The first suberate lanthanum(III) complex without uncoordinated water

catena-Poly­[[aqua­lanthanum(III)]-μ-(8-carboxy­octanoato)-μ-octanedioato], [La(C₈H₁₂O₄)(C₈H₁₃O₄)(H₂O)]_n, is, to our knowledge, the first reported rare-earth complex containing a flexible long-chain ligand that crystallizes without water of crystallization. The layered polymeric structure is built from infinite chains of one-edge-sharing LaO₈(H₂O) polyhedra, connected through the carbon backbone chains of the ligands. The two chemically different ligands act in the same coordination modes, exhibiting chelating bonds and μ-1,1-bridging monodentate linkage, and adopting the same extended conformation. In the relatively limited hydrogen-bonding network, a very strong hydrogen bond between the deprotonated and protonated ligand ends stabilizes the framework.

S1. Comment

In the past decade, a particular emphasis on design, crystal packing and properties of organic–inorganic compounds has appeared, as a result of the wide variety of structural types leading, when the framework is open, to microporous materials. ?These polynuclear complexes are constructed of flexible dicarboxylate ligands, completely or partially deprotonated, linked to metal centers that assume high coordination numbers, such as lanthanides; such complexes can be used successfully as drying agents in catalysis or in ?the environmental? domain. Other applications have also been reported (Piguet & Bünzli, 1999; Parker et al., 2002). Most of the resulting neutral lanthanide polymers are hydrated, owing to the fact that their layered structures can accommodate interlayer guest molecules. These uncoordinated molecules are thought to play a crucial role in the crystalline stability, in that one characteristic common to most of these solid compounds is the inclusion, in channels, of water molecules (Antivec-Fidancev et al., 2002), which are difficult to remove without destroying the crystallinity.

We report here the crystal structure of the title compound, (I), [aqua(suberato)(hydrogensuberato)lanthanum(III)] (Benmerad et al., 2002), which has high stability and good crystallinity, despite the presence of long alkyl chains and the lack of any uncoordinated water molecules.

The complex [La(C₈H₁₂O₄)(C₈H₁₃O₄)(H₂O)] has a chemical formula similar to those of the isostructural lanthanum(III) glutarate (Benmerad et al., 2000a) and pimelate complexes (Dimos et al., 2002). Like these two compounds, (I) contains both protonated (HL) and deprotonated (L) ligands. Nevertheless, the crystal structure of the complex is completely different from the glutarate and pimelate analogues, from the point of view of connectivity, interlayer interactions, framework characteristics and packing arrangement. Despite its long-alkyl-chain ligand (eight C atoms) and its open framework, complex (I) remains stable up to 550 K, which is a very high temperature compared with the thermal stability of suberic acid (293–421 K) or of the only known suberato complex Co(C₈H₁₂O₄)·1.5(H₂O), which decomposes at 333 K (Allan & Dalrymple, 1993).

Fig. 1 shows the general features of the structure, without the hydrogen bonding. This layer-type polymeric structure is built up from infinite chains of one-edge-sharing LaO₈(H₂O) polyhedra, running along the [100] direction, connected through the carbon backbone of the ligands. The resulting cross-linked single chains form stable layers, despite the lack of additional hydrogen bonds involving water guest molecules. Adjacent metal centers are doubly bridged by pairs of ligands to form repeated four-membered La/O/La/O rings, within which the distances between two neighbour La³⁺ ions are almost equal [4.287 (1) Å (connection across O6 atoms) and 4.328 (1) Å (connection across O3 atoms)]. Fig. 2 shows the coordination around the La atom and reveals eight O atoms belonging to carboxylate ligands, equally distributed between three non-independent HL and L ligands on one hand, and one aqua ligand on the other hand. Unlike other known lanthanum dicarboxylates (Marrot & Trombe 1993, 1994; Kiritsis et al., 1998; Benmerad et al., 2000a, 2000b; Dimos et al., 2002) and despite the fact that this long-alkyl-chain ligand is more sterically demanding, the dispersion of the La—O bond lengths of is smaller [2.477 (4)–2.679 (7) Å; Table 1].

