The first coordination polymer of lanthanum(III) with a naphthalene-1,4,5,8-tetra­carboxylic 1,8-anhydride derivative

The title compound, catena-poly[[[hepta­aqualanthanum(III)]-μ-­1,3-dioxo-2-oxa-1H,3H-phenalene-6,7-dicarboxyl­ato-κ²O⁶:O⁷] hemi(4,8-di­carboxy­naphthalene-1,5-dicarboxyl­ate) di­hydrate], {[La(C₁₄H₄O₇)(H₂O)₇](C₁₄H₆O₈)_0.5·2H₂O}_n, is a dihydrate of a coordination polymer between the dianion of naphthalene-1,4,5,8-tetra­carboxylic 1,8-anhydride and the hepta­hydrated lanthanum(III) ion, charge balanced by an additional 4,8-dicarboxy­naphthalene-1,5-dicarboxyl­ate di­an­ion that is located on an inversion centre and is not coordinated to the metal ion. The linear polymeric arrays adopt a comb-like structure, and these pack in pairs with one chain inter­penetrating another, like two parts of a zip, to optimize stacking inter­actions between their ligand fragments. All the components of this compound are further inter­linked by an extensive pattern of O—H...O hydrogen bonds throughout the crystal structure. The main scientific significance of the results reported here is that they demonstrate for the first time the feasibility of coordination polymerization of the above organic ligand with lanthanide ions. The resulting polymer has a unique architecture. Finally, the reported structure is a rare example where the tetra­acid and the diacid anhydride ligand species co-exist in the same crystal.

S1. Comment

Naphthalene-1,4,5,8-tetracarboxylic acid, (I), and its anhydrated derivative, naphthalene-1,4,5,8-tetracarboxylic acid 1,8-anhydrate, (II), are attractive ligands for the formulation of coordination polymers with metal ions and functional metal–organic complexes. They bear multiple functional groups and have a rigid molecular framework, allowing for simultaneous coordination of several metal ions in different directions. Usually, the metal–ligand interaction is associated with deprotonation of the carboxylic acid functions, and thus it is strengthened by electrostatic attraction. Not surprisingly, therefore, (I) and (II) have been the subject of considerable attention in this context in recent years. However, only a small number of extended coordination polymeric structures with rare earth and transition metal ions have been reported to date (Senkovska, 2006; Surble et al., 2006; Chen et al., 2005; Xu, Yuan, Wu et al., 2005; Zhao & Tao, 2004), as the reactions of (I) and (II) with metal ions are often terminated with the formation of discrete complexes (Wang et al., 2005; Fitzgerald & Gerkin, 1994; Fitzgerald et al., 1993). The coordination features of these ligands with lanthanide ions have not been explored until now. The crystal structure of the free ligand, (II), has been reported only recently (Xu, Yuan, Zhou et al., 2005). As part of our ongoing investigation of coordination polymers that involve organic carboxylic ligands and lanthanide ions (George et al., 2006; Muniappan et al., 2007; Lipstman et al., 2007), we report here the title compound, (III), a new material and the first coordination polymer of (II) with a lanthanum ion La³⁺, which co-crystallized with (I).

The molecular structure of (III) is shown in Fig. 1. In the crystal structure, the metal ion is heptahydrated. The asymmetric unit consists of one La(H₂O)₇ moiety, one doubly deprotonated ligand (II), one half of a doubly deprotonated ligand (I) which resides on an inversion at (0, 0, 1/2), and two additional water molecules of hydration. The lanthanide ion bridges by coordination [to atoms O9 and O28 at (x - 1, y, z)] between the carboxylate groups of two adjacent ligands, revealing a total coordination number of 9 (which is common for La³⁺ ions). Its coordination geometry can be best described as a tricapped trigonal prism. Similarly, each ligand moiety links to two different metal ions at (x, y, z) and (x + 1, y, z), leading to the formation of linear one-dimensional coordination polymers that extend parallel to the a axis of the crystal structure (Fig. 2). All the La—O coordination distances are within 2.495–2.647 (2) Å (Table 1). As the two carboxylate functions available for bonding are located on the same side of the ligand moiety, the polymeric arrays adopt a comb shape, with the planes of the ligands oriented nearly perpendicular to (and on the same side of) the propagation axis of the polymer. Moreover, the proximity of the two carboxylate groups and optimization of the polymeric coordination are associated with a slight deformation of the naphthalene backbone from planarity and a marked twist of the carboxylates in opposite directions with respect to the naphthalene ring. Thus, the dihedral angle between the two aryl rings (C12–C15/C25/C26 and C21–C26) is 4.84 (2)°, while the C11—C12···C24—C26 torsion angle is 29.16 (18)°.

