Poly[bis­(μ₄-benzene-1,2-dicar­boxylato)di-μ₃-isonicotinato-di­lanthanum(III)]

In the title compound, [La₂(C₈H₄O₄)₂(C₆H₄NO₂)₂]_n, there are two crystallographically independent La centres, both nine-coordinated in tricapped trigonal prismatic coordination geometries by eight carboxylate O atoms and one pyridyl N atom. The La centres are linked by the carboxyl­ate groups of isonicotinate (IN⁻) and benzene-1,2-dicarboxyl­ate (BDC²⁻) ligands to form La–carboxyl­ate chains, which are further expanded into a three-dimensional framework with nanometre-sized channels by La—N bonds. In the construction of the resultant architecture, in tricapped trigonal prismatic coordination geometries by eight carboxylate O atoms and one pyridyl N atom, while the BDC ligands link to four different cations each, displaying penta- and hepta­dentate chelating–bridging modes, respectively.

S1. Comment

The rational design and construction of metal–organic coordination networks have aroused great interest owing to their intriguing topological architectures and their potential application as functional materials (Meares & Wensel, 1984; Scott & Horrocks, 1992; Reineke et al., 1999; Eddaoudi et al., 2001). Carboxylate lanthanide networks in particular have attracted increasing attention due to their ability to both chelate to a metal and simultaneously bridge to adjacent metals, especially with the larger and less rigid coordination spheres of rare earth elements. To design such coordination polymers, an effective synthetic approach is based on the deliberate combination of appropriate metal ions and multifunctional ligands. Up to now, a variety of multicarboxylate ligands such as pyridinecarboxylate, imidazoledicarboxylic acid and pyrazinecarboxylic acid etc. have been successfully employed as bridging groups to construct one-, two- and three-dimensional networks (Choi et al., 1998; MacGillivray et al., 1998; Evans et al., 1999; Chen et al., 2001; Suresh et al., 2001; Kumagai et al., 2002; Lu & Babb, 2003; Song et al., 2003). Our interest is to explore the cooperativity of mixed organic ligands in coordinating metal centres, and to construct novel coordination polymers with interesting and complicated architectures and topologies. As a continuation of our previous work (Wang, Li et al., 2007; Wang, Huang et al., 2007), here we report a new lanthanide coordination polymer, [La₂(C₆H₄NO₂)₂(C₈H₄O₄)₂]_n, (I), which displays an interesting three-dimensional coordination framework with nanometre-sized channels.

As shown in Fig. 1, the asymmetric unit contains two unique lanthanum(III) atoms, two BDC^2- ligands and two IN^- ligands. The La1 and La2 atoms are both nine-coordinate with distorted tricapped trigonal prismatic geometries. Each La atom is surrounded by two carboxylate O atoms from two IN ligands, six carboxylate O atoms from four BDC ligands and one pyridyl N atom. Interestingly, there are no hydroxo or aqua ligands within the structure, despite the synthesis being carried out in aqueous condition. The La—O bond distances are rather disperse and range from 2.366 (3) to 2.811 (3) Å; the La—N bond distances, however, are more even, with a range of 2.734 (4)-2.782 (4) Å.