The two ligands are involved in the same coordination modes. They are bridging–chelating by one function, exhibiting µ-1,1-bridging via atom O6 for HL and atom O3 for L. They are monodentate by the second function, involving atom O7 for HL and atom O1 for L. As a consequence, all O atoms of the ligands are bonded to the metal cation, except O8, which is bonded to an H atom (the ligand being protonated), and atom O2 of the deprotonated ligand, which shares the same H atom (H8) with O8 in a hydrogen bond. The HL and L ligands clearly have different chemical characteristics, despite their identical coordination modes. The L ligand exhibits two functions typical of carboxylate groups, whereas in the HL ligand, the two different end functional groups seem to have the same character, related to carboxylate geometry. A similar bonding situation is found in related? complexes containing protonated ligands (Benmerad et al., 2000a; Dimos et al., 2002). As indicated by the torsion angles (Table 1), the conformations of the L and HL ligands are almost identical; they adopt an extended conformation. However, the two end functional groups involved in the bridging–chelating mode deviate significantly from the ideal anti–anti value (180°) for the HL ligand [O6—C9—C10—C11 = −168.2 (2)° and O5—C9—C10—C11 = 13.0 (3)°] and from the syn–anti values (60 and 180°) for the L ligand [O4—C8—C7—C6 = 50.7 (3)° and O3—C8—C7—C6 = −131.0 (3)°].

The La atom is nine-coordinate (Fig. 3), forming a monocapped dodecahedron, the cap being atom O7ⁱⁱ. This configuration is confirmed by the dihedral angle between the OW1/O3^iv/O6ⁱⁱⁱ/O1 and O5/O3ⁱ/O4^iv/O6 planes [65 (s.u.?)°], which is close to the value for an idealized D₂ geometry (ca 60°; Drew, 1977). As shown in Table 2, the hydrogen-bonding network is relatively limited. However, as mentioned above, there is a very strong hydrogen bond between the HL and L ligands; the protonated acid group donates atom H8 via a very short hydrogen bond [1.54 (1) Å] to atom O2.

In the absence of any uncoordinated water molecules lying between the layers and playing a templating role during crystallization, it can reasonably be assumed that this strong bond stabilizes the open framework. This new lanthanum dicarboxylate is noteworthy for several characteristics. The lack of any uncoordinated water molecule is very rare in this kind of material.

While 20 hydrated rare-earth complexes obtained with aliphatic HOOC-(CH₂)_n-COOH acids have been structurally characterized, only two have been reported that contain no water of crystallization, and these contain ligands having either a short alkyl spacer unit (n = 1; Hansson, 1973; Hernandez-Molina et al., 2002) or no alkyl spacer (n = 0; Trollet et al., 1997). In the higher series (n > 1),, only one family has been reported (Thomas & Trombe, 2001).

The structure of a suberato nickel(II) complex has been published recently (Zhang, 2003). This complex, like (I), is distinguished by its good crystallinity, which is unexpected when the acid has a long aliphatic chain (Bussien-Gaillard et al., 1998). These results highlight the need for caution about the specific character of the rare-earth dicarboxylates, the templating role of water molecules during crystallization and the effect of the hydrogen-bond network on enhancing the crystalline stability. One important structural crystallographic feature influencing the kind of framework seems to be the subfeature including four-membered rings and creating, in some cases, packing with a grid arrangement of the metal ions. In view of the limited number of complexes studied (Kiritsis et al., 1998; Wang et al., 2000; Sun et al., 2002), we cannot yet assess whether this feature? depends on the parity of n, but we note that an even number of C atoms in the alkyl spacer can introduce higher local symmetry, which in turn may influence the interlayer interactions.

S2. Experimental

Compound (I) was prepared using the procedure described by Benmerad et al. (2000a, 2000b), using a mixture of La₂O₃ and suberic acid in a 1:3 molar ratio and a reflux time of 10 h. Single crystals of the complex were deposited after one week when the cooled reaction mixture was allowed to stand in air at 313 K.

S3. Refinement

All H atoms bonded to C atoms were initially located from difference Fourier maps, and were then placed in calculated positions, 0.97 Å from their parent atoms, and modelled as riding. Atom H8 bonded to atom O8 was located from the Fourier syntheses and its position was refined freely, with U_iso(H) constrained to 1.2U_eq(O8).