A similar comb-type arrangement has only been observed before in the photoluminescent polymeric structure of (II) with Cd(1,10-phenanthroline)²⁺ ions (Xu, Yuan, Wu et al., 2005). In that case, the Cd-bound phenanthroline (phen) ligand is inserted between neighbouring moieties of (II) along the polymer, stabilizing the polymeric arrangement by stacking interactions. The reported distance between the phen and naphthalene planes is 3.739 Å. The situation is somewhat different in the present study. There are no aromatic fragments in the analysed compound other than (II), and an additional negative ion is needed to balance the 3+ charge of the lanthanide ion. Nature solved the first problem by sn interpenetrating arrangement of inversion-related polymeric chains, where the ligand fragments of one polymeric chain penetrate between the ligands of another polymer (Fig. 2) as in a zip fastener. The distance between the mean planes of the overlapping fragments is 3.279 (2) Å (this value refers to the interplanar distance of the flat antiparallel fragments C15–C21 at (x, y, z) and (1 - x, 2 - y, -z). The charge-balance issue is resolved by the inclusion in the crystal of a doubly deprotonated ligand (I), not coordinated to the metal ions, which is located on an inversion (Fig. 3). These species are arranged in planes which interface between the coupled polymeric chains. Further stabilization of the observed structure is provided by the very extensive array of cross-linking O—H···O hydrogen bonds, which involves the nine water molecules in the asymmetric unit, along with the carboxylic and carboxylate groups (Table 2 lists 19 unique hydrogen-bonding interactions). The rigidity of the resulting structure is well reflected in the negligible solubility of this solid in water and common organic solvents.

In summary, we have demonstrated that the naphthalene carboxylic acid ligand can form coordination polymers not only with transition metals but also with lanthanide ions. This first example represents a double-chain one-dimensional polymer, and further studies are underway to construct similar polymers with two- and three-dimensional architectures. Such materials may reveal features of microporosity (e.g. for gas sorption) and photoluminescence (e.g. for photophysical applications) (Xu, Yuan, Wu et al., 2005; Surble et al., 2006) and have considerable potential significance.

S2. Experimental

1,4,5,8-Naphthalenetetracarboxylic acid and lanthanum nitrate hexahydrate were purchased commercially and used without further purification. The tetrasodium salt of the acid was prepared according to the reported method (Fitzgerald et al., 1991). A mixture of La(NO₃)₃.6H₂O (0.044 g, 0.1 mmol) and tetrasodium naphthalene-1,4,5,8-tetracarboxylate (0.055 g, 0.1 mmol) was dissolved in water (15 ml). The mixture was allowed to stand in a capped vial for 10 d at room temperature. Needle-shaped crystals of (III) were deposited. They were collected by filtration, washed with water and air-dried. The product is insoluble in water and in common organic solvents. IR (KBr, cm^-1): 3454 and 3260 (water stretching vibrations), 1718 (COOH), 1608 and 1566 (COO^- asymmetric stretching), 1434 and 1391 (COO^- symmetric stretching). The solid IR spectrum confirms the presence of both carboxylic acid and carboxylate groups in the structure. Formation of the anhydrated species (II) from (I) has occurred during the crystallization process.

S3. Refinement

H atoms bound to C atoms were located in calculated positions and were constrained to ride on their parent atoms, with C—H = 0.95 Å and with U_iso(H) = 1.2U_eq(C). All H atoms bound to O atoms were located in a difference Fourier map. The corresponding O—H distances were modified and constrained [restrained?] to be near 0.90 Å, with U_iso(H) = 1.2U_eq(O).

Computing details

Data collection: COLLECT (Nonius, 1999); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure of (III), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level at ca 110 K. The uncoordinated ligand is located on an inversion at (0, 0, 1/2), and only atoms of the asymmetric unit are labelled. H atoms have been omitted. The coordination of La1 to O28 [symmetry code: (i) x - 1, y, z] is shown by a dashed line.
	Fig. 2. A stick diagram illustrating the coordination polymerization along the a axis in (III). H atoms have been omitted. Heptahydrated lanthanum ions are depicted as small spheres. Two interpenetrating polymeric chains are shown, exhibiting efficient stacking interactions between the aromatic ligands of the two chains.
	Fig. 3. The crystal packing of (III), omitting the H atoms. The lanthanum ions and water molecules of crystallization are depicted as small spheres. Note that the double polymeric chains are centred at z = 0 (and z = 1), while layers of the uncoordinated naphthalenetetracarboxylic acid ligand are centred at z = 1/2. The latter are hydrogen bonded to the former with the aid of interstitial water (Table 2).

catena-poly[[[heptaaqualanthanum(III)]-µ-1,3-dioxo-2-oxa-1H,3H-phenalene- 6,7-dicarboxylato-κ²O⁶:O⁷] hemi(4,8-dicarboxynaphthalene-1,5-dicarboxylate) dihydrate]

