0.5205 (9) | 0.7018 (7) | 0.037 (3) | |
C22 | 0.1554 (5) | 0.4338 (7) | 0.6528 (6) | 0.040 (3) | |
C23 | 0.2200 (6) | 0.3807 (7) | 0.6145 (6) | 0.046 (3) | |
C24 | 0.3022 (5) | 0.4114 (6) | 0.6238 (5) | 0.036 (3) | |
C25 | 0.0657 (6) | 0.4015 (9) | 0.6432 (8) | 0.072 (4) | |
C26 | 0.4194 (4) | 0.4447 (5) | 0.3766 (5) | 0.026 (2) | |
C27 | 0.4138 (4) | 0.3371 (5) | 0.3910 (5) | 0.021 (2) | |
C28 | 0.4841 (5) | 0.2750 (6) | 0.3899 (5) | 0.031 (3) | |
C29 | 0.4791 (5) | 0.1733 (6) | 0.4079 (5) | 0.034 (3) | |
C30 | 0.4029 (5) | 0.1277 (7) | 0.4265 (6) | 0.038 (3) | |
C31 | 0.3335 (5) | 0.1875 (6) | 0.4267 (5) | 0.035 (3) | |
C32 | 0.3384 (4) | 0.2881 (6) | 0.4098 (5) | 0.029 (3) | |
C33 | 0.3974 (6) | 0.0178 (6) | 0.4438 (7) | 0.055 (4) | |
H1 | 0.53078 | 0.72056 | 0.25841 | 0.0434* | |
H1' | 0.44138 | 0.71308 | 0.30625 | 0.0434* | |
H1" | 0.49031 | 0.61416 | 0.27820 | 0.0434* | |
H2 | 0.48600 | 0.81541 | 0.42505 | 0.0293* | |
H2' | 0.57850 | 0.82323 | 0.38504 | 0.0293* | |
H3 | 0.63494 | 0.77068 | 0.52416 | 0.0279* | |
H3' | 0.57277 | 0.86035 | 0.54611 | 0.0279* | |
H4 | 0.43657 | 0.74540 | 0.68233 | 0.0510* | |
H4' | 0.44036 | 0.83164 | 0.60649 | 0.0510* | |
H4" | 0.50685 | 0.82916 | 0.68859 | 0.0510* | |
H5 | 0.55402 | 0.63267 | 0.69473 | 0.0359* | |
H5' | 0.62387 | 0.71578 | 0.68081 | 0.0359* | |
H6 | 0.68080 | 0.63280 | 0.55709 | 0.0319* | |
H6' | 0.66970 | 0.55285 | 0.63775 | 0.0319* | |
H7 | 0.55386 | 0.38668 | 0.52597 | 0.0471* | |
H7' | 0.56762 | 0.42763 | 0.62852 | 0.0471* | |
H7" | 0.64602 | 0.40238 | 0.56477 | 0.0471* | |
H8 | 0.59143 | 0.48335 | 0.39933 | 0.0336* | |
H8' | 0.68119 | 0.50912 | 0.43990 | 0.0336* | |
H9 | 0.66090 | 0.67770 | 0.41886 | 0.0327* | |
H9' | 0.63612 | 0.62481 | 0.32392 | 0.0327* | |
H10 | 0.29025 | 0.75419 | 0.53844 | 0.0358* | |
H10' | 0.34600 | 0.79464 | 0.45204 | 0.0358* | |
H12 | 0.23978 | 0.56764 | 0.51519 | 0.0272* | |
H13 | 0.17403 | 0.46042 | 0.41431 | 0.0385* | |
H15 | 0.23209 | 0.63725 | 0.19969 | 0.0384* | |
H16 | 0.29529 | 0.74670 | 0.29695 | 0.0372* | |
H17 | 0.18329 | 0.39693 | 0.23883 | 0.0829* | |
H17' | 0.16258 | 0.48543 | 0.16883 | 0.0829* | |
H17" | 0.09784 | 0.45682 | 0.24834 | 0.0829* | |
H18 | 0.44667 | 0.47909 | 0.69341 | 0.0472* | |
H18' | 0.41477 | 0.58965 | 0.71908 | 0.0472* | |
H20 | 0.26771 | 0.61225 | 0.74396 | 0.0393* | |
H21 | 0.13254 | 0.55797 | 0.72952 | 0.0446* | |
H23 | 0.20818 | 0.32177 | 0.58104 | 0.0551* | |
H24 | 0.34527 | 0.37269 | 0.59700 | 0.0434* | |
H25 | 0.06367 | 0.33119 | 0.62588 | 0.1081* | |
H25' | 0.03851 | 0.44133 | 0.59537 | 0.1081* | |
H25" | 0.03692 | 0.41096 | 0.70214 | 0.1081* | |
H26 | 0.37140 | 0.46186 | 0.33690 | 0.0314* | |
H26' | 0.46948 | 0.45477 | 0.33802 | 0.0314* | |
H28 | 0.53683 | 0.30329 | 0.37646 | 0.0374* | |
H29 | 0.52835 | 0.13446 | 0.40751 | 0.0415* | |
H31 | 0.28070 | 0.15862 | 0.43891 | 0.0414* | |
H32 | 0.28870 | 0.32608 | 0.41078 | 0.0344* | |
H33 | 0.35714 | −0.01173 | 0.40115 | 0.0816* | |
H33' | 0.37950 | 0.00605 | 0.50751 | 0.0816* | |
H33" | 0.45208 | −0.01251 | 0.43400 | 0.0816* |
U11 | U22 | U33 | U12 | U13 | U23 | |