The BDC ligands in the asymmetric unit exhibit two types of coordination modes as depicted in Fig. 2: one coordinates four La^III ions in a pentadentate chelating–bridging mode (Fig. 2a), while the other binds to four La^III ions in a heptadentate chelating–bridging mode (Fig. 2b). The IN ligands, however, adopt the same tridentate bridging mode with both carboxylate groups adopting a bimonodenate coordination mode, connecting two La^III ions, while the N atom simultaneously coordinates a third La^III centre (Fig. 2c). On the basis of these connection schemes of the BDC ligands, the lanthanum centres are bridged by oxo groups to form an infinite ladder-like chain along the a axis, with separations between adjacent La^III ions of 4.326 (3), 4.375 (1), 4.499 (7) and 5.572 (1) Å, respectively (Fig. 3a). The remaining coordination sites of La^III ions, however, are filled by the IN ligands. Thus, an interesting one-dimensional La–carboxylate chain with mixed ligands is formed (Fig. 3b), which is somewhat similar to that of {[Ln₂(C₆H₄NO₂)₂(C₈H₄O₄)(OH)₂(H₂O)].H₂O} _n (Ln = Er and Tm) (Wang, Huang et al., 2007). However, what makes the difference is that the pyridyl N atom in that case is free and noncoordinated, thus making no contribution to the expansion of such chains into high-dimensional architecture, whereas the IN ligands in the present structure, acting as tri-connectors, not only afford the carboxylate groups as donor atoms, but also provide their pyridyl N atoms to covalently coordinate the La^III ions. It is worth noting that carboxylate O atoms usually prefer to bind hard lanthanide ions while the softer N atom is ideally suited to bind soft transition metal ions such as Ag and Cu, according to the hard–soft acid–base theory. A search of the literature and the Cambridge Structural Database (CSD, Februry 2009; Allen, 2002) reveals that, despite the existence of several 3d–4f and 4d–4f heterometallic Ln–TM [TM = transition metal?] coordination polymers incorporating the IN ligand (Zhang et al., 2005; Luo et al., 2006; Gu & Xue, 2006; Liu et al., 2006; Gu & Xue, 2007a,b; Cheng et al., 2008; Wang et al., 2008; Lian et al., 2009), the lanthanide frameworks directly assembled from the covalent N—Ln linkage mode are relatively rare (Gu & Xue, 2007a,b). In the title compound, however, adjacent La–carboxylate chains are directly interconnected with each other by the covalent N—Ln linkages, forming a three-dimensional framework and leaving in between rectangular one-dimensional channels parallel to the chains, in part occupied by BDC ligands and with approximate dimensions 12 x 17 Å, as defined by the limiting La centres (Fig. 4).

Related literature

For related literature, see: Chen et al. (2001); Cheng et al. (2008); Choi & Suh (1998); Eddaoudi et al. (2001); Evans et al. (1999); Gu & Xue (2006, 2007a,b); Kumagai et al. (2002); Lian et al. (2009); Liu et al. (2006); Lu & Babb (2003); Luo et al. (2006); MacGillivray et al. (1998); Meares & Wensel (1984); Reineke et al. (1999); Scott & Horrocks (1992); Song et al. (2003); Suresh et al. (2001); Wang, Li et al. (2007); Wang, Huang et al. (2007); Zhang et al. (2005).

S2. Experimental

The title compound was synthesized under mild hydrothermal conditions. Typically, La₂O₃ (0.5 mmol, 0.163 g), HIN (2.30 mmol, 0.284 g), H₂BDC (0.75 mmol, 0.122 g) and H₂O (10 ml) were sealed in a 25 ml Teflon-lined steel autoclave and heated under autogenous pressure at 443 K for 9 d. The yellow prism-like crystals obtained were recovered by filtration, washed with distilled water and dried in air.

S3. Refinement

All H atoms bound to C atoms were positioned geometrically, with C—H = 0.93 Å for aromatic H atoms, and constrained to ride on their parent atoms [U_iso(H) = 1.2U_eq(C)].

Computing details

Data collection: APEX2 (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i) 1 + x, y, z; (ii) 2 - x, 1 - y, 1 - z; (iii) 1 - x, 1 - y, 1 - z; (iv) 1 - x, -1/2 + y, 1/2 - z.
	Fig. 2. Coordination modes of IN and BDC ligands in (I).
	Fig. 3. Different views of the one-dimensional infinite chains constructed from the BDC ligands only (a), and those from IN and BDC mixed ligands (b).
	Fig. 4. A view of the three-dimensional La–carboxylate framework with one-dimensional rectangle-like channels.