Crystal data

[La(C14H4O7)(H2O)7](C14H6O8)0.5·2H2O	Z = 2
Mr = 736.32	F(000) = 736
Triclinic, P1	Dx = 1.925 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.6222 (2) Å	Cell parameters from 4123 reflections
b = 9.4831 (2) Å	θ = 1.0–27.8°
c = 20.5543 (7) Å	µ = 1.78 mm^−1
α = 91.3625 (9)°	T = 110 K
β = 98.9233 (12)°	Needle, colourless
γ = 94.5506 (14)°	0.30 × 0.15 × 0.10 mm
V = 1270.29 (6) Å^3

Data collection

Nonius KappaCCD diffractometer	5821 independent reflections
Radiation source: fine-focus sealed tube	5404 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.031
Detector resolution: 12.8 pixels mm^-1	θmax = 27.8°, θmin = 1.0°
1° ϕ and ω scans	h = −8→8
Absorption correction: multi-scan (Blessing, 1995)	k = −12→12
Tmin = 0.617, Tmax = 0.842	l = −26→26
12656 measured reflections

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)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.058	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0101P)^2 + 2.3943P] where P = (Fo^2 + 2Fc^2)/3
5821 reflections	(Δ/σ)max = 0.001
379 parameters	Δρmax = 1.34 e Å^−3
0 restraints	Δρmin = −1.27 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	0.350060 (19)	0.626183 (13)	0.260635 (6)	0.00822 (5)
O2	0.0077 (3)	0.46884 (18)	0.26311 (9)	0.0137 (3)
H2A	−0.0852	0.4652	0.2261	0.016*
H2B	0.0051	0.3803	0.2775	0.016*
O3	0.2021 (3)	0.53923 (18)	0.13794 (8)	0.0128 (3)
H3A	0.2204	0.6059	0.1086	0.015*
H3B	0.0658	0.5181	0.1330	0.015*
O4	0.7149 (3)	0.62057 (18)	0.33006 (9)	0.0144 (4)
H4A	0.7390	0.6036	0.3733	0.017*
H4B	0.8015	0.5759	0.3089	0.017*
O5	0.3574 (3)	0.48964 (18)	0.36443 (8)	0.0131 (3)
H5A	0.2509	0.4613	0.3846	0.016*
H5B	0.4528	0.4317	0.3801	0.016*
O6	0.5018 (3)	0.87634 (19)	0.27588 (10)	0.0192 (4)
H6A	0.6348	0.8892	0.2714	0.023*
H6B	0.4537	0.9618	0.2795	0.023*
O7	0.1858 (3)	0.75198 (19)	0.35132 (9)	0.0158 (4)
H7A	0.1665	0.7284	0.3922	0.019*
H7B	0.0829	0.8045	0.3361	0.019*
O8	0.4731 (3)	0.38597 (19)	0.23513 (9)	0.0182 (4)
H8A	0.4338	0.2984	0.2466	0.022*
H8B	0.5322	0.3783	0.1988	0.022*
O9	0.6125 (3)	0.66463 (18)	0.18586 (8)	0.0124 (3)
O10	0.7754 (3)	0.48980 (17)	0.14696 (8)	0.0137 (3)
C11	0.7121 (3)	0.6128 (2)	0.14540 (12)	0.0102 (4)
C12	0.7458 (3)	0.7009 (2)	0.08698 (12)	0.0104 (4)
C13	0.7107 (4)	0.6315 (3)	0.02621 (12)	0.0133 (5)
H13	0.6983	0.5310	0.0238	0.016*
C14	0.6929 (4)	0.7062 (3)	−0.03237 (12)	0.0137 (5)
H14	0.6697	0.6568	−0.0739	0.016*
C15	0.7093 (4)	0.8519 (3)	−0.02874 (12)	0.0128 (5)
C16	0.6766 (4)	0.9289 (3)	−0.09014 (12)	0.0152 (5)
O17	0.6291 (3)	0.8781 (2)	−0.14444 (9)	0.0241 (4)
O18	0.7046 (3)	1.07743 (19)	−0.08489 (9)	0.0166 (4)
C19	0.7532 (4)	1.1547 (3)	−0.02622 (12)	0.0143 (5)