La | 0.0182 (1) | 0.0200 (2) | 0.0252 (2) | 0.0003 (2) | −0.0014 (4) | 0.0005 (4) |
N1 | 0.024 (4) | 0.022 (4) | 0.031 (4) | −0.004 (3) | 0.000 (3) | −0.003 (3) |
N2 | 0.025 (4) | 0.033 (5) | 0.022 (4) | −0.003 (4) | 0.004 (3) | −0.002 (4) |
N3 | 0.025 (3) | 0.024 (4) | 0.025 (5) | 0.001 (2) | −0.002 (2) | −0.001 (3) |
C1 | 0.036 (4) | 0.026 (5) | 0.025 (4) | −0.005 (3) | −0.007 (3) | −0.002 (4) |
C2 | 0.029 (4) | 0.014 (5) | 0.030 (5) | −0.002 (3) | 0.002 (4) | −0.006 (4) |
C3 | 0.023 (3) | 0.016 (3) | 0.030 (8) | −0.001 (3) | 0.007 (3) | −0.007 (3) |
C4 | 0.030 (4) | 0.034 (5) | 0.038 (5) | 0.005 (4) | −0.001 (4) | −0.009 (4) |
C5 | 0.024 (5) | 0.039 (6) | 0.027 (5) | −0.011 (4) | 0.003 (4) | −0.011 (4) |
C6 | 0.018 (4) | 0.031 (6) | 0.031 (5) | 0.001 (4) | −0.008 (3) | 0.009 (4) |
C7 | 0.037 (4) | 0.026 (5) | 0.032 (5) | 0.004 (3) | −0.002 (3) | 0.002 (4) |
C8 | 0.020 (4) | 0.022 (5) | 0.042 (6) | −0.003 (4) | −0.005 (4) | 0.001 (4) |
C9 | 0.028 (5) | 0.028 (6) | 0.026 (5) | −0.001 (4) | 0.004 (4) | −0.003 (4) |
C10 | 0.018 (3) | 0.024 (4) | 0.048 (8) | 0.005 (3) | 0.001 (3) | 0.005 (4) |
C11 | 0.018 (3) | 0.026 (5) | 0.034 (5) | 0.008 (3) | −0.006 (3) | −0.001 (4) |
C12 | 0.017 (3) | 0.028 (4) | 0.023 (4) | 0.005 (3) | −0.008 (3) | 0.013 (4) |
C13 | 0.020 (4) | 0.027 (5) | 0.049 (6) | 0.002 (3) | 0.004 (4) | 0.000 (4) |
C14 | 0.027 (5) | 0.043 (7) | 0.026 (5) | 0.000 (4) | −0.001 (4) | −0.014 (5) |
C15 | 0.032 (4) | 0.050 (6) | 0.014 (4) | 0.011 (4) | −0.001 (3) | 0.011 (4) |
C16 | 0.016 (4) | 0.036 (5) | 0.042 (5) | 0.000 (3) | 0.003 (4) | 0.008 (4) |
C17 | 0.031 (5) | 0.082 (8) | 0.052 (6) | −0.006 (5) | −0.002 (4) | −0.019 (6) |
C18 | 0.035 (5) | 0.050 (6) | 0.033 (5) | 0.002 (4) | −0.004 (4) | 0.009 (4) |
C19 | 0.034 (4) | 0.038 (5) | 0.019 (4) | −0.001 (4) | 0.001 (3) | 0.012 (4) |
C20 | 0.039 (5) | 0.041 (6) | 0.019 (5) | −0.003 (4) | 0.000 (4) | 0.008 (4) |
C21 | 0.029 (5) | 0.053 (7) | 0.030 (6) | 0.011 (5) | 0.006 (4) | 0.002 (5) |
C22 | 0.043 (5) | 0.045 (6) | 0.031 (5) | −0.006 (4) | −0.004 (4) | 0.016 (4) |
C23 | 0.075 (7) | 0.034 (6) | 0.029 (5) | −0.007 (5) | −0.014 (5) | 0.007 (4) |
C24 | 0.051 (5) | 0.035 (5) | 0.023 (4) | 0.017 (4) | 0.003 (4) | 0.010 (4) |
C25 | 0.055 (6) | 0.090 (9) | 0.071 (8) | −0.026 (6) | −0.017 (5) | 0.038 (6) |
C26 | 0.027 (4) | 0.016 (4) | 0.035 (4) | 0.001 (3) | −0.001 (3) | −0.003 (3) |
C27 | 0.028 (4) | 0.019 (4) | 0.017 (4) | 0.004 (3) | −0.003 (3) | −0.005 (3) |
C28 | 0.037 (4) | 0.028 (5) | 0.029 (4) | −0.001 (3) | 0.003 (3) | 0.000 (4) |
C29 | 0.050 (5) | 0.025 (5) | 0.028 (5) | 0.008 (4) | −0.009 (4) | −0.007 (4) |
C30 | 0.059 (6) | 0.025 (5) | 0.031 (5) | 0.000 (4) | 0.001 (4) | 0.001 (4) |
C31 | 0.039 (5) | 0.028 (5) | 0.037 (5) | −0.005 (4) | 0.001 (4) | 0.005 (4) |
C32 | 0.026 (4) | 0.025 (5) | 0.035 (5) | 0.002 (3) | 0.000 (3) | 0.001 (4) |
C33 | 0.087 (7) | 0.032 (6) | 0.045 (6) | 0.003 (5) | −0.013 (5) | 0.002 (5) |
La—N1 | 2.717 (7) | C1—H1' | 0.9800 |
La—N2 | 2.806 (7) | C1—H1" | 0.9800 |
La—N3 | 2.761 (6) | C2—H2 | 0.9900 |
