Tetrakis(μ-2,3-dimethoxybenzoato)bis[(2,2′-bipyridine)(2,3-dimethoxybenzoato)lanthanum(III)]

The title compound, tetrakis(μ-2,3-di­methoxy­benzoato)-κ⁴O:O′;κ⁶O,O′:O′-bis[(2,2′-bi­pyridine-N,N′)(2,3-di­methoxy­benzoato-O,O′)lanthanum(III)], [La₂(2,3-DMOBA)₆(2,2′-bpy)₂], where 2,3-DMOBA is 2,3-di­methoxy­benzoate (C₉H₉O₄) and 2,2′-bpy is 2,2′-bi­pyridine (C₁₀H₈N₂), is a dimer with a centre of inversion between the La atoms bridged by four carboxyl­ate ligands. The central La atom is ennea-coordinated and has a distorted monocapped square-antiprism geometry.

S1. Comment

Lanthanoid(III) carboxylates have been widely studied in recent years due to the variety of structural types and their potential uses as fluorescent sensors. In ennea-coordinated lanthanoid(III) complexes, the central metal atom is in a monocapped square antiprism or a tricapped trigonal prism geometry. The geometries of the complexes are thought to depend on the size of the ligand compared with that of the metal atom, as well as on the substituted groups of the carboxylate. Herein, we report the preparation and crystal structure of the title compound, (I). \sch

Complex (I) is a centrosymmetric dimer, with a centre of inversion between the metal atoms, bridged by four carboxylate ligands (Fig. 1). Each La atom is coordinated with seven O atoms of five different carboxylate ligands and two N atoms of one 2,2'-bipyridine ligand. They adopt a distorted monocapped square antiprism arrangement; atoms O22, O31, O32 and N2, and O12, O21ⁱ, O32ⁱ and N1, form lower and upper square planes with mean deviations of 0.0041 (4) and 0.1832 (4) Å, respectively, with a dihedral angle between them of 6.32 (3)°; atom O11 caps the upper plane (Fig. 2) [symmetry code (i): 1 - x, -y, -z]. A similar coordination environment has been previously observed for lanthanoid(III) complexes such as Pr₂(pivalate)₆(2,2'-bpy)₂ (Pisaresky et al., 1995), La₂(propionato)₆(2,2'-bpy)₂ (Brodkin et al., 1996), Ce₂(CH₃COO)₆(phen)₂ (phen is phenanthroline?; Panagiotopoulos et al., 1995) and Sm₂(PhCOO)₆(phen)₂ (Niu et al., 1999).

The carboxylate ligands adopt three different coordination modes in the crystal of (I): O11—C11—O12 groups are in a chelating mode in which two O atoms coordinate to the same La atom, forming a four-membered ring, O21—C21—O22 groups are in a bridging mode in which two O atoms coordinate to two different La atoms, forming a conventional carboxylate bridge, and O31—C31—O32 groups are in a bridging-chelating mode in which two O atoms chelate one La atom and one of the two O atoms is also linked to another La atom at the same time, to form a tridentate bridge.

In the chelating mode, the two C—O bond lengths of the carboxylate (C11—O11 and C11—O12) are not significantly different; the longer C—O bond has the longer La—O bond length (La1—O11), while the double-bonded O atom of the carboxyl group bonds with the La atom more strongly (La1—O12).

In the bridging mode, the two C—O bond lengths of the carboxylate (C21—O21 and C21—O22) are also not significantly different; the longer C—O bond has the shorter La—O bond length (La1—O21ⁱ), and this single-bonded O atom of the carboxyl group bonds with the La atom more strongly.

In the bridging-chelating mode, the two C—O bond lengths of the carboxylate (C31—O31 and C31—O32) are significantly different. This shows that the C—O double bond is localized. The O atom of the longer C—O bond bridges two La atoms (La1—O32 and La1ⁱ—O32), the O atom of the shorter C—O bond coordinates to one of the La atoms to form a chelating ring (La1—O31), and the single-bonded O atom of the carboxyl group (O32) bonds with the La atom more (not less?) strongly.

The 2,2'-bipyridine ligand chelates to the La atom to form a five-membered ring. The two pyrindine ring planes are not coplanar, the dihedral angle being 9.9 (3)°. The La—N bond lengths are comparable with the corresponding values found in the analogous complexes La₂(propionato)₆(2,2'-bpy)₂ (Brodkin et al., 1996) and La₂(Cl₃CCOO)₆(2,2'-bpy)₂ (Cheng et al., 1994).