Computing details

Data collection: COLLECT (Nonius, 1999); cell refinement: DENZO–SMN (Otwinowski & Minor, 1997); data reduction: DENZO–SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: enCIFer (Allen et al., 2004).

Figures

	Fig. 1. The packing of (I), viewed along the a axis. All H atoms have been omitted for clarity.
	Fig. 2. The coordination around the La atom, with the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i) 1 − x, −y, −z; (ii) 1/2 − x, 1/2 + y, 1/2 − z; (iii) x − 1/2, 1/2 − y, 1/2 + z; (iv) 3/2 − x, 1/2 + y, 3/2 − z.]
	Fig. 3. A polyhedral representation of the coordination around the La atom.

catena-Poly[[aqualanthanum(III)]-µ-(8-carboxyoctanoato)-µ-octanedioato]

Crystal data

[La(C8H12O4)(C8H13O4)(H2O)]	Z = 2
Mr = 502.28	F(000) = 504
Triclinic, P1	Dx = 1.743 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.582 (2) Å	Cell parameters from 38534 reflections
b = 9.079 (1) Å	θ = 2.5–30.5°
c = 13.092 (4) Å	µ = 2.28 mm^−1
α = 100.59 (1)°	T = 293 K
β = 103.66 (1)°	Prism, colourless
γ = 97.83 (1)°	0.4 × 0.3 × 0.3 mm
V = 957.0 (4) Å^3

Data collection

Nonius KappaCCD diffractometer	5739 independent reflections
Radiation source: fine-focus sealed tube	5279 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.039
ϕ and ω scans	θmax = 30.5°, θmin = 2.5°
Absorption correction: empirical (DENZO–SMN; Otwinowski & Minor, 1997)	h = −11→12
Tmin = 0.47, Tmax = 0.51	k = −11→12
38534 measured reflections	l = −18→17

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)] = 0.023	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.060	w = 1/[σ^2(Fo^2) + (0.0417P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max = 0.008
5739 reflections	Δρmax = 1.03 e Å^−3
239 parameters	Δρmin = −1.21 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0549 (15)