La—C10 | 2.641 (7) | C2—H2' | 0.9900 |
La—C11 | 2.959 (7) | C3—H3 | 0.9900 |
La—C12 | 3.111 (7) | C3—H3' | 0.9900 |
La—C18 | 2.605 (9) | C4—H4 | 0.9800 |
La—C19 | 3.165 (7) | C4—H4' | 0.9800 |
La—C26 | 2.662 (7) | C4—H4" | 0.9800 |
La—C27 | 3.744 (7) | C5—H5 | 0.9900 |
N1—C1 | 1.485 (10) | C5—H5' | 0.9900 |
N1—C2 | 1.494 (11) | C6—H6 | 0.9900 |
N1—C9 | 1.486 (11) | C6—H6' | 0.9900 |
N2—C3 | 1.478 (10) | C7—H7 | 0.9800 |
N2—C4 | 1.480 (10) | C7—H7' | 0.9800 |
N2—C5 | 1.475 (11) | C7—H7" | 0.9800 |
N3—C6 | 1.507 (10) | C8—H8 | 0.9900 |
N3—C7 | 1.476 (9) | C8—H8' | 0.9900 |
N3—C8 | 1.446 (10) | C9—H9 | 0.9900 |
C2—C3 | 1.516 (11) | C9—H9' | 0.9900 |
C5—C6 | 1.520 (12) | C10—H10 | 0.9900 |
C8—C9 | 1.533 (12) | C10—H10' | 0.9900 |
C10—C11 | 1.438 (10) | C12—H12 | 0.9500 |
C11—C12 | 1.422 (10) | C13—H13 | 0.9500 |
C11—C16 | 1.432 (10) | C15—H15 | 0.9500 |
C12—C13 | 1.388 (11) | C16—H16 | 0.9500 |
C13—C14 | 1.378 (13) | C17—H17 | 0.9800 |
C14—C15 | 1.406 (14) | C17—H17' | 0.9800 |
C14—C17 | 1.499 (14) | C17—H17" | 0.9800 |
C15—C16 | 1.359 (11) | C18—H18 | 0.9900 |
C18—C19 | 1.445 (9) | C18—H18' | 0.9900 |
C19—C20 | 1.405 (11) | C20—H20 | 0.9500 |
C19—C24 | 1.414 (11) | C21—H21 | 0.9500 |
C20—C21 | 1.376 (13) | C23—H23 | 0.9500 |
C21—C22 | 1.406 (15) | C24—H24 | 0.9500 |
C22—C23 | 1.379 (13) | C25—H25 | 0.9800 |
C22—C25 | 1.514 (13) | C25—H25' | 0.9800 |
C23—C24 | 1.393 (13) | C25—H25" | 0.9800 |
C26—C27 | 1.467 (10) | C26—H26 | 0.9900 |
C27—C28 | 1.407 (10) | C26—H26' | 0.9900 |
C27—C32 | 1.408 (9) | C28—H28 | 0.9500 |
C28—C29 | 1.397 (11) | C29—H29 | 0.9500 |
C29—C30 | 1.398 (12) | C31—H31 | 0.9500 |
C30—C31 | 1.377 (12) | C32—H32 | 0.9500 |
C30—C33 | 1.504 (12) | C33—H33 | 0.9800 |
C31—C32 | 1.380 (11) | C33—H33' | 0.9800 |
C1—H1 | 0.9800 | C33—H33" | 0.9800 |
La···H24 | 3.4300 | H3···C12i | 2.7800 |
N1···N2 | 2.904 (10) | H3···H10i | 2.5300 |
N1···N3 | 2.942 (9) | H3'···H4' | 2.3400 |
N1···C3 | 2.493 (10) | H3'···H4" | 2.3600 |
N1···C8 | 2.516 (11) | H3'···C12i | 3.0900 |
N2···N1 | 2.904 (10) | H4···C18 | 2.9000 |
N2···N3 | 2.933 (10) | H4···H5 | 2.4300 |
N2···C2 | 2.486 (11) | H4···H18' | 2.1900 |
N2···C6 | 2.497 (11) | H4'···C10 | 2.9400 |
N3···N1 | 2.942 (9) | H4'···H3' | 2.3400 |
N3···N2 | 2.933 (10) | H4'···C17ii | 2.9800 |
N3···C5 | 2.529 (11) | H4"···H3' | 2.3600 |
N3···C9 | 2.505 (11) | H4"···H5' | 2.4300 |
C3···C12i | 3.289 (9) | H4"···H17"ii | 2.5600 |
C3···C11i | 3.575 (9) | H4"···H21i | 2.6000 |
C4···C17ii | 3.383 (12) | H5···C18 | 2.7200 |
C5···C27iii | 3.523 (11) | H5···H4 | 2.4300 |
C9···C16i | 3.554 (11) | H5···H18' | 2.3400 |
C10···C12 | 2.486 (9) | H5···C26iii | 2.8700 |
C10···C4 | 3.497 (10) | H5···C27iii | 2.9200 |
C10···C16 | 2.531 (10) | H5···H26'iii | 2.4200 |
C11···C3iv | 3.575 (9) | H5'···H3 | 2.3900 |
C12···C24 | 3.561 (10) | H5'···H4" | 2.4300 |
C12···C3iv | 3.289 (9) | H6···C3 | 2.7600 |
C16···C9iv | 3.554 (11) | H6···C9 | 2.6200 |
C17···C4v | 3.383 (12) | H6···H3 | 2.0500 |
C18···C5 | 3.437 (11) | H6···H8' | 2.3800 |
C24···C32 | 3.565 (11) | H6···H9 | 2.1200 |
C24···C12 | 3.561 (10) | H6···C10i | 3.0700 |