S2. Experimental

2,3-Dimethoxybenzonic acid (3 mmol, 510 mg) and 2,2'-bpy (1 mmol, 156 mg) were dissolved in ethanol (25 ml). The pH of the solution was adjusted to 7 with 2M NaOH solution. To the resulting solution was added La(NO₃)₃·6H₂O (1 mmol, 433 mg) in water (5 ml). The reaction was stirred for 4 h at 343 K. A white precipitate was formed. Crystals of (I) suitable for X-ray analysis were obtained from the mother liquor at room temperature after a few days. Analysis found: C 52.61, H 4.34, N 3.14%; calculated for C₇₄H₇₆La₂N₄O₂₄: C 52.99, H 4.57, N 3.34%.

S3. Refinement

H atoms were placed at calculated positions and refined in riding mode, with C—H = 0.93–0.96 Å and U_iso(H) = 1.2U_eq(C). Final difference Fourier maps showed the highest and lowest electron densities to be 1.519 and -1.665 e Å^-3, respectively, which were too close to the La atom position to be suitable for the accommodation of any additional atoms.

Computing details

Data collection: XSCANS (Siemens, 1991); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens, 1994); software used to prepare material for publication: SHELXTL (Siemens, 1995).

Figures

	Fig. 1. The molecular structure of (I) showing 30% probability displacement ellipsoids and the atom-numbering scheme. H atoms have been omitted for clarity.
	Fig. 2. A schematic representation of the coordination geometry of the La atom [symmetry code (i): 1 - x, -y, -z].

tetrakis(µ-2,3-dimethoxybenzoato)-κ⁴O:O';κ⁶O,O':O'- bis[(2,2'-bipyridine-N,N')(2,3-dimethoxybenzoato-O,O')lanthanum(III)]

Crystal data

[La2(C10H8N2)2(C9H9O4)6]	Z = 1
Mr = 1677.16	F(000) = 848
Triclinic, P1	Dx = 1.531 Mg m^−3
a = 11.0203 (11) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.2390 (13) Å	Cell parameters from 25 reflections
c = 15.3540 (15) Å	θ = 5–16°
α = 66.785 (7)°	µ = 1.24 mm^−1
β = 83.551 (5)°	T = 293 K
γ = 72.854 (8)°	Block, colourless
V = 1818.6 (3) Å^3	0.60 × 0.45 × 0.28 mm

Data collection

Siemens P4 diffractometer	5830 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.016
Graphite monochromator	θmax = 25.0°, θmin = 1.9°
ω scans	h = −1→13
Absorption correction: empirical (using intensity measurements) via ψ scans (North et al., 1968)	k = −13→13
Tmin = 0.521, Tmax = 0.707	l = −18→18
7311 measured reflections	3 standard reflections every 97 reflections
6235 independent reflections	intensity decay: none