Poly[bis(µ₄-benzene-1,2-dicarboxylato)di-µ₃-isonicotinato- dilanthanum(III)]

Crystal data

[La2(C8H4O4)2(C6H4NO2)2]	F(000) = 1632
Mr = 850.25	Dx = 2.124 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 20786 reflections
a = 9.9357 (3) Å	θ = 1.9–26.5°
b = 12.4348 (5) Å	µ = 3.24 mm^−1
c = 21.6047 (3) Å	T = 295 K
β = 95.067 (4)°	Prism, yellow
V = 2658.80 (14) Å^3	0.25 × 0.13 × 0.12 mm
Z = 4

Data collection

Bruker APEXII area-detector diffractometer	5502 independent reflections
Radiation source: fine-focus sealed tube	4666 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.049
ϕ and ω scans	θmax = 26.5°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→12
Tmin = 0.498, Tmax = 0.697	k = −15→15
20786 measured reflections	l = −27→26

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.082	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0352P)^2 + 2.5719P] where P = (Fo^2 + 2Fc^2)/3
5502 reflections	(Δ/σ)max = 0.001
397 parameters	Δρmax = 1.08 e Å^−3
0 restraints	Δρmin = −1.02 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	0.46777 (3)	0.46595 (2)	0.401637 (12)	0.01631 (8)
La2	0.90824 (3)	0.44818 (2)	0.405811 (12)	0.01683 (8)
O1	0.0605 (3)	0.4668 (3)	0.32027 (16)	0.0253 (8)
O2	0.2654 (4)	0.5299 (3)	0.34815 (17)	0.0328 (9)
O3	0.5565 (4)	0.4610 (3)	0.29888 (16)	0.0270 (8)
O4	0.7745 (3)	0.5028 (3)	0.30861 (15)	0.0285 (8)
O5	0.5362 (3)	0.6585 (3)	0.37493 (15)	0.0252 (8)
O6	0.7022 (3)	0.5700 (3)	0.42640 (16)	0.0233 (7)
O7	0.6876 (3)	0.6504 (3)	0.54723 (15)	0.0289 (8)
O8	0.9108 (3)	0.6722 (3)	0.55799 (16)	0.0283 (8)
O9	0.5872 (3)	0.4120 (3)	0.50911 (14)	0.0213 (7)
O10	0.6893 (3)	0.3420 (3)	0.43266 (15)	0.0216 (7)
O11	0.9024 (3)	0.4232 (3)	0.52382 (15)	0.0242 (7)
O12	1.0246 (3)	0.3584 (3)	0.60537 (16)	0.0277 (8)
C1	0.1563 (5)	0.5289 (4)	0.3139 (2)	0.0218 (10)
C2	0.1443 (5)	0.6107 (4)	0.2622 (2)	0.0232 (11)
C3	0.0291 (5)	0.6155 (4)	0.2212 (2)	0.0322 (12)
H3A	−0.0415	0.5671	0.2239	0.039*
C4	0.0227 (5)	0.6943 (4)	0.1764 (2)	0.0333 (13)
H4A	−0.0547	0.6973	0.1489	0.040*
C5	0.2289 (5)	0.7586 (4)	0.2087 (3)	0.0325 (13)
H5A	0.2994	0.8064	0.2041	0.039*
C6	0.2449 (5)	0.6842 (4)	0.2558 (2)	0.0310 (12)
H6A	0.3229	0.6837	0.2830	0.037*
C7	0.6562 (5)	0.5149 (4)	0.2854 (2)	0.0196 (10)
C8	0.6316 (5)	0.6018 (4)	0.2385 (2)	0.0208 (10)