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	0.749250 (10)	0.980319 (11)	0.002455 (7)	0.01794 (5)
O1	0.87079 (19)	0.81489 (19)	0.11802 (12)	0.0366 (4)
O2	0.8784 (2)	0.5755 (2)	0.05009 (14)	0.0428 (4)
O3	1.46480 (15)	1.04292 (18)	0.90033 (10)	0.0259 (3)
O4	1.63649 (17)	0.9950 (2)	0.80454 (11)	0.0369 (4)
O5	0.88275 (16)	1.1578 (2)	0.19201 (11)	0.0335 (4)
O6	1.05355 (15)	1.12127 (17)	0.09302 (10)	0.0257 (3)
O7	1.56729 (19)	1.72928 (19)	0.91111 (14)	0.0442 (4)
O8	1.6359 (3)	1.5037 (2)	0.89694 (17)	0.0602 (6)
H8	1.723 (3)	1.558 (5)	0.969 (2)	0.072*
C1	0.9249 (2)	0.6965 (2)	0.12373 (15)	0.0267 (4)
C2	1.0510 (3)	0.6869 (3)	0.22411 (16)	0.0350 (5)
H2A	1.1502	0.6695	0.2045	0.042*
H2B	1.0109	0.5990	0.2494	0.042*
C3	1.0932 (3)	0.8264 (3)	0.31637 (15)	0.0316 (4)
H3A	1.1441	0.9128	0.2942	0.038*
H3B	0.9934	0.8499	0.3325	0.038*
C4	1.2074 (3)	0.8036 (3)	0.41753 (17)	0.0394 (5)
H4A	1.1593	0.7130	0.4366	0.047*
H4B	1.3094	0.7862	0.4023	0.047*
C5	1.2431 (2)	0.9372 (3)	0.51283 (15)	0.0363 (5)
H5A	1.1407	0.9563	0.5268	0.044*
H5B	1.2937	1.0272	0.4943	0.044*
C6	1.3542 (3)	0.9135 (3)	0.61547 (17)	0.0391 (5)
H6A	1.3068	0.8205	0.6320	0.047*
H6B	1.4590	0.9005	0.6029	0.047*
C7	1.3813 (3)	1.0446 (3)	0.71186 (16)	0.0324 (5)
H7A	1.4212	1.1390	0.6937	0.039*
H7B	1.2778	1.0527	0.7281	0.039*
C8	1.5009 (2)	1.0250 (2)	0.81013 (14)	0.0239 (4)
C9	1.0241 (2)	1.1770 (2)	0.18295 (14)	0.0235 (4)
C10	1.1649 (2)	1.2680 (3)	0.27484 (15)	0.0291 (4)
H10A	1.2015	1.3638	0.2573	0.035*
H10B	1.2544	1.2125	0.2809	0.035*
C11	1.1285 (2)	1.3028 (3)	0.38381 (15)	0.0313 (4)
H11A	1.0837	1.2083	0.3997	0.038*
H11B	1.0469	1.3672	0.3808	0.038*
C12	1.2805 (2)	1.3825 (3)	0.47384 (15)	0.0316 (4)
H12A	1.3229	1.4781	0.4584	0.038*
H12B	1.3632	1.3194	0.4743	0.038*
C13	1.2519 (2)	1.4152 (3)	0.58578 (16)	0.0340 (5)
H13A	1.1726	1.4817	0.5866	0.041*
H13B	1.2061	1.3202	0.6006	0.041*
C14	1.4075 (2)	1.4897 (3)	0.67466 (15)	0.0314 (4)
H14A	1.4520	1.5856	0.6605	0.038*
H14B	1.4875	1.4241	0.6728	0.038*
C15	1.3803 (2)	1.5197 (3)	0.78707 (15)	0.0348 (5)
H15A	1.3015	1.5864	0.7898	0.042*
H15B	1.3359	1.4242	0.8018	0.042*