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.091	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0687P)^2 + 0.353P] where P = (Fo^2 + 2Fc^2)/3
6235 reflections	(Δ/σ)max = 0.001
469 parameters	Δρmax = 1.52 e Å^−3
0 restraints	Δρmin = −1.67 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
La1	0.392754 (15)	0.130686 (13)	0.050872 (11)	0.03542 (9)
O11	0.1572 (2)	0.1418 (3)	0.08551 (17)	0.0538 (6)
O12	0.2742 (2)	0.1012 (3)	0.20616 (18)	0.0714 (8)
O13	0.0606 (3)	0.2505 (3)	0.2879 (2)	0.0793 (9)
O14	−0.1218 (5)	0.1942 (5)	0.4136 (3)	0.1263 (17)
O21	0.6797 (2)	−0.1708 (2)	0.10864 (16)	0.0516 (6)
O22	0.5609 (2)	−0.0300 (2)	0.16341 (16)	0.0510 (6)
O23	0.6269 (2)	−0.0892 (2)	0.34954 (16)	0.0515 (6)
O24	0.6438 (3)	−0.2674 (3)	0.52023 (18)	0.0780 (9)
O31	0.5387 (3)	0.2592 (3)	−0.0579 (3)	0.0864 (11)
O32	0.6066 (2)	0.0718 (2)	−0.05300 (18)	0.0519 (6)
O33	0.6586 (2)	0.3322 (3)	−0.26066 (18)	0.0610 (7)
O34	0.8765 (3)	0.3893 (3)	−0.3227 (2)	0.0878 (10)
N1	0.2689 (3)	0.3697 (2)	0.00326 (19)	0.0453 (6)
N2	0.4664 (3)	0.2671 (3)	0.1267 (2)	0.0487 (7)
C1	0.1733 (4)	0.4179 (4)	−0.0585 (3)	0.0558 (9)
H1A	0.1535	0.3667	−0.0829	0.067*
C2	0.1025 (4)	0.5391 (4)	−0.0881 (3)	0.0635 (10)
H2A	0.0384	0.5698	−0.1330	0.076*
C3	0.1281 (5)	0.6137 (4)	−0.0502 (3)	0.0728 (12)
H3A	0.0801	0.6956	−0.0674	0.087*
C4	0.2262 (5)	0.5655 (4)	0.0140 (3)	0.0664 (11)
H4A	0.2446	0.6147	0.0411	0.080*
C5	0.2977 (3)	0.4433 (3)	0.0383 (2)	0.0468 (8)
C6	0.4103 (3)	0.3885 (3)	0.1024 (2)	0.0455 (7)
C7	0.4588 (4)	0.4613 (4)	0.1314 (3)	0.0583 (9)
H7A	0.4178	0.5450	0.1142	0.070*
C8	0.5665 (5)	0.4098 (4)	0.1852 (3)	0.0687 (11)
H8A	0.5998	0.4579	0.2048	0.082*
C9	0.6247 (4)	0.2865 (4)	0.2099 (3)	0.0695 (11)
H9A	0.6988	0.2492	0.2461	0.083*
C10	0.5711 (4)	0.2182 (4)	0.1799 (3)	0.0609 (10)
H10A	0.6101	0.1340	0.1977	0.073*
C11	0.1711 (3)	0.1145 (3)	0.1718 (2)	0.0448 (7)
C12	0.0610 (3)	0.0917 (3)	0.2372 (2)	0.0501 (8)
C13	0.0172 (4)	0.1529 (4)	0.2972 (3)	0.0601 (9)
C14	−0.0824 (5)	0.1210 (5)	0.3619 (3)	0.0814 (15)
C15	−0.1307 (5)	0.0290 (6)	0.3619 (4)	0.0948 (18)
H15A	−0.1932	0.0052	0.4053	0.114*
C16	−0.0888 (5)	−0.0266 (6)	0.2999 (5)	0.0988 (19)
H16A	−0.1245	−0.0865	0.2996	0.119*
C17	0.0049 (4)	0.0036 (5)	0.2379 (4)	0.0754 (12)
H17A	0.0321	−0.0353	0.1952	0.090*
C18	0.1453 (7)	0.2272 (7)	0.3607 (5)	0.128 (3)
H18A	0.1709	0.3004	0.3487	0.192*
H18B	0.2188	0.1609	0.3617	0.192*
H18C	0.1033	0.2048	0.4209	0.192*
C19	−0.2107 (9)	0.1593 (9)	0.4864 (5)	0.204 (6)
H19A	−0.2323	0.2158	0.5184	0.306*
H19B	−0.1740	0.0772	0.5309	0.306*
H19C	−0.2859	0.1612	0.4591	0.306*
C21	0.6309 (3)	−0.1357 (3)	0.1747 (2)	0.0422 (7)
C22	0.6542 (3)	−0.2332 (3)	0.2739 (2)	0.0446 (7)