C26···C1 | 3.600 (10) | H6···H10i | 2.3400 |
C26···C8 | 3.585 (10) | H6'···H7' | 2.3600 |
C27···C5vi | 3.523 (11) | H6'···H7" | 2.3200 |
C32···C24 | 3.565 (11) | H7···C27 | 3.0600 |
C1···H18vi | 2.8300 | H7···C28 | 2.7200 |
C1···H7'vi | 3.0800 | H7···H8 | 2.3300 |
C2···H33"vii | 3.0900 | H7···H28 | 2.4600 |
C3···H9 | 2.5600 | H7'···C18 | 3.0200 |
C3···H6 | 2.7600 | H7'···H6' | 2.3600 |
C4···H17"ii | 2.9400 | H7'···H18 | 2.2700 |
C4···H18' | 3.0300 | H7'···C1iii | 3.0800 |
C6···H3 | 2.5700 | H7'···H1"iii | 2.4300 |
C6···H9 | 2.7900 | H7"···H6' | 2.3200 |
C7···H18 | 3.0300 | H7"···H8' | 2.3800 |
C8···H26' | 3.0400 | H8···C26 | 2.8400 |
C9···H6 | 2.6200 | H8···H7 | 2.3300 |
C9···H3 | 2.7000 | H8···H26' | 2.1900 |
C10···H4' | 2.9400 | H8'···H6 | 2.3800 |
C10···H2 | 2.9800 | H8'···H7" | 2.3800 |
C10···H3iv | 3.0600 | H9···C3 | 2.5600 |
C10···H9iv | 2.9700 | H9···C6 | 2.7900 |
C10···H6iv | 3.0700 | H9···H2' | 2.4200 |
C11···H10' | 2.0500 | H9···H3 | 2.0200 |
C11···H10 | 2.0500 | H9···H6 | 2.1200 |
C11···H9iv | 2.7200 | H9···C10i | 2.9700 |
C11···H3iv | 2.8100 | H9···C11i | 2.7200 |
C12···H3iv | 2.7800 | H9···C16i | 2.8900 |
C12···H2'iv | 3.0200 | H9'···H1 | 2.3300 |
C12···H3'iv | 3.0900 | H9'···H1" | 2.4400 |
C13···H32 | 2.9700 | H9'···C18vi | 3.1000 |
C13···H26 | 2.9700 | H9'···C19vi | 2.8400 |
C13···H2'iv | 2.9000 | H10···H3iv | 2.5300 |
C14···H2'iv | 3.0000 | H10···H6iv | 2.3400 |
C14···H26 | 3.0100 | H10'···H2 | 2.3000 |
C16···H1' | 2.7700 | H10'···H16 | 2.4800 |
C16···H9iv | 2.8900 | H12···C19 | 2.8000 |
C17···H4'v | 2.9800 | H12···C20 | 2.8600 |
C18···H26'iii | 3.0700 | H12···C21 | 2.9600 |
C18···H1"iii | 2.9700 | H12···C22 | 3.0100 |
C18···H9'iii | 3.1000 | H12···C23 | 2.9200 |
C18···H5 | 2.7200 | H12···C24 | 2.8100 |
C18···H7' | 3.0200 | H13···H32 | 2.5900 |
C18···H4 | 2.9000 | H15···H17' | 2.3700 |
C19···H12 | 2.8000 | H16···H1' | 2.4000 |
C19···H9'iii | 2.8400 | H16···H10' | 2.4800 |
C20···H12 | 2.8600 | H17'···H15 | 2.3700 |
C21···H12 | 2.9600 | H17'···H33'ix | 2.4500 |
C21···H33ii | 2.9700 | H17"···C4v | 2.9400 |
C22···H12 | 3.0100 | H17"···H4"v | 2.5600 |
C23···H12 | 2.9200 | H18···C7 | 3.0300 |
C24···H12 | 2.8100 | H18···H7' | 2.2700 |
C26···H1" | 2.9200 | H18···H24 | 2.5800 |
C26···H5vi | 2.8700 | H18···C1iii | 2.8300 |
C26···H8 | 2.8400 | H18···H1"iii | 2.0300 |
C27···H7 | 3.0600 | H18'···C4 | 3.0300 |
C27···H5vi | 2.9200 | H18'···H4 | 2.1900 |
C28···H7 | 2.7200 | H18'···H5 | 2.3400 |
C30···H21v | 3.0600 | H18'···H20 | 2.4100 |
C32···H24 | 2.9400 | H20···H18' | 2.4100 |
C33···H2viii | 3.0900 | H21···H25" | 2.5400 |
H1···H2' | 2.4200 | H21···C30ii | 3.0600 |
H1···H9' | 2.3300 | H21···H4"iv | 2.6000 |
H1'···C16 | 2.7700 | H23···H25 | 2.4200 |
H1'···H2 | 2.3200 | H24···La | 3.4300 |
H1'···H16 | 2.4000 | H24···C32 | 2.9400 |
H1"···C26 | 2.9200 | H24···H18 | 2.5800 |
H1"···H9' | 2.4400 | H25···H23 | 2.4200 |
H1"···H26' | 2.3400 | H25"···H21 | 2.5400 |
H1"···C18vi | 2.9700 | H26···C13 | 2.9700 |
H1"···H7'vi | 2.4300 | H26···C14 | 3.0100 |
H1"···H18vi | 2.0300 | H26···H32 | 2.5000 |
H2···C10 | 2.9800 | H26'···C8 | 3.0400 |