C16	1.5373 (3)	1.5923 (3)	0.87196 (15)	0.0302 (4)
OW1	0.7704 (2)	1.2610 (2)	−0.01016 (15)	0.0488 (5)
H2W	0.8409	1.3510	0.0292	0.073*
H1W	0.6694	1.2727	−0.0476	0.073*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
La1	0.01515 (6)	0.02157 (7)	0.01572 (7)	0.00430 (4)	0.00269 (4)	0.00205 (4)
O1	0.0453 (9)	0.0316 (8)	0.0288 (8)	0.0139 (7)	−0.0021 (7)	0.0071 (6)
O2	0.0517 (10)	0.0323 (9)	0.0341 (9)	0.0159 (8)	−0.0045 (7)	−0.0034 (7)
O3	0.0213 (6)	0.0381 (8)	0.0195 (6)	0.0078 (6)	0.0058 (5)	0.0073 (6)
O4	0.0288 (7)	0.0649 (12)	0.0220 (7)	0.0208 (8)	0.0085 (6)	0.0108 (7)
O5	0.0215 (6)	0.0467 (10)	0.0254 (7)	0.0024 (6)	0.0069 (6)	−0.0073 (7)
O6	0.0205 (6)	0.0332 (8)	0.0191 (6)	0.0061 (5)	0.0042 (5)	−0.0042 (5)
O7	0.0377 (8)	0.0281 (8)	0.0506 (10)	0.0017 (7)	−0.0057 (7)	−0.0051 (7)
O8	0.0702 (13)	0.0337 (10)	0.0524 (12)	0.0136 (10)	−0.0214 (10)	−0.0047 (9)
C1	0.0297 (9)	0.0300 (10)	0.0227 (9)	0.0094 (8)	0.0075 (7)	0.0078 (8)
C2	0.0383 (11)	0.0380 (12)	0.0265 (10)	0.0147 (9)	0.0005 (9)	0.0071 (9)
C3	0.0337 (10)	0.0368 (12)	0.0208 (9)	0.0080 (9)	−0.0003 (8)	0.0065 (8)
C4	0.0419 (12)	0.0463 (14)	0.0247 (10)	0.0143 (10)	−0.0028 (9)	0.0054 (10)
C5	0.0391 (12)	0.0453 (12)	0.0222 (10)	0.0124 (9)	0.0008 (9)	0.0086 (9)
C6	0.0444 (12)	0.0431 (13)	0.0248 (10)	0.0164 (10)	−0.0023 (9)	0.0042 (9)
C7	0.0346 (10)	0.0445 (13)	0.0203 (9)	0.0176 (9)	0.0037 (8)	0.0099 (9)
C8	0.0232 (8)	0.0299 (10)	0.0186 (8)	0.0068 (7)	0.0044 (7)	0.0056 (7)
C9	0.0214 (8)	0.0266 (9)	0.0196 (8)	0.0051 (7)	0.0033 (7)	0.0007 (7)
C10	0.0214 (9)	0.0373 (11)	0.0222 (9)	0.0022 (8)	0.0029 (7)	−0.0028 (8)
C11	0.0267 (9)	0.0406 (12)	0.0205 (9)	0.0037 (8)	0.0025 (7)	−0.0016 (8)
C12	0.0294 (10)	0.0381 (12)	0.0210 (9)	0.0018 (8)	0.0026 (8)	−0.0007 (8)
C13	0.0293 (10)	0.0439 (13)	0.0217 (9)	0.0009 (9)	0.0036 (8)	−0.0017 (9)
C14	0.0309 (10)	0.0364 (11)	0.0201 (9)	−0.0014 (8)	0.0036 (8)	−0.0009 (8)
C15	0.0333 (11)	0.0407 (12)	0.0216 (10)	−0.0050 (9)	0.0057 (8)	−0.0039 (9)
C16	0.0370 (11)	0.0296 (10)	0.0172 (9)	−0.0034 (8)	0.0045 (8)	−0.0009 (7)
OW1	0.0428 (9)	0.0262 (8)	0.0634 (12)	0.0032 (7)	−0.0126 (8)	0.0123 (8)