C23	0.6430 (3)	−0.2068 (3)	0.3551 (2)	0.0457 (7)
C24	0.6562 (4)	−0.3031 (4)	0.4446 (3)	0.0572 (9)
C25	0.6805 (5)	−0.4234 (4)	0.4523 (3)	0.0738 (12)
H25A	0.6864	−0.4865	0.5119	0.089*
C26	0.6963 (5)	−0.4511 (4)	0.3719 (3)	0.0752 (12)
H26A	0.7161	−0.5329	0.3775	0.090*
C27	0.6825 (4)	−0.3568 (3)	0.2831 (3)	0.0610 (10)
H27A	0.6920	−0.3755	0.2292	0.073*
C28	0.5037 (5)	−0.0302 (4)	0.3748 (3)	0.0712 (12)
H28A	0.5012	0.0515	0.3688	0.107*
H28B	0.4858	−0.0774	0.4391	0.107*
H28C	0.4413	−0.0251	0.3335	0.107*
C29	0.6109 (6)	−0.3504 (6)	0.6092 (3)	0.0993 (18)
H29A	0.6050	−0.3159	0.6564	0.149*
H29B	0.6751	−0.4282	0.6276	0.149*
H29C	0.5307	−0.3629	0.6035	0.149*
C31	0.6227 (3)	0.1762 (3)	−0.0729 (2)	0.0437 (7)
C32	0.7491 (3)	0.1985 (3)	−0.1083 (2)	0.0424 (7)
C33	0.7610 (3)	0.2793 (3)	−0.2003 (2)	0.0470 (8)
C34	0.8759 (4)	0.3082 (4)	−0.2305 (3)	0.0553 (9)
C35	0.9772 (4)	0.2562 (4)	−0.1689 (3)	0.0613 (10)
H35A	1.0536	0.2759	−0.1887	0.074*
C36	0.9658 (4)	0.1752 (4)	−0.0779 (3)	0.0611 (10)
H36A	1.0347	0.1403	−0.0366	0.073*
C37	0.8536 (4)	0.1456 (3)	−0.0476 (3)	0.0548 (9)
H37A	0.8472	0.0900	0.0138	0.066*
C38	0.6579 (5)	0.2670 (5)	−0.3188 (3)	0.0834 (14)
H38A	0.5846	0.3080	−0.3594	0.125*
H38B	0.6555	0.1842	−0.2797	0.125*
H38C	0.7334	0.2647	−0.3567	0.125*
C39	0.9903 (6)	0.4249 (7)	−0.3561 (5)	0.139 (3)
H39A	0.9792	0.4815	−0.4210	0.209*
H39B	1.0588	0.3530	−0.3514	0.209*
H39C	1.0095	0.4644	−0.3183	0.209*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
La1	0.02989 (12)	0.03774 (12)	0.03722 (12)	−0.00840 (8)	0.00257 (7)	−0.01405 (8)
O11	0.0339 (12)	0.0808 (16)	0.0447 (13)	−0.0154 (11)	−0.0010 (10)	−0.0217 (12)
O12	0.0375 (14)	0.132 (3)	0.0482 (15)	−0.0278 (16)	0.0036 (11)	−0.0356 (16)
O13	0.079 (2)	0.084 (2)	0.079 (2)	−0.0082 (17)	−0.0095 (17)	−0.0432 (17)
O14	0.120 (4)	0.153 (4)	0.081 (2)	0.002 (3)	0.035 (2)	−0.056 (3)
O21	0.0490 (14)	0.0546 (13)	0.0434 (13)	−0.0035 (11)	−0.0013 (10)	−0.0181 (10)
O22	0.0505 (14)	0.0508 (13)	0.0433 (12)	0.0001 (11)	−0.0086 (10)	−0.0171 (10)
O23	0.0513 (14)	0.0611 (14)	0.0457 (13)	−0.0206 (11)	−0.0004 (11)	−0.0201 (11)
O24	0.097 (2)	0.094 (2)	0.0357 (13)	−0.0362 (19)	−0.0011 (14)	−0.0100 (13)
O31	0.077 (2)	0.0551 (15)	0.136 (3)	−0.0353 (15)	0.065 (2)	−0.0508 (18)
O32	0.0451 (14)	0.0456 (12)	0.0670 (15)	−0.0164 (11)	0.0043 (11)	−0.0218 (11)
O33	0.0366 (13)	0.0829 (18)	0.0520 (15)	−0.0112 (12)	−0.0042 (11)	−0.0165 (13)
O34	0.0512 (17)	0.111 (2)	0.0688 (19)	−0.0337 (17)	0.0125 (14)	0.0037 (17)
N1	0.0361 (15)	0.0445 (14)	0.0511 (16)	−0.0052 (12)	0.0016 (12)	−0.0185 (12)
N2	0.0488 (17)	0.0477 (15)	0.0501 (16)	−0.0145 (13)	−0.0065 (13)	−0.0163 (12)
