Two lanthanum(III) complexes containing η²-pyrazolate and η²-1,2,4-triazolate ligands: intra­molecular C—H...N/O inter­actions and coordination geometries

The lanthanum(III) complexes tris­(3,5-diphenyl­pyrazolato-κ²N,N′)tris­(tetra­hydro­furan-κO)lanthanum(III) tetra­hydro­furan monosolvate, [La(C₁₅H₁₁N₂)₃(C₄H₈O)₃]·C₄H₈O, (I), and tris­(3,5-diphenyl-1,2,4-triazolato-κ²N¹,N²)tris­(tetra­hydrofuran-κO)lanthanum(III), [La(C₁₄H₁₀N₃)₃(C₄H₈O)₃], (II), both contain La^III atoms coordinated by three heterocyclic ligands and three tetra­hydro­furan ligands, but their coordination geometries differ. Complex (I) has a mer-distorted octa­hedral geometry, while complex (II) has a fac-distorted configuration. The difference in the coordination geometries and the existence of asymmetric La—N bonding in the two complexes is associated with intra­molecular C—H...N/O inter­actions between the ligands.

S1. Comment

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).

Related literature

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).

S2. Experimental

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.

S3. Refinement

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 U_iso(H) = 1.2U_eq(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).

Computing details

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).

Figures

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).

(I) tris(3,5-diphenylpyrazolato-κ²N,N')tris(tetrahydrofuran- κO)lanthanum(III) tetrahydrofuran monosolvate

Crystal data

[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) Å^3	Prism, colourless
Z = 4	0.20 × 0.20 × 0.20 mm

Data collection

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

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.029	H-atom parameters constrained
wR(F^2) = 0.054	w = 1/[σ^2(Fo^2) + (0.0219P)^2] where P = (Fo^2 + 2Fc^2)/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)

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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

Hydrogen-bond geometry (Å, º)

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

(II) tris(3,5-diphenyl-1,2,4-triazolato- κ²N¹,N²)tris(tetrahydrofuran- κO)lanthanum(III)

Crystal data

[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) Å^3	0.20 × 0.20 × 0.20 mm
Z = 4

Data collection

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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.063	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.031P)^2 + 2.4124P] where P = (Fo^2 + 2Fc^2)/3
8861 reflections	(Δ/σ)max = 0.001
636 parameters	Δρmax = 0.86 e Å^−3
124 restraints	Δρmin = −0.49 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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

Hydrogen-bond geometry (Å, º)

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