C9	0.5290 (5)	0.5985 (4)	0.1916 (2)	0.0335 (13)
H9A	0.4743	0.5379	0.1863	0.040*
C10	0.5077 (6)	0.6852 (5)	0.1526 (3)	0.0391 (14)
H10A	0.4381	0.6812	0.1210	0.047*
C11	0.6813 (6)	0.7757 (5)	0.2016 (3)	0.0484 (17)
H11A	0.7348	0.8371	0.2054	0.058*
C12	0.7117 (6)	0.6929 (4)	0.2420 (3)	0.0375 (14)
H12A	0.7855	0.6978	0.2716	0.045*
C13	0.6465 (5)	0.6575 (4)	0.4081 (2)	0.0206 (10)
C14	0.7107 (5)	0.7629 (4)	0.4263 (2)	0.0213 (10)
C15	0.6956 (5)	0.8483 (4)	0.3846 (3)	0.0324 (12)
H15A	0.6435	0.8396	0.3470	0.039*
C16	0.7578 (6)	0.9465 (4)	0.3986 (3)	0.0395 (15)
H16A	0.7510	1.0023	0.3699	0.047*
C17	0.8295 (6)	0.9602 (4)	0.4556 (3)	0.0410 (15)
H17A	0.8680	1.0267	0.4660	0.049*
C18	0.8448 (5)	0.8757 (4)	0.4973 (2)	0.0304 (12)
H18A	0.8968	0.8851	0.5348	0.036*
C19	0.7835 (5)	0.7773 (4)	0.4839 (2)	0.0208 (10)
C20	0.7943 (5)	0.6912 (3)	0.5331 (2)	0.0183 (10)
C21	0.6643 (4)	0.3428 (4)	0.4891 (2)	0.0189 (10)
C22	0.7124 (5)	0.2529 (4)	0.5313 (2)	0.0195 (10)
C23	0.6270 (5)	0.1657 (4)	0.5363 (2)	0.0299 (12)
H23A	0.5445	0.1632	0.5124	0.036*
C24	0.6638 (6)	0.0839 (5)	0.5762 (3)	0.0434 (15)
H24A	0.6053	0.0263	0.5799	0.052*
C25	0.7856 (6)	0.0855 (5)	0.6108 (3)	0.0423 (15)
H25A	0.8102	0.0287	0.6375	0.051*
C26	0.8719 (5)	0.1711 (4)	0.6062 (2)	0.0327 (12)
H26A	0.9541	0.1725	0.6304	0.039*
C27	0.8374 (5)	0.2550 (4)	0.5660 (2)	0.0205 (10)
C28	0.9286 (5)	0.3505 (4)	0.5645 (2)	0.0223 (10)
N1	0.1191 (4)	0.7665 (3)	0.16935 (19)	0.0284 (10)
N2	0.5802 (5)	0.7735 (4)	0.1574 (2)	0.0364 (11)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
La1	0.01523 (15)	0.01797 (14)	0.01548 (15)	−0.00097 (10)	−0.00009 (10)	0.00008 (10)
La2	0.01534 (15)	0.01883 (15)	0.01610 (15)	−0.00079 (10)	0.00009 (10)	0.00103 (10)
O1	0.0210 (18)	0.0292 (19)	0.0262 (19)	−0.0026 (15)	0.0052 (15)	0.0046 (15)
O2	0.026 (2)	0.038 (2)	0.033 (2)	−0.0015 (16)	−0.0067 (16)	0.0108 (17)
O3	0.032 (2)	0.0280 (19)	0.0215 (19)	−0.0030 (15)	0.0049 (15)	0.0014 (14)
O4	0.0252 (19)	0.036 (2)	0.0234 (19)	0.0030 (16)	−0.0030 (15)	0.0031 (16)
O5	0.0249 (18)	0.0256 (18)	0.0239 (19)	−0.0046 (14)	−0.0043 (15)	0.0008 (15)
O6	0.0235 (18)	0.0188 (17)	0.0277 (19)	0.0038 (14)	0.0023 (14)	0.0020 (14)
O7	0.0280 (19)	0.034 (2)	0.0251 (19)	−0.0086 (16)	0.0042 (15)	0.0035 (16)
O8	0.0239 (19)	0.0289 (19)	0.031 (2)	0.0036 (15)	−0.0047 (15)	0.0021 (15)