C1	0.043 (2)	0.061 (2)	0.058 (2)	−0.0055 (17)	−0.0048 (16)	−0.0220 (17)
C2	0.047 (2)	0.063 (2)	0.065 (2)	0.0000 (18)	−0.0091 (18)	−0.0165 (19)
C3	0.070 (3)	0.048 (2)	0.081 (3)	0.0094 (19)	−0.008 (2)	−0.020 (2)
C4	0.075 (3)	0.049 (2)	0.071 (3)	−0.006 (2)	−0.006 (2)	−0.0263 (19)
C5	0.0476 (19)	0.0434 (16)	0.0460 (18)	−0.0101 (15)	0.0089 (15)	−0.0176 (14)
C6	0.0486 (19)	0.0444 (16)	0.0448 (17)	−0.0175 (15)	0.0077 (14)	−0.0167 (14)
C7	0.072 (3)	0.053 (2)	0.056 (2)	−0.0261 (19)	0.0051 (19)	−0.0214 (17)
C8	0.082 (3)	0.077 (3)	0.064 (2)	−0.043 (2)	0.001 (2)	−0.030 (2)
C9	0.067 (3)	0.085 (3)	0.064 (2)	−0.033 (2)	−0.016 (2)	−0.023 (2)
C10	0.062 (2)	0.054 (2)	0.064 (2)	−0.0160 (18)	−0.0175 (19)	−0.0147 (17)
C11	0.0324 (17)	0.0559 (18)	0.0461 (18)	−0.0120 (14)	0.0032 (14)	−0.0203 (15)
C12	0.0318 (17)	0.064 (2)	0.0465 (18)	−0.0086 (15)	0.0031 (14)	−0.0174 (16)
C13	0.047 (2)	0.071 (2)	0.051 (2)	−0.0023 (18)	−0.0034 (16)	−0.0198 (18)
C14	0.058 (3)	0.105 (4)	0.053 (2)	0.012 (3)	0.009 (2)	−0.028 (2)
C15	0.055 (3)	0.099 (4)	0.097 (4)	−0.019 (3)	0.024 (3)	−0.012 (3)
C16	0.060 (3)	0.102 (4)	0.133 (5)	−0.038 (3)	0.030 (3)	−0.040 (4)
C17	0.051 (2)	0.087 (3)	0.096 (3)	−0.029 (2)	0.014 (2)	−0.039 (3)
C18	0.135 (6)	0.148 (6)	0.129 (5)	−0.022 (5)	−0.045 (5)	−0.081 (5)
C19	0.190 (9)	0.225 (10)	0.097 (5)	0.030 (8)	0.087 (6)	−0.042 (6)
C21	0.0351 (16)	0.0499 (17)	0.0413 (17)	−0.0108 (14)	−0.0054 (13)	−0.0164 (14)
C22	0.0338 (16)	0.0498 (17)	0.0452 (17)	−0.0102 (14)	−0.0024 (13)	−0.0132 (14)
C23	0.0360 (17)	0.0557 (18)	0.0419 (17)	−0.0151 (14)	−0.0023 (13)	−0.0124 (14)
C24	0.049 (2)	0.070 (2)	0.0426 (18)	−0.0196 (18)	−0.0038 (16)	−0.0084 (16)
C25	0.077 (3)	0.062 (2)	0.055 (2)	−0.017 (2)	−0.007 (2)	0.0074 (19)
C26	0.086 (3)	0.052 (2)	0.072 (3)	−0.019 (2)	−0.002 (2)	−0.0073 (19)
C27	0.064 (2)	0.054 (2)	0.061 (2)	−0.0126 (18)	−0.0018 (19)	−0.0185 (17)
C28	0.071 (3)	0.080 (3)	0.059 (2)	−0.012 (2)	0.011 (2)	−0.031 (2)
C29	0.105 (4)	0.119 (4)	0.048 (2)	−0.034 (4)	0.014 (3)	−0.007 (3)
C31	0.0488 (19)	0.0414 (16)	0.0419 (17)	−0.0176 (15)	0.0079 (14)	−0.0153 (13)
C32	0.0430 (18)	0.0430 (16)	0.0455 (17)	−0.0162 (14)	0.0050 (14)	−0.0192 (13)
C33	0.0318 (17)	0.0589 (19)	0.0481 (18)	−0.0135 (15)	−0.0011 (14)	−0.0170 (15)
C34	0.0375 (19)	0.066 (2)	0.056 (2)	−0.0195 (17)	0.0047 (16)	−0.0139 (17)
C35	0.0373 (19)	0.067 (2)	0.082 (3)	−0.0175 (17)	−0.0016 (18)	−0.028 (2)
C36	0.046 (2)	0.065 (2)	0.075 (3)	−0.0022 (18)	−0.0210 (19)	−0.033 (2)
C37	0.061 (2)	0.0510 (18)	0.0491 (19)	−0.0092 (17)	−0.0064 (17)	−0.0181 (15)
C38	0.067 (3)	0.128 (4)	0.061 (3)	−0.033 (3)	−0.008 (2)	−0.034 (3)
C39	0.072 (4)	0.161 (6)	0.129 (5)	−0.056 (4)	0.034 (4)	0.010 (5)