Geometric parameters (Å, º)

La1—O3^i	2.4772 (12)	C5—C6	1.524 (3)
La1—O1	2.4799 (15)	C5—H5A	0.9700
La1—O7^ii	2.4920 (16)	C5—H5B	0.9700
La1—O6^iii	2.5057 (12)	C6—C7	1.516 (3)
La1—OW1	2.5688 (18)	C6—H6A	0.9700
La1—O4^iv	2.5779 (14)	C6—H6B	0.9700
La1—O5	2.5984 (14)	C7—C8	1.500 (3)
La1—O6	2.6331 (13)	C7—H7A	0.9700
La1—O3^iv	2.6807 (13)	C7—H7B	0.9700
La1—C9	3.0010 (18)	C9—C10	1.505 (3)
La1—C8^iv	3.0205 (18)	C10—C11	1.518 (3)
O1—C1	1.235 (3)	C10—H10A	0.9700
O2—C1	1.267 (2)	C10—H10B	0.9700
O3—C8	1.278 (2)	C11—C12	1.522 (3)
O4—C8	1.246 (2)	C11—H11A	0.9700
O5—C9	1.239 (2)	C11—H11B	0.9700
O6—C9	1.289 (2)	C12—C13	1.525 (3)
O7—C16	1.221 (3)	C12—H12A	0.9700
O8—C16	1.273 (3)	C12—H12B	0.9700
O8—H8	1.04 (3)	C13—C14	1.525 (3)
C1—C2	1.517 (3)	C13—H13A	0.9700
C2—C3	1.519 (3)	C13—H13B	0.9700
C2—H2A	0.9700	C14—C15	1.525 (3)
C2—H2B	0.9700	C14—H14A	0.9700
C3—C4	1.516 (3)	C14—H14B	0.9700
C3—H3A	0.9700	C15—C16	1.504 (3)
C3—H3B	0.9700	C15—H15A	0.9700
C4—C5	1.513 (3)	C15—H15B	0.9700
C4—H4A	0.9700	OW1—H2W	0.9284
C4—H4B	0.9700	OW1—H1W	0.9212
O3^i—La1—O1	83.14 (5)	H3A—C3—H3B	107.9
O3^i—La1—O7^ii	74.50 (5)	C5—C4—C3	113.5 (2)
O1—La1—O7^ii	79.29 (6)	C5—C4—H4A	108.9
O3^i—La1—O6^iii	153.83 (5)	C3—C4—H4A	108.9
O1—La1—O6^iii	77.43 (5)	C5—C4—H4B	108.9
O7^ii—La1—O6^iii	84.72 (5)	C3—C4—H4B	108.9
O3^i—La1—OW1	100.61 (6)	H4A—C4—H4B	107.7
O1—La1—OW1	141.61 (5)	C4—C5—C6	113.8 (2)
O7^ii—La1—OW1	138.80 (6)	C4—C5—H5A	108.8
O6^iii—La1—OW1	105.52 (6)	C6—C5—H5A	108.8
O3^i—La1—O4^iv	113.13 (4)	C4—C5—H5B	108.8
O1—La1—O4^iv	143.12 (6)	C6—C5—H5B	108.8
O7^ii—La1—O4^iv	74.22 (6)	H5A—C5—H5B	107.7
O6^iii—La1—O4^iv	75.04 (4)	C7—C6—C5	113.24 (19)
OW1—La1—O4^iv	70.44 (6)	C7—C6—H6A	108.9
O3^i—La1—O5	75.60 (4)	C5—C6—H6A	108.9
O1—La1—O5	74.22 (5)	C7—C6—H6B	108.9
O7^ii—La1—O5	141.95 (6)	C5—C6—H6B	108.9
O6^iii—La1—O5	114.88 (4)	H6A—C6—H6B	107.7
OW1—La1—O5	69.91 (6)	C8—C7—C6	112.58 (18)
O4^iv—La1—O5	140.34 (7)	C8—C7—H7A	109.1
O3^i—La1—O6	124.41 (4)	C6—C7—H7A	109.1
O1—La1—O6	74.98 (5)	C8—C7—H7B	109.1
O7^ii—La1—O6	145.04 (5)	C6—C7—H7B	109.1
O6^iii—La1—O6	66.96 (5)	H7A—C7—H7B	107.8
OW1—La1—O6	71.56 (5)	O4—C8—O3	120.06 (16)
O4^iv—La1—O6	114.90 (5)	O4—C8—C7	120.22 (17)
O5—La1—O6	49.55 (4)	O3—C8—C7	119.70 (16)
O3^i—La1—O3^iv	65.98 (5)	O4—C8—La1^v	57.64 (10)
O1—La1—O3^iv	143.27 (5)	O3—C8—La1^v	62.46 (9)
O7^ii—La1—O3^iv	73.83 (5)	C7—C8—La1^v	177.80 (13)
O6^iii—La1—O3^iv	123.47 (4)	O5—C9—O6	120.36 (16)