O9	0.0197 (17)	0.0220 (17)	0.0221 (18)	0.0028 (14)	0.0021 (14)	0.0009 (14)
O10	0.0236 (18)	0.0224 (17)	0.0189 (18)	−0.0007 (14)	0.0030 (13)	−0.0017 (14)
O11	0.0251 (18)	0.0218 (17)	0.0256 (19)	−0.0032 (15)	0.0022 (15)	0.0024 (15)
O12	0.0219 (18)	0.0272 (19)	0.032 (2)	−0.0025 (15)	−0.0072 (15)	0.0017 (15)
C1	0.017 (2)	0.029 (3)	0.020 (3)	0.006 (2)	0.0044 (19)	−0.003 (2)
C2	0.026 (3)	0.022 (3)	0.022 (3)	0.000 (2)	0.005 (2)	0.001 (2)
C3	0.023 (3)	0.039 (3)	0.033 (3)	−0.007 (2)	−0.005 (2)	0.007 (2)
C4	0.027 (3)	0.044 (3)	0.026 (3)	−0.010 (2)	−0.011 (2)	0.012 (2)
C5	0.030 (3)	0.029 (3)	0.038 (3)	−0.006 (2)	0.001 (2)	0.015 (2)
C6	0.021 (3)	0.034 (3)	0.037 (3)	−0.001 (2)	−0.005 (2)	0.008 (2)
C7	0.022 (3)	0.021 (2)	0.016 (2)	−0.001 (2)	0.0023 (19)	−0.0033 (19)
C8	0.021 (2)	0.023 (2)	0.019 (3)	0.006 (2)	0.0037 (19)	−0.001 (2)
C9	0.035 (3)	0.031 (3)	0.032 (3)	−0.004 (2)	−0.011 (2)	0.009 (2)
C10	0.044 (4)	0.037 (3)	0.033 (3)	0.006 (3)	−0.008 (3)	0.005 (3)
C11	0.050 (4)	0.033 (3)	0.060 (4)	−0.013 (3)	−0.004 (3)	0.014 (3)
C12	0.034 (3)	0.031 (3)	0.047 (4)	0.000 (2)	−0.003 (3)	0.008 (3)
C13	0.022 (2)	0.027 (3)	0.013 (2)	−0.006 (2)	0.0035 (19)	0.0008 (19)
C14	0.020 (2)	0.021 (2)	0.023 (3)	−0.0032 (19)	0.0036 (19)	0.004 (2)
C15	0.033 (3)	0.027 (3)	0.036 (3)	−0.001 (2)	−0.007 (2)	0.008 (2)
C16	0.045 (4)	0.028 (3)	0.043 (4)	−0.011 (3)	−0.004 (3)	0.017 (3)
C17	0.042 (4)	0.022 (3)	0.056 (4)	−0.011 (2)	−0.012 (3)	0.004 (3)
C18	0.029 (3)	0.027 (3)	0.034 (3)	−0.008 (2)	−0.005 (2)	0.002 (2)
C19	0.019 (2)	0.024 (2)	0.020 (3)	0.000 (2)	0.0029 (19)	0.002 (2)
C20	0.025 (3)	0.016 (2)	0.013 (2)	−0.0015 (19)	−0.0017 (19)	−0.0036 (18)
C21	0.016 (2)	0.016 (2)	0.024 (3)	−0.0025 (18)	−0.0015 (19)	0.0005 (19)
C22	0.022 (2)	0.020 (2)	0.017 (2)	−0.0001 (19)	0.0053 (19)	−0.0014 (19)
C23	0.026 (3)	0.028 (3)	0.036 (3)	−0.004 (2)	0.001 (2)	0.005 (2)
C24	0.041 (3)	0.032 (3)	0.058 (4)	−0.009 (3)	0.010 (3)	0.017 (3)
C25	0.049 (4)	0.027 (3)	0.050 (4)	−0.003 (3)	−0.008 (3)	0.019 (3)
C26	0.028 (3)	0.033 (3)	0.036 (3)	0.003 (2)	−0.006 (2)	0.008 (2)
C27	0.021 (2)	0.018 (2)	0.022 (3)	0.0019 (19)	0.004 (2)	0.0027 (19)
C28	0.021 (3)	0.023 (3)	0.024 (3)	0.002 (2)	0.006 (2)	−0.003 (2)
N1	0.030 (2)	0.030 (2)	0.027 (2)	0.0041 (19)	0.0065 (19)	0.0079 (19)
N2	0.041 (3)	0.036 (3)	0.034 (3)	0.011 (2)	0.012 (2)	0.012 (2)