Geometric parameters (Å, º)

La1—O11	2.565 (2)	C21—C22	1.512 (4)
La1—O12	2.534 (3)	C22—C23	1.391 (5)
La1—O21^i	2.477 (2)	C22—C27	1.403 (5)
La1—O22	2.486 (2)	C23—C24	1.402 (5)
La1—O31	2.582 (3)	C24—C25	1.375 (6)
La1—O32	2.770 (2)	C25—C26	1.384 (7)
La1—O32^i	2.463 (2)	C26—C27	1.384 (6)
La1—N1	2.672 (3)	C31—C32	1.499 (5)
La1—N2	2.710 (3)	C32—C33	1.388 (5)
La1—La1^i	4.1125 (5)	C32—C37	1.393 (5)
O11—C11	1.248 (4)	C33—C34	1.395 (5)
O12—C11	1.246 (4)	C34—C35	1.375 (6)
O13—C13	1.366 (5)	C35—C36	1.375 (6)
O13—C18	1.424 (6)	C36—C37	1.371 (6)
O14—C14	1.371 (6)	C1—H1A	0.9300
O14—C19	1.419 (8)	C2—H2A	0.9300
O21—C21	1.259 (4)	C3—H3A	0.9300
O21—La1^i	2.477 (2)	C4—H4A	0.9300
O22—C21	1.251 (4)	C7—H7A	0.9300
O23—C23	1.366 (4)	C8—H8A	0.9300
O23—C28	1.428 (5)	C9—H9A	0.9300
O24—C24	1.374 (5)	C10—H10A	0.9300
O24—C29	1.429 (5)	C15—H15A	0.9300
O31—C31	1.233 (4)	C16—H16A	0.9300
O32—C31	1.253 (4)	C17—H17A	0.9300
O32—La1^i	2.463 (2)	C18—H18A	0.9600
O33—C33	1.372 (4)	C18—H18B	0.9600
O33—C38	1.414 (6)	C18—H18C	0.9600
O34—C34	1.372 (5)	C19—H19A	0.9600
O34—C39	1.424 (6)	C19—H19B	0.9600
N1—C1	1.332 (5)	C19—H19C	0.9600
N1—C5	1.338 (4)	C25—H25A	0.9300
N2—C10	1.332 (5)	C26—H26A	0.9300
N2—C6	1.342 (4)	C27—H27A	0.9300
C1—C2	1.372 (5)	C28—H28A	0.9600
C2—C3	1.363 (6)	C28—H28B	0.9600
C3—C4	1.376 (6)	C28—H28C	0.9600
C4—C5	1.388 (5)	C29—H29A	0.9600
C5—C6	1.490 (5)	C29—H29B	0.9600
C6—C7	1.387 (5)	C29—H29C	0.9600
C7—C8	1.362 (6)	C35—H35A	0.9300
C8—C9	1.366 (7)	C36—H36A	0.9300
C9—C10	1.384 (5)	C37—H37A	0.9300
C11—C12	1.505 (5)	C38—H38A	0.9600
C12—C13	1.367 (5)	C38—H38B	0.9600
C12—C17	1.389 (6)	C38—H38C	0.9600
C13—C14	1.430 (6)	C39—H39A	0.9600
C14—C15	1.379 (8)	C39—H39B	0.9600
C15—C16	1.345 (9)	C39—H39C	0.9600
C16—C17	1.355 (7)
O32^i—La1—O21^i	74.06 (8)	C12—C13—C14	119.1 (4)
O32^i—La1—O22	72.13 (8)	O14—C14—C15	128.4 (5)
O21^i—La1—O22	135.31 (8)	O14—C14—C13	112.8 (5)
O32^i—La1—O12	93.87 (10)	C15—C14—C13	118.8 (4)
O21^i—La1—O12	131.05 (8)	C16—C15—C14	120.9 (5)
O22—La1—O12	79.79 (9)	C15—C16—C17	120.7 (6)
O32^i—La1—O11	80.62 (8)	C16—C17—C12	121.0 (5)
O21^i—La1—O11	80.34 (8)	O22—C21—O21	125.0 (3)
O22—La1—O11	121.10 (8)	O22—C21—C22	118.9 (3)