H2···C33vii | 3.0900 | H26'···H1" | 2.3400 |
H2···H1' | 2.3200 | H26'···H8 | 2.1900 |
H2···H10' | 2.3000 | H26'···H28 | 2.3800 |
H2···H33"vii | 2.3900 | H26'···C18vi | 3.0700 |
H2'···H1 | 2.4200 | H26'···H5vi | 2.4200 |
H2'···H9 | 2.4200 | H28···H7 | 2.4600 |
H2'···C12i | 3.0200 | H28···H26' | 2.3800 |
H2'···C13i | 2.9000 | H29···H33" | 2.3600 |
H2'···C14i | 3.0000 | H32···C13 | 2.9700 |
H3···C6 | 2.5700 | H32···H13 | 2.5900 |
H3···C9 | 2.7000 | H32···H26 | 2.5000 |
H3···H5' | 2.3900 | H33···C21v | 2.9700 |
H3···H6 | 2.0500 | H33'···H17'x | 2.4500 |
H3···H9 | 2.0200 | H33"···C2viii | 3.0900 |
H3···C10i | 3.0600 | H33"···H2viii | 2.3900 |
H3···C11i | 2.8100 | H33"···H29 | 2.3600 |
N1—La—N2 | 63.4 (2) | N2—C3—H3' | 109.00 |
N1—La—N3 | 64.94 (19) | C2—C3—H3 | 109.00 |
N1—La—C10 | 89.5 (2) | C2—C3—H3' | 109.00 |
N1—La—C11 | 96.3 (2) | H3—C3—H3' | 108.00 |
N1—La—C18 | 139.9 (2) | N2—C4—H4 | 110.00 |
N1—La—C26 | 86.9 (2) | N2—C4—H4' | 109.00 |
N2—La—N3 | 63.6 (2) | N2—C4—H4" | 109.00 |
N2—La—C10 | 85.5 (2) | H4—C4—H4' | 109.00 |
N2—La—C11 | 113.8 (2) | H4—C4—H4" | 110.00 |
N2—La—C18 | 80.4 (2) | H4'—C4—H4" | 109.00 |
N2—La—C26 | 143.9 (2) | N2—C5—H5 | 109.00 |
N3—La—C10 | 146.0 (2) | N2—C5—H5' | 109.00 |
N3—La—C11 | 160.62 (19) | C6—C5—H5 | 109.00 |
N3—La—C18 | 84.36 (19) | C6—C5—H5' | 109.00 |
N3—La—C26 | 86.17 (19) | H5—C5—H5' | 108.00 |
C10—La—C11 | 29.0 (2) | N3—C6—H6 | 109.00 |
C10—La—C18 | 105.1 (2) | N3—C6—H6' | 109.00 |
C10—La—C26 | 115.9 (2) | C5—C6—H6 | 109.00 |
C11—La—C18 | 114.6 (2) | C5—C6—H6' | 109.00 |
C11—La—C26 | 88.0 (2) | H6—C6—H6' | 108.00 |
C18—La—C26 | 117.6 (3) | N3—C7—H7 | 110.00 |
La—N1—C1 | 104.7 (4) | N3—C7—H7' | 109.00 |
La—N1—C2 | 106.6 (5) | N3—C7—H7" | 109.00 |
La—N1—C9 | 114.8 (5) | H7—C7—H7' | 109.00 |
C1—N1—C2 | 107.4 (6) | H7—C7—H7" | 109.00 |
C1—N1—C9 | 111.4 (6) | H7'—C7—H7" | 109.00 |
C2—N1—C9 | 111.3 (6) | N3—C8—H8 | 109.00 |
La—N2—C3 | 114.7 (5) | N3—C8—H8' | 109.00 |
La—N2—C4 | 105.2 (4) | C9—C8—H8 | 109.00 |
La—N2—C5 | 105.8 (5) | C9—C8—H8' | 109.00 |
C3—N2—C4 | 109.5 (6) | H8—C8—H8' | 108.00 |
C3—N2—C5 | 110.9 (6) | N1—C9—H9 | 109.00 |
C4—N2—C5 | 110.5 (6) | N1—C9—H9' | 109.00 |
La—N3—C6 | 115.9 (5) | C8—C9—H9 | 109.00 |
La—N3—C7 | 107.5 (4) | C8—C9—H9' | 109.00 |
La—N3—C8 | 103.5 (4) | H9—C9—H9' | 108.00 |
C6—N3—C7 | 109.1 (6) | La—C10—H10 | 114.00 |
C6—N3—C8 | 111.4 (6) | La—C10—H10' | 114.00 |
C7—N3—C8 | 109.1 (6) | C11—C10—H10 | 114.00 |
N1—C2—C3 | 111.9 (6) | C11—C10—H10' | 114.00 |
N2—C3—C2 | 112.2 (6) | H10—C10—H10' | 111.00 |
N2—C5—C6 | 113.1 (7) | C11—C12—H12 | 119.00 |
N3—C6—C5 | 113.3 (6) | C13—C12—H12 | 119.00 |
N3—C8—C9 | 114.5 (7) | C12—C13—H13 | 119.00 |
N1—C9—C8 | 112.9 (7) | C14—C13—H13 | 119.00 |
La—C10—C11 | 87.9 (4) | C14—C15—H15 | 119.00 |
La—C11—C10 | 63.1 (4) | C16—C15—H15 | 119.00 |
La—C11—C12 | 82.5 (4) | C11—C16—H16 | 119.00 |
La—C11—C16 | 120.1 (4) | C15—C16—H16 | 119.00 |
C10—C11—C12 | 120.8 (6) | C14—C17—H17 | 110.00 |
C10—C11—C16 | 123.8 (7) | C14—C17—H17' | 109.00 |
C12—C11—C16 | 114.9 (7) | C14—C17—H17" | 109.00 |