OW1—La1—O3^iv	67.25 (5)	O5—C9—C10	121.34 (16)
O4^iv—La1—O3^iv	49.09 (4)	O6—C9—C10	118.29 (15)
O5—La1—O3^iv	113.91 (5)	O5—C9—La1	59.38 (10)
O6—La1—O3^iv	138.80 (5)	O6—C9—La1	61.15 (9)
O3^i—La1—C9	99.28 (5)	C10—C9—La1	176.94 (15)
O1—La1—C9	71.91 (5)	C9—C10—C11	115.39 (16)
O7^ii—La1—C9	151.10 (6)	C9—C10—H10A	108.4
O6^iii—La1—C9	91.23 (4)	C11—C10—H10A	108.4
OW1—La1—C9	69.77 (5)	C9—C10—H10B	108.4
O4^iv—La1—C9	132.21 (6)	C11—C10—H10B	108.4
O5—La1—C9	24.21 (4)	H10A—C10—H10B	107.5
O6—La1—C9	25.38 (4)	C10—C11—C12	112.05 (16)
O3^iv—La1—C9	130.20 (5)	C10—C11—H11A	109.2
O3^i—La1—C8^iv	89.85 (5)	C12—C11—H11A	109.2
O1—La1—C8^iv	151.15 (5)	C10—C11—H11B	109.2
O7^ii—La1—C8^iv	71.88 (6)	C12—C11—H11B	109.2
O6^iii—La1—C8^iv	98.75 (4)	H11A—C11—H11B	107.9
OW1—La1—C8^iv	67.18 (5)	C11—C12—C13	114.20 (17)
O4^iv—La1—C8^iv	24.09 (4)	C11—C12—H12A	108.7
O5—La1—C8^iv	130.92 (5)	C13—C12—H12A	108.7
O6—La1—C8^iv	130.36 (5)	C11—C12—H12B	108.7
O3^iv—La1—C8^iv	25.01 (4)	C13—C12—H12B	108.7
C9—La1—C8^iv	136.93 (5)	H12A—C12—H12B	107.6
C1—O1—La1	147.96 (14)	C14—C13—C12	112.96 (17)
C8—O3—La1^i	147.97 (12)	C14—C13—H13A	109.0
C8—O3—La1^v	92.54 (10)	C12—C13—H13A	109.0
La1^i—O3—La1^v	114.02 (5)	C14—C13—H13B	109.0
C8—O4—La1^v	98.26 (11)	C12—C13—H13B	109.0
C9—O5—La1	96.41 (11)	H13A—C13—H13B	107.8
C9—O6—La1^iii	148.14 (11)	C13—C14—C15	113.20 (16)
C9—O6—La1	93.47 (10)	C13—C14—H14A	108.9
La1^iii—O6—La1	113.03 (5)	C15—C14—H14A	108.9
C16—O7—La1^vi	154.95 (16)	C13—C14—H14B	108.9
C16—O8—H8	109 (2)	C15—C14—H14B	108.9
O1—C1—O2	123.85 (19)	H14A—C14—H14B	107.8
O1—C1—C2	120.73 (19)	C16—C15—C14	111.20 (16)
O2—C1—C2	115.40 (19)	C16—C15—H15A	109.4
C1—C2—C3	115.15 (18)	C14—C15—H15A	109.4
C1—C2—H2A	108.5	C16—C15—H15B	109.4
C3—C2—H2A	108.5	C14—C15—H15B	109.4
C1—C2—H2B	108.5	H15A—C15—H15B	108.0
C3—C2—H2B	108.5	O7—C16—O8	123.2 (2)
H2A—C2—H2B	107.5	O7—C16—C15	120.7 (2)
C4—C3—C2	112.39 (19)	O8—C16—C15	116.0 (2)
C4—C3—H3A	109.1	La1—OW1—H2W	134.3
C2—C3—H3A	109.1	La1—OW1—H1W	107.5
C4—C3—H3B	109.1	H2W—OW1—H1W	115.1
C2—C3—H3B	109.1
O3^i—La1—O1—C1	126.0 (3)	C5—C6—C7—C8	−175.64 (19)
O7^ii—La1—O1—C1	50.5 (3)	La1^v—O4—C8—O3	2.3 (2)
O6^iii—La1—O1—C1	−36.4 (3)	La1^v—O4—C8—C7	−179.38 (17)
OW1—La1—O1—C1	−135.6 (3)	La1^i—O3—C8—O4	−149.24 (19)
O4^iv—La1—O1—C1	6.1 (3)	La1^v—O3—C8—O4	−2.2 (2)
O5—La1—O1—C1	−157.1 (3)	La1^i—O3—C8—C7	32.4 (4)
O6—La1—O1—C1	−105.6 (3)	La1^v—O3—C8—C7	179.48 (18)