O12—La1—O11	50.73 (8)	O21—C21—C22	116.0 (3)
O32^i—La1—O31	122.89 (8)	C23—C22—C27	119.2 (3)
O21^i—La1—O31	78.20 (11)	C23—C22—C21	123.9 (3)
O22—La1—O31	96.62 (11)	C27—C22—C21	116.9 (3)
O12—La1—O31	140.34 (11)	O23—C23—C22	121.2 (3)
O11—La1—O31	141.26 (10)	O23—C23—C24	119.0 (3)
O32^i—La1—N1	147.22 (9)	C22—C23—C24	119.7 (3)
O21^i—La1—N1	82.14 (8)	O24—C24—C25	124.5 (3)
O22—La1—N1	139.01 (8)	O24—C24—C23	115.2 (4)
O12—La1—N1	84.92 (10)	C25—C24—C23	120.3 (4)
O11—La1—N1	73.33 (9)	C24—C25—C26	120.4 (4)
O31—La1—N1	72.07 (9)	C25—C26—C27	119.9 (4)
O32^i—La1—N2	150.22 (9)	C26—C27—C22	120.5 (4)
O21^i—La1—N2	134.07 (8)	O31—C31—O32	121.0 (3)
O22—La1—N2	78.79 (8)	O31—C31—C32	118.9 (3)
O12—La1—N2	74.50 (9)	O32—C31—C32	119.9 (3)
O11—La1—N2	110.04 (9)	O31—C31—La1	56.80 (18)
O31—La1—N2	66.13 (10)	O32—C31—La1	65.59 (18)
N1—La1—N2	60.47 (8)	C32—C31—La1	163.4 (2)
O32^i—La1—O32	76.58 (8)	C33—C32—C37	119.1 (3)
O21^i—La1—O32	72.50 (8)	C33—C32—C31	120.1 (3)
O22—La1—O32	71.91 (8)	C37—C32—C31	120.6 (3)
O12—La1—O32	151.67 (9)	O33—C33—C32	119.6 (3)
O11—La1—O32	148.33 (8)	O33—C33—C34	120.4 (3)
O31—La1—O32	47.55 (8)	C32—C33—C34	120.0 (3)
N1—La1—O32	117.49 (8)	O34—C34—C35	125.3 (3)
N2—La1—O32	100.59 (8)	O34—C34—C33	114.9 (3)
O32^i—La1—C11	86.06 (9)	C35—C34—C33	119.9 (3)
O21^i—La1—C11	105.70 (9)	C34—C35—C36	120.2 (4)
O22—La1—C11	100.24 (9)	C37—C36—C35	120.5 (3)
O12—La1—C11	25.34 (9)	C36—C37—C32	120.3 (3)
O11—La1—C11	25.43 (8)	N1—C1—H1A	118.3
O31—La1—C11	150.01 (9)	C2—C1—H1A	118.3
N1—La1—C11	78.95 (9)	C3—C2—H2A	120.7
N2—La1—C11	93.03 (9)	C1—C2—H2A	120.7
O32—La1—C11	162.40 (9)	C2—C3—H3A	120.6
O32^i—La1—C31	100.78 (8)	C4—C3—H3A	120.6
O21^i—La1—C31	76.90 (9)	C3—C4—H4A	120.0
O22—La1—C31	81.62 (9)	C5—C4—H4A	120.0
O12—La1—C31	151.48 (9)	C8—C7—H7A	120.1
O11—La1—C31	155.78 (9)	C6—C7—H7A	120.1
O31—La1—C31	23.56 (9)	C7—C8—H8A	120.5
N1—La1—C31	95.28 (8)	C9—C8—H8A	120.5
N2—La1—C31	80.82 (9)	C8—C9—H9A	120.8
O32—La1—C31	24.33 (8)	C10—C9—H9A	120.8
C11—La1—C31	173.15 (9)	N2—C10—H10A	118.3
O32^i—La1—La1^i	40.94 (6)	C9—C10—H10A	118.3
O21^i—La1—La1^i	68.46 (5)	C16—C15—H15A	119.6
O22—La1—La1^i	66.85 (5)	C14—C15—H15A	119.6
O12—La1—La1^i	129.30 (8)	C15—C16—H16A	119.7