C11—C12—C13 | 121.2 (7) | H17—C17—H17' | 110.00 |
C12—C13—C14 | 122.5 (8) | H17—C17—H17" | 110.00 |
C13—C14—C15 | 117.2 (8) | H17'—C17—H17" | 109.00 |
C13—C14—C17 | 121.1 (9) | La—C18—H18 | 112.00 |
C15—C14—C17 | 121.7 (8) | La—C18—H18' | 112.00 |
C14—C15—C16 | 121.5 (7) | C19—C18—H18 | 112.00 |
C11—C16—C15 | 122.6 (7) | C19—C18—H18' | 112.00 |
La—C18—C19 | 98.8 (5) | H18—C18—H18' | 110.00 |
C18—C19—C20 | 122.7 (7) | C19—C20—H20 | 119.00 |
C18—C19—C24 | 120.4 (7) | C21—C20—H20 | 120.00 |
C20—C19—C24 | 116.8 (7) | C20—C21—H21 | 119.00 |
C19—C20—C21 | 121.0 (8) | C22—C21—H21 | 119.00 |
C20—C21—C22 | 122.2 (9) | C22—C23—H23 | 119.00 |
C21—C22—C23 | 117.2 (8) | C24—C23—H23 | 119.00 |
C21—C22—C25 | 120.6 (8) | C19—C24—H24 | 119.00 |
C23—C22—C25 | 122.2 (9) | C23—C24—H24 | 119.00 |
C22—C23—C24 | 121.6 (8) | C22—C25—H25 | 109.00 |
C19—C24—C23 | 121.3 (7) | C22—C25—H25' | 109.00 |
La—C26—C27 | 127.7 (5) | C22—C25—H25" | 109.00 |
C26—C27—C28 | 122.4 (6) | H25—C25—H25' | 109.00 |
C26—C27—C32 | 122.9 (6) | H25—C25—H25" | 109.00 |
C28—C27—C32 | 114.6 (6) | H25'—C25—H25" | 110.00 |
C27—C28—C29 | 122.3 (7) | La—C26—H26 | 105.00 |
C28—C29—C30 | 121.2 (8) | La—C26—H26' | 105.00 |
C29—C30—C31 | 117.1 (8) | C27—C26—H26 | 105.00 |
C29—C30—C33 | 121.1 (8) | C27—C26—H26' | 105.00 |
C31—C30—C33 | 121.9 (8) | H26—C26—H26' | 106.00 |
C30—C31—C32 | 121.9 (7) | C27—C28—H28 | 119.00 |
C27—C32—C31 | 123.0 (7) | C29—C28—H28 | 119.00 |
N1—C1—H1 | 109.00 | C28—C29—H29 | 119.00 |
N1—C1—H1' | 110.00 | C30—C29—H29 | 119.00 |
N1—C1—H1" | 109.00 | C30—C31—H31 | 119.00 |
H1—C1—H1' | 109.00 | C32—C31—H31 | 119.00 |
H1—C1—H1" | 109.00 | C27—C32—H32 | 118.00 |
H1'—C1—H1" | 109.00 | C31—C32—H32 | 119.00 |
N1—C2—H2 | 109.00 | C30—C33—H33 | 109.00 |
N1—C2—H2' | 109.00 | C30—C33—H33' | 109.00 |
C3—C2—H2 | 109.00 | C30—C33—H33" | 109.00 |
C3—C2—H2' | 109.00 | H33—C33—H33' | 110.00 |
H2—C2—H2' | 108.00 | H33—C33—H33" | 109.00 |
N2—C3—H3 | 109.00 | H33'—C33—H33" | 109.00 |
N2—La—N1—C1 | −150.7 (5) | N2—La—C18—C19 | 147.4 (5) |
N2—La—N1—C2 | −37.0 (5) | N3—La—C18—C19 | −148.5 (5) |
N2—La—N1—C9 | 86.7 (6) | C10—La—C18—C19 | 64.8 (6) |
N3—La—N1—C1 | 137.7 (5) | C11—La—C18—C19 | 35.5 (6) |
N3—La—N1—C2 | −108.7 (5) | C26—La—C18—C19 | −65.8 (6) |
N3—La—N1—C9 | 15.1 (5) | N1—La—C26—C27 | 141.4 (6) |
C10—La—N1—C1 | −65.5 (5) | N2—La—C26—C27 | 108.2 (6) |
C10—La—N1—C2 | 48.2 (5) | N3—La—C26—C27 | 76.4 (5) |
C10—La—N1—C9 | 172.0 (5) | C10—La—C26—C27 | −130.7 (5) |
C11—La—N1—C1 | −37.2 (5) | C11—La—C26—C27 | −122.2 (6) |
C11—La—N1—C2 | 76.5 (5) | C18—La—C26—C27 | −5.2 (6) |
C11—La—N1—C9 | −159.8 (5) | La—N1—C2—C3 | 63.5 (6) |
C18—La—N1—C1 | −178.7 (5) | C1—N1—C2—C3 | 175.3 (6) |
C18—La—N1—C2 | −65.0 (6) | C9—N1—C2—C3 | −62.4 (8) |
C18—La—N1—C9 | 58.8 (7) | La—N1—C9—C8 | 8.8 (8) |
C26—La—N1—C1 | 50.4 (5) | C1—N1—C9—C8 | −110.1 (8) |
C26—La—N1—C2 | 164.1 (5) | C2—N1—C9—C8 | 130.0 (7) |
C26—La—N1—C9 | −72.1 (5) | La—N2—C3—C2 | 14.2 (7) |
N1—La—N2—C3 | 12.5 (4) | C4—N2—C3—C2 | −103.8 (7) |
N1—La—N2—C4 | 132.9 (5) | C5—N2—C3—C2 | 134.0 (7) |
N1—La—N2—C5 | −110.1 (5) | La—N2—C5—C6 | 60.3 (7) |