O3^iv—La1—O1—C1	93.9 (3)	La1^i—O3—C8—La1^v	−147.0 (3)
C9—La1—O1—C1	−131.9 (3)	C6—C7—C8—O4	50.7 (3)
C8^iv—La1—O1—C1	48.9 (3)	C6—C7—C8—O3	−131.0 (2)
O3^i—La1—O5—C9	167.62 (15)	La1—O5—C9—O6	4.8 (2)
O1—La1—O5—C9	80.82 (14)	La1—O5—C9—C10	−176.53 (18)
O7^ii—La1—O5—C9	128.49 (13)	La1^iii—O6—C9—O5	−151.85 (19)
O6^iii—La1—O5—C9	13.15 (15)	La1—O6—C9—O5	−4.7 (2)
OW1—La1—O5—C9	−85.15 (14)	La1^iii—O6—C9—C10	29.4 (4)
O4^iv—La1—O5—C9	−83.37 (15)	La1—O6—C9—C10	176.57 (17)
O6—La1—O5—C9	−2.67 (12)	La1^iii—O6—C9—La1	−147.1 (3)
O3^iv—La1—O5—C9	−137.38 (13)	O3^i—La1—C9—O5	−12.15 (14)
C8^iv—La1—O5—C9	−115.44 (13)	O1—La1—C9—O5	−91.74 (14)
O3^i—La1—O6—C9	−8.88 (14)	O7^ii—La1—C9—O5	−86.80 (17)
O1—La1—O6—C9	−79.38 (12)	O6^iii—La1—C9—O5	−168.08 (14)
O7^ii—La1—O6—C9	−123.35 (13)	OW1—La1—C9—O5	85.82 (14)
O6^iii—La1—O6—C9	−161.86 (15)	O4^iv—La1—C9—O5	121.13 (14)
OW1—La1—O6—C9	81.51 (12)	O6—La1—C9—O5	175.3 (2)
O4^iv—La1—O6—C9	138.57 (12)	O3^iv—La1—C9—O5	54.15 (16)
O5—La1—O6—C9	2.55 (12)	C8^iv—La1—C9—O5	87.69 (15)
O3^iv—La1—O6—C9	83.03 (13)	O3^i—La1—C9—O6	172.59 (11)
C8^iv—La1—O6—C9	116.44 (12)	O1—La1—C9—O6	93.00 (12)
O3^i—La1—O6—La1^iii	152.99 (6)	O7^ii—La1—C9—O6	97.93 (15)
O1—La1—O6—La1^iii	82.48 (7)	O6^iii—La1—C9—O6	16.65 (14)
O7^ii—La1—O6—La1^iii	38.51 (12)	OW1—La1—C9—O6	−89.44 (12)
O6^iii—La1—O6—La1^iii	0.0	O4^iv—La1—C9—O6	−54.13 (14)
OW1—La1—O6—La1^iii	−116.63 (7)	O5—La1—C9—O6	−175.3 (2)
O4^iv—La1—O6—La1^iii	−59.57 (8)	O3^iv—La1—C9—O6	−121.12 (11)
O5—La1—O6—La1^iii	164.41 (10)	C8^iv—La1—C9—O6	−87.58 (13)
O3^iv—La1—O6—La1^iii	−115.11 (6)	O5—C9—C10—C11	13.1 (3)
C9—La1—O6—La1^iii	161.86 (15)	O6—C9—C10—C11	−168.2 (2)
C8^iv—La1—O6—La1^iii	−81.70 (8)	C9—C10—C11—C12	174.9 (2)
La1—O1—C1—O2	−28.9 (4)	C10—C11—C12—C13	−178.0 (2)
La1—O1—C1—C2	153.0 (2)	C11—C12—C13—C14	177.9 (2)
O1—C1—C2—C3	4.3 (3)	C12—C13—C14—C15	−178.8 (2)
O2—C1—C2—C3	−174.0 (2)	C13—C14—C15—C16	179.6 (2)
C1—C2—C3—C4	174.54 (19)	La1^vi—O7—C16—O8	22.8 (5)
C2—C3—C4—C5	−176.4 (2)	La1^vi—O7—C16—C15	−155.0 (3)
C3—C4—C5—C6	178.5 (2)	C14—C15—C16—O7	101.4 (3)
C4—C5—C6—C7	−176.8 (2)	C14—C15—C16—O8	−76.5 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O8—H8···O2^vi	1.04 (3)	1.46 (3)	2.441 (3)	153
OW1—H2W···O2^vii	0.929	1.976	2.782 (3)	144
OW1—H1W···O8^iv	0.921	2.374	2.947 (3)	120
OW1—H1W···O3^iv	0.921	2.411	2.908 (3)	114

Symmetry codes: (iv) x−1, y, z−1; (vi) x+1, y+1, z+1; (vii) x, y+1, z.