Geometric parameters (Å, º)

La1—O2	2.366 (3)	C5—H5A	0.9300
La1—O3	2.461 (3)	C6—H6A	0.9300
La1—O5	2.569 (3)	C7—C8	1.487 (6)
La1—O6	2.677 (3)	C8—C9	1.373 (6)
La1—O7^i	2.449 (3)	C8—C12	1.383 (7)
La1—O9^i	2.551 (3)	C9—C10	1.374 (7)
La1—O9	2.601 (3)	C9—H9A	0.9300
La1—O10	2.723 (3)	C10—N2	1.312 (7)
La1—N2^ii	2.734 (4)	C10—H10A	0.9300
La2—O1^iii	2.500 (3)	C11—N2	1.324 (7)
La2—O4	2.479 (3)	C11—C12	1.366 (8)
La2—O6	2.616 (3)	C11—H11A	0.9300
La2—O8^iv	2.416 (3)	C12—H12A	0.9300
La2—O10	2.652 (3)	C13—C14	1.495 (6)
La2—O11	2.574 (3)	C14—C15	1.393 (7)
La2—O11^iv	2.811 (3)	C14—C19	1.394 (6)
La2—O12^iv	2.513 (3)	C15—C16	1.389 (7)
La2—N1^ii	2.782 (4)	C15—H15A	0.9300
O1—C1	1.243 (6)	C16—C17	1.377 (8)
O2—C1	1.258 (6)	C16—H16A	0.9300
O3—C7	1.251 (6)	C17—C18	1.384 (7)
O4—C7	1.246 (6)	C17—H17A	0.9300
O5—C13	1.255 (5)	C18—C19	1.385 (6)
O6—C13	1.268 (5)	C18—H18A	0.9300
O7—C20	1.238 (5)	C19—C20	1.506 (6)
O8—C20	1.255 (5)	C21—C22	1.494 (6)
O10—C21	1.266 (5)	C22—C23	1.387 (7)
O11—C28	1.272 (6)	C22—C27	1.392 (6)
O12—C28	1.245 (5)	C23—C24	1.362 (7)
C1—C2	1.508 (7)	C23—H23A	0.9300
C2—C6	1.370 (7)	C24—C25	1.365 (8)
C2—C3	1.385 (6)	C24—H24A	0.9300
C3—C4	1.375 (7)	C25—C26	1.376 (7)
C3—H3A	0.9300	C25—H25A	0.9300
C4—N1	1.331 (6)	C26—C27	1.382 (7)
C4—H4A	0.9300	C26—H26A	0.9300
C5—N1	1.326 (6)	C27—C28	1.495 (6)
C5—C6	1.375 (7)
O2—La1—O7^i	82.91 (12)	C6—C2—C1	120.9 (4)
O2—La1—O3	85.67 (12)	C3—C2—C1	120.6 (4)
O7^i—La1—O3	133.05 (11)	C4—C3—C2	117.7 (5)
O2—La1—O9^i	86.54 (12)	C4—C3—H3A	121.1
O7^i—La1—O9^i	79.90 (11)	C2—C3—H3A	121.1
O3—La1—O9^i	144.55 (10)	N1—C4—C3	124.9 (5)
O2—La1—O5	78.89 (11)	N1—C4—H4A	117.6
O7^i—La1—O5	147.33 (11)	C3—C4—H4A	117.6
O3—La1—O5	72.40 (11)	N1—C5—C6	124.0 (5)
O9^i—La1—O5	72.17 (10)	N1—C5—H5A	118.0
O2—La1—O9	145.46 (11)	C6—C5—H5A	118.0
O7^i—La1—O9	72.61 (10)	C2—C6—C5	119.1 (5)
O3—La1—O9	128.86 (11)	C2—C6—H6A	120.5
O9^i—La1—O9	65.79 (11)	C5—C6—H6A	120.5