N3—La—N2—C3 | 86.2 (5) | C3—N2—C5—C6 | −64.7 (9) |
N3—La—N2—C4 | −153.4 (5) | C4—N2—C5—C6 | 173.6 (7) |
N3—La—N2—C5 | −36.4 (5) | La—N3—C6—C5 | 11.0 (8) |
C10—La—N2—C3 | −79.2 (5) | C7—N3—C6—C5 | −110.4 (7) |
C10—La—N2—C4 | 41.2 (5) | C8—N3—C6—C5 | 129.0 (7) |
C10—La—N2—C5 | 158.2 (5) | La—N3—C8—C9 | 61.3 (7) |
C11—La—N2—C3 | −72.5 (5) | C6—N3—C8—C9 | −63.9 (8) |
C11—La—N2—C4 | 47.9 (5) | C7—N3—C8—C9 | 175.5 (6) |
C11—La—N2—C5 | 164.8 (5) | N1—C2—C3—N2 | −53.0 (8) |
C18—La—N2—C3 | 174.7 (5) | N2—C5—C6—N3 | −50.1 (9) |
C18—La—N2—C4 | −64.9 (5) | N3—C8—C9—N1 | −50.4 (9) |
C18—La—N2—C5 | 52.0 (5) | La—C10—C11—C12 | 61.8 (6) |
C26—La—N2—C3 | 50.2 (7) | La—C10—C11—C16 | −109.7 (7) |
C26—La—N2—C4 | 170.6 (4) | La—C11—C12—C13 | −121.6 (6) |
C26—La—N2—C5 | −72.4 (6) | C10—C11—C12—C13 | −174.0 (6) |
N1—La—N3—C6 | 84.9 (5) | C16—C11—C12—C13 | −1.8 (10) |
N1—La—N3—C7 | −152.8 (5) | La—C11—C16—C15 | 97.0 (7) |
N1—La—N3—C8 | −37.4 (4) | C10—C11—C16—C15 | 173.0 (7) |
N2—La—N3—C6 | 13.5 (5) | C12—C11—C16—C15 | 1.1 (10) |
N2—La—N3—C7 | 135.8 (5) | C11—C12—C13—C14 | 2.8 (11) |
N2—La—N3—C8 | −108.8 (5) | C12—C13—C14—C15 | −2.7 (13) |
C10—La—N3—C6 | 40.2 (7) | C12—C13—C14—C17 | 179.5 (8) |
C10—La—N3—C7 | 162.5 (4) | C13—C14—C15—C16 | 1.9 (13) |
C10—La—N3—C8 | −82.1 (6) | C17—C14—C15—C16 | 179.7 (8) |
C18—La—N3—C6 | −68.6 (5) | C14—C15—C16—C11 | −1.2 (12) |
C18—La—N3—C7 | 53.8 (4) | La—C18—C19—C20 | −106.7 (7) |
C18—La—N3—C8 | 169.2 (5) | La—C18—C19—C24 | 69.7 (8) |
C26—La—N3—C6 | 173.2 (5) | C18—C19—C20—C21 | 176.7 (8) |
C26—La—N3—C7 | −64.5 (4) | C24—C19—C20—C21 | 0.2 (12) |
C26—La—N3—C8 | 50.9 (5) | C18—C19—C24—C23 | −176.1 (8) |
N1—La—C10—C11 | 104.1 (4) | C20—C19—C24—C23 | 0.5 (11) |
N2—La—C10—C11 | 167.4 (4) | C19—C20—C21—C22 | −0.8 (14) |
N3—La—C10—C11 | 143.6 (4) | C20—C21—C22—C23 | 0.7 (14) |
C18—La—C10—C11 | −113.8 (4) | C20—C21—C22—C25 | −179.2 (9) |
C26—La—C10—C11 | 17.8 (5) | C21—C22—C23—C24 | 0.0 (13) |
N1—La—C11—C10 | −77.4 (4) | C25—C22—C23—C24 | 179.9 (9) |
N1—La—C11—C12 | 152.4 (4) | C22—C23—C24—C19 | −0.6 (13) |
N1—La—C11—C16 | 37.9 (6) | La—C26—C27—C28 | −96.6 (8) |
N2—La—C11—C10 | −13.7 (5) | La—C26—C27—C32 | 81.4 (8) |
N2—La—C11—C12 | −143.9 (4) | C26—C27—C28—C29 | 176.9 (7) |
N2—La—C11—C16 | 101.6 (6) | C32—C27—C28—C29 | −1.2 (11) |
C10—La—C11—C12 | −130.2 (6) | C26—C27—C32—C31 | −177.5 (7) |
C10—La—C11—C16 | 115.3 (8) | C28—C27—C32—C31 | 0.6 (11) |
C18—La—C11—C10 | 76.4 (5) | C27—C28—C29—C30 | 1.1 (12) |
C18—La—C11—C12 | −53.8 (5) | C28—C29—C30—C31 | −0.3 (12) |
C18—La—C11—C16 | −168.4 (6) | C28—C29—C30—C33 | 178.6 (8) |
C26—La—C11—C10 | −164.0 (4) | C29—C30—C31—C32 | −0.3 (12) |
C26—La—C11—C12 | 65.8 (4) | C33—C30—C31—C32 | −179.3 (8) |
C26—La—C11—C16 | −48.8 (6) | C30—C31—C32—C27 | 0.2 (12) |
N1—La—C18—C19 | 172.5 (4) |
Symmetry codes: (i) x+1/2, −y+3/2, z; (ii) −x+1/2, y+1/2, z+1/2; (iii) −x+1, −y+1, z+1/2; (iv) x−1/2, −y+3/2, z; (v) −x+1/2, y−1/2, z−1/2; (vi) −x+1, −y+1, z−1/2; (vii) x, y+1, z; (viii) x, y−1, z; (ix) −x+1/2, y+1/2, z−1/2; (x) −x+1/2, y−1/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [La(C8H9)3(C9H21N3)] |