O11—La1—La1^i	118.41 (6)	C17—C16—H16A	119.7
O31—La1—La1^i	82.57 (6)	C16—C17—H17A	119.5
N1—La1—La1^i	144.55 (6)	C12—C17—H17A	119.5
N2—La1—La1^i	130.07 (6)	O13—C18—H18A	109.5
O32—La1—La1^i	35.64 (5)	O13—C18—H18B	109.5
C11—La1—La1^i	126.93 (7)	H18A—C18—H18B	109.5
C31—La1—La1^i	59.88 (6)	O13—C18—H18C	109.5
C11—O11—La1	92.64 (19)	H18A—C18—H18C	109.5
C11—O12—La1	94.1 (2)	H18B—C18—H18C	109.5
C13—O13—C18	115.0 (4)	O14—C19—H19A	109.5
C14—O14—C19	115.8 (7)	O14—C19—H19B	109.5
C21—O21—La1^i	134.4 (2)	H19A—C19—H19B	109.5
C21—O22—La1	137.4 (2)	O14—C19—H19C	109.5
C23—O23—C28	115.3 (3)	H19A—C19—H19C	109.5
C24—O24—C29	116.9 (4)	H19B—C19—H19C	109.5
C31—O31—La1	99.6 (2)	C24—C25—H25A	119.8
C31—O32—La1^i	165.3 (2)	C26—C25—H25A	119.8
C31—O32—La1	90.1 (2)	C25—C26—H26A	120.1
La1^i—O32—La1	103.42 (8)	C27—C26—H26A	120.1
C33—O33—C38	113.0 (3)	C26—C27—H27A	119.8
C34—O34—C39	117.1 (4)	C22—C27—H27A	119.8
C1—N1—C5	118.4 (3)	O23—C28—H28A	109.5
C1—N1—La1	118.2 (2)	O23—C28—H28B	109.5
C5—N1—La1	123.5 (2)	H28A—C28—H28B	109.5
C10—N2—C6	117.7 (3)	O23—C28—H28C	109.5
C10—N2—La1	119.9 (2)	H28A—C28—H28C	109.5
C6—N2—La1	121.8 (2)	H28B—C28—H28C	109.5
N1—C1—C2	123.5 (4)	O24—C29—H29A	109.5
C3—C2—C1	118.6 (4)	O24—C29—H29B	109.5
C2—C3—C4	118.8 (4)	H29A—C29—H29B	109.5
C3—C4—C5	119.9 (4)	O24—C29—H29C	109.5
N1—C5—C4	120.8 (4)	H29A—C29—H29C	109.5
N1—C5—C6	116.9 (3)	H29B—C29—H29C	109.5
C4—C5—C6	122.3 (3)	C34—C35—H35A	119.9
N2—C6—C7	121.6 (3)	C36—C35—H35A	119.9
N2—C6—C5	117.1 (3)	C37—C36—H36A	119.7
C7—C6—C5	121.2 (3)	C35—C36—H36A	119.7
C8—C7—C6	119.8 (4)	C36—C37—H37A	119.8
C7—C8—C9	119.1 (4)	C32—C37—H37A	119.8
C8—C9—C10	118.5 (4)	O33—C38—H38A	109.5
N2—C10—C9	123.3 (4)	O33—C38—H38B	109.5
O12—C11—O11	122.3 (3)	H38A—C38—H38B	109.5
O12—C11—C12	118.8 (3)	O33—C38—H38C	109.5
O11—C11—C12	118.8 (3)	H38A—C38—H38C	109.5
O12—C11—La1	60.53 (18)	H38B—C38—H38C	109.5
O11—C11—La1	61.93 (17)	O34—C39—H39A	109.5
C12—C11—La1	174.0 (2)	O34—C39—H39B	109.5
C13—C12—C17	119.5 (4)	H39A—C39—H39B	109.5
C13—C12—C11	122.0 (4)	O34—C39—H39C	109.5
C17—C12—C11	118.6 (4)	H39A—C39—H39C	109.5
O13—C13—C12	119.4 (4)	H39B—C39—H39C	109.5
O13—C13—C14	121.2 (4)

Symmetry code: (i) −x+1, −y, −z.