O5—La1—O9	109.40 (10)	O4—C7—O3	125.4 (5)
O2—La1—O6	128.46 (11)	O4—C7—C8	117.0 (4)
O7^i—La1—O6	140.12 (11)	O3—C7—C8	117.5 (4)
O3—La1—O6	79.49 (11)	C9—C8—C12	116.9 (5)
O9^i—La1—O6	78.58 (10)	C9—C8—C7	123.2 (4)
O5—La1—O6	49.57 (10)	C12—C8—C7	119.9 (4)
O9—La1—O6	68.02 (10)	C8—C9—C10	119.5 (5)
O2—La1—O10	160.78 (11)	C8—C9—H9A	120.3
O7^i—La1—O10	94.75 (11)	C10—C9—H9A	120.3
O3—La1—O10	82.05 (10)	N2—C10—C9	123.7 (5)
O9^i—La1—O10	111.92 (10)	N2—C10—H10A	118.1
O5—La1—O10	111.03 (10)	C9—C10—H10A	118.1
O9—La1—O10	48.61 (9)	N2—C11—C12	123.8 (6)
O6—La1—O10	63.51 (10)	N2—C11—H11A	118.1
O2—La1—N2^ii	87.75 (14)	C12—C11—H11A	118.1
O7^i—La1—N2^ii	66.60 (12)	C11—C12—C8	119.2 (5)
O3—La1—N2^ii	67.57 (12)	C11—C12—H12A	120.4
O9^i—La1—N2^ii	146.47 (12)	C8—C12—H12A	120.4
O5—La1—N2^ii	138.56 (12)	O5—C13—O6	121.5 (4)
O9—La1—N2^ii	103.77 (13)	O5—C13—C14	118.2 (4)
O6—La1—N2^ii	128.97 (12)	O6—C13—C14	120.3 (4)
O10—La1—N2^ii	73.92 (12)	O5—C13—La1	59.5 (2)
O8^iv—La2—O4	140.53 (12)	O6—C13—La1	64.5 (2)
O8^iv—La2—O1^iii	79.36 (11)	C14—C13—La1	162.9 (3)
O4—La2—O1^iii	70.26 (11)	C15—C14—C19	119.8 (4)
O8^iv—La2—O12^iv	115.34 (11)	C15—C14—C13	118.6 (4)
O4—La2—O12^iv	77.47 (11)	C19—C14—C13	121.6 (4)
O1^iii—La2—O12^iv	69.95 (11)	C16—C15—C14	120.5 (5)
O8^iv—La2—O11	71.68 (11)	C16—C15—H15A	119.8
O4—La2—O11	144.59 (11)	C14—C15—H15A	119.8
O1^iii—La2—O11	144.22 (11)	C17—C16—C15	119.3 (5)
O12^iv—La2—O11	103.89 (11)	C17—C16—H16A	120.3
O8^iv—La2—O6	151.03 (11)	C15—C16—H16A	120.3
O4—La2—O6	67.45 (11)	C16—C17—C18	120.4 (5)
O1^iii—La2—O6	127.26 (10)	C16—C17—H17A	119.8
O12^iv—La2—O6	71.36 (10)	C18—C17—H17A	119.8
O11—La2—O6	79.35 (11)	C17—C18—C19	120.9 (5)
O8^iv—La2—O10	102.81 (11)	C17—C18—H18A	119.5
O4—La2—O10	86.18 (11)	C19—C18—H18A	119.5
O1^iii—La2—O10	140.28 (10)	C18—C19—C14	118.9 (4)
O12^iv—La2—O10	136.66 (10)	C18—C19—C20	118.6 (4)
O11—La2—O10	68.45 (10)	C14—C19—C20	122.5 (4)
O6—La2—O10	65.30 (10)	O7—C20—O8	126.5 (4)