Mr | 625.67 |
Crystal system, space group | Orthorhombic, Pna21 |
Temperature (K) | 100 |
a, b, c (Å) | 16.094 (2), 13.472 (1), 14.488 (1) |
V (Å3) | 3141.3 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.38 |
Crystal size (mm) | 0.22 × 0.15 × 0.06 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2006)) |
Tmin, Tmax | 0.758, 0.920 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 23512, 6249, 4265 |
Rint | 0.093 |
(sin θ/λ)max (Å−1) | 0.625 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.109, 0.97 |
No. of reflections | 6249 |
No. of parameters | 340 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.47, −0.60 |
Absolute structure | Flack & Bernardinelli (1999, 2000), 2909 Friedel pairs |
Absolute structure parameter | 0.05 (2) |
Computer programs: SMART (Bruker, 2006), SAINT-Plus (Bruker, 2006), DIRDIF99 (Beurskens et al., 1999), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), PLATON (Spek, 2003).
La—N1 | 2.717 (7) | La—C12 | 3.111 (7) |
La—N2 | 2.806 (7) | La—C18 | 2.605 (9) |
La—N3 | 2.761 (6) | La—C19 | 3.165 (7) |
La—C10 | 2.641 (7) | La—C26 | 2.662 (7) |
La—C11 | 2.959 (7) | La—C27 | 3.744 (7) |
N1—La—N2 | 63.4 (2) | C18—La—C26 | 117.6 (3) |
N1—La—N3 | 64.94 (19) | La—C10—C11 | 87.9 (4) |
N2—La—N3 | 63.6 (2) | La—C18—C19 | 98.8 (5) |
C10—La—C18 | 105.1 (2) | La—C26—C27 | 127.7 (5) |
C10—La—C26 | 115.9 (2) |
Homoleptic trialkyl complexes of the type M(CH2SiMe3)3(THF)n (n = 2, 3) of the group 3 metals and lanthanides are valuable starting materials for organo-rare-earth-metal chemistry. These, however, are only available for the small to medium sized metals (M = Sc—Sm). For the larger metals such as neodymium and lanthanum they can not be isolated. Nevertheless, trialkyl complexes of lanthanum have been reported. Examples are La[CH(SiMe3)2]3 with relatively large alkyls and La(CH2C6H4-2-NMe2)3 with an internal Lewis base. Recently we have described the synthesis, structures and reactivity studies of La(CH2C6H4-4-R)3(THF)3 (R = H, Me). Here we report the molecular structure of (Me3—TACN)La(CH2C6H4-4-Me)3 (Me3—TACN = 1,4.7-trimethyl-l,4,7-triazacyclononane) (I) that has been generated by addition of Me3—TACN to a solution of La(CH2C6H4-4-Me)3(THF)3 in THF. Compound I could be isolated as yellow-orange crystals that are thermally much more stable than its precursor. The asymmetric unit of I contains one formula unit of the title compound shown in Figure 1. As expected the TACN ligand is facially coordinated to the metal center as opposed to the structure of La(CH2C6H4-2-NMe2)3 (Harder, 2005) were the coordination of one of the aminobenzyl ligands is "upside-down". It appears that the fac-κ3 coordination of the TACN ligand increases steric congestion around the metal center compared to La(CH2C6H4-4-Me)3(THF)3. This is evidenced by the bonding mode of the benzyl ligands, of which two are clearly η1 bound to La and one that is bound in a η2-fashion. The former have rather large La—C—C bond angles of 98.8 (5)° and 127.7 (5)°, while the latter has a acute angle of 87.9 (4)°.