O8^iv—La2—N1^ii	73.56 (12)	O7—C20—C19	117.2 (4)
O4—La2—N1^ii	73.19 (12)	O8—C20—C19	116.2 (4)
O1^iii—La2—N1^ii	71.22 (11)	O9—C21—O10	121.0 (4)
O12^iv—La2—N1^ii	137.25 (12)	O9—C21—C22	118.4 (4)
O11—La2—N1^ii	118.07 (11)	O10—C21—C22	120.2 (4)
O6—La2—N1^ii	122.15 (11)	O9—C21—La1	59.0 (2)
O10—La2—N1^ii	71.55 (11)	O10—C21—La1	64.6 (2)
O8^iv—La2—O11^iv	74.59 (11)	C22—C21—La1	156.6 (3)
O4—La2—O11^iv	125.81 (11)	C23—C22—C27	119.7 (4)
O1^iii—La2—O11^iv	85.83 (10)	C23—C22—C21	117.8 (4)
O12^iv—La2—O11^iv	48.46 (10)	C27—C22—C21	122.4 (4)
O11—La2—O11^iv	66.77 (11)	C24—C23—C22	120.1 (5)
O6—La2—O11^iv	94.29 (10)	C24—C23—H23A	120.0
O10—La2—O11^iv	133.44 (10)	C22—C23—H23A	120.0
N1^ii—La2—O11^iv	143.52 (11)	C23—C24—C25	120.7 (5)
C1—O1—La2^v	131.2 (3)	C23—C24—H24A	119.6
C1—O2—La1	159.3 (3)	C25—C24—H24A	119.6
C7—O3—La1	123.4 (3)	C24—C25—C26	120.0 (5)
C7—O4—La2	142.2 (3)	C24—C25—H25A	120.0
C13—O5—La1	95.6 (3)	C26—C25—H25A	120.0
C13—O6—La2	140.4 (3)	C25—C26—C27	120.5 (5)
C13—O6—La1	90.2 (3)	C25—C26—H26A	119.7
La2—O6—La1	111.49 (11)	C27—C26—H26A	119.7
C20—O7—La1^i	160.3 (3)	C26—C27—C22	118.9 (4)
C20—O8—La2^iv	152.5 (3)	C26—C27—C28	119.7 (4)
C21—O9—La1^i	147.9 (3)	C22—C27—C28	121.1 (4)
C21—O9—La1	96.6 (3)	O12—C28—O11	122.1 (4)
La1^i—O9—La1	114.21 (11)	O12—C28—C27	118.4 (4)
C21—O10—La2	116.2 (3)	O11—C28—C27	119.5 (4)
C21—O10—La1	90.5 (3)	O12—C28—La2^iv	54.6 (2)
La2—O10—La1	108.97 (11)	O11—C28—La2^iv	68.3 (3)
C28—O11—La2	138.5 (3)	C27—C28—La2^iv	165.5 (3)
C28—O11—La2^iv	86.8 (3)	C5—N1—C4	115.9 (4)
La2—O11—La2^iv	113.23 (11)	C5—N1—La2^vi	117.8 (3)
C28—O12—La2^iv	101.6 (3)	C4—N1—La2^vi	125.5 (3)
O1—C1—O2	124.7 (5)	C10—N2—C11	116.8 (5)
O1—C1—C2	119.3 (4)	C10—N2—La1^vi	128.6 (4)
O2—C1—C2	115.9 (4)	C11—N2—La1^vi	114.1 (4)
C6—C2—C3	118.4 (5)

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, y−1/2, −z+1/2; (iii) x+1, y, z; (iv) −x+2, −y+1, −z+1; (v) x−1, y, z; (vi) −x+1, y+1/2, −z+1/2.