O20	0.7687 (3)	1.28135 (19)	−0.02948 (9)	0.0182 (4)
C21	0.7817 (4)	1.0772 (3)	0.03547 (12)	0.0116 (5)
C22	0.8325 (4)	1.1514 (3)	0.09482 (12)	0.0135 (5)
H22	0.8393	1.2519	0.0963	0.016*
C23	0.8742 (4)	1.0775 (3)	0.15338 (12)	0.0134 (5)
H23	0.9133	1.1293	0.1941	0.016*
C24	0.8593 (3)	0.9311 (2)	0.15282 (12)	0.0106 (4)
C25	0.7879 (3)	0.8512 (2)	0.09261 (12)	0.0100 (4)
C26	0.7595 (3)	0.9268 (2)	0.03309 (12)	0.0105 (5)
C27	0.9505 (3)	0.8630 (2)	0.21573 (12)	0.0093 (4)
O28	1.0630 (3)	0.76474 (17)	0.20851 (8)	0.0118 (3)
O29	0.9187 (3)	0.91326 (17)	0.27005 (8)	0.0121 (3)
O30	0.2382 (3)	0.42421 (17)	0.52858 (8)	0.0123 (3)
H30	0.2370	0.5091	0.5099	0.015*
O31	0.0753 (2)	0.34637 (17)	0.42930 (8)	0.0112 (3)
C32	0.1451 (3)	0.3257 (2)	0.48718 (12)	0.0097 (4)
C33	0.1465 (3)	0.1795 (2)	0.51287 (11)	0.0090 (4)
C34	0.3282 (4)	0.1463 (2)	0.54886 (12)	0.0104 (4)
H34	0.4300	0.2197	0.5658	0.013*
C35	0.3643 (4)	0.0049 (2)	0.56082 (12)	0.0106 (4)
H35	0.4907	−0.0164	0.5857	0.013*
C36	0.2195 (3)	−0.1034 (2)	0.53711 (11)	0.0093 (4)
C37	0.0188 (3)	−0.0722 (2)	0.50627 (11)	0.0088 (4)
C38	0.2885 (3)	−0.2507 (2)	0.53914 (12)	0.0099 (4)
O39	0.2324 (2)	−0.33054 (17)	0.48753 (8)	0.0110 (3)
O40	0.4019 (3)	−0.28492 (18)	0.58944 (9)	0.0161 (4)
O41	−0.0066 (3)	0.19469 (19)	0.31360 (9)	0.0189 (4)
H41A	−0.0614	0.1053	0.3047	0.023*
H41B	−0.0046	0.2160	0.3565	0.023*
O42	0.3950 (3)	0.14493 (19)	0.29958 (9)	0.0192 (4)
H42A	0.4738	0.1758	0.3376	0.023*
H42B	0.2649	0.1544	0.3052	0.023*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
La1	0.00824 (7)	0.00834 (7)	0.00851 (7)	0.00145 (5)	0.00211 (5)	0.00176 (5)
O2	0.0122 (8)	0.0130 (8)	0.0145 (9)	−0.0008 (6)	−0.0015 (7)	0.0048 (7)
O3	0.0134 (8)	0.0146 (8)	0.0105 (8)	0.0018 (7)	0.0017 (7)	0.0027 (6)
O4	0.0113 (8)	0.0205 (9)	0.0119 (8)	0.0037 (7)	0.0020 (7)	0.0012 (7)
O5	0.0118 (8)	0.0134 (8)	0.0157 (9)	0.0049 (6)	0.0037 (7)	0.0081 (7)
O6	0.0133 (9)	0.0120 (9)	0.0337 (11)	−0.0004 (7)	0.0094 (8)	−0.0027 (8)
O7	0.0172 (9)	0.0220 (9)	0.0103 (8)	0.0099 (7)	0.0043 (7)	0.0047 (7)
O8	0.0271 (10)	0.0124 (9)	0.0171 (9)	0.0053 (7)	0.0072 (8)	0.0021 (7)
O9	0.0116 (8)	0.0145 (8)	0.0124 (8)	0.0012 (6)	0.0055 (7)	0.0004 (7)
O10	0.0175 (9)	0.0101 (8)	0.0134 (8)	0.0017 (7)	0.0020 (7)	0.0012 (6)
C11	0.0092 (11)	0.0096 (11)	0.0110 (11)	−0.0017 (8)	0.0003 (9)	0.0006 (8)
C12	0.0076 (10)	0.0134 (11)	0.0103 (11)	0.0027 (9)	0.0013 (9)	0.0005 (9)
C13	0.0124 (11)	0.0128 (11)	0.0144 (12)	0.0012 (9)	0.0017 (9)	−0.0005 (9)
C14	0.0134 (12)	0.0179 (12)	0.0099 (11)	0.0017 (9)	0.0024 (9)	−0.0005 (9)
C15	0.0108 (11)	0.0185 (12)	0.0095 (11)	0.0013 (9)	0.0025 (9)	0.0010 (9)
C16	0.0140 (12)	0.0197 (13)	0.0124 (12)	0.0030 (10)	0.0025 (9)	0.0022 (10)
O17	0.0338 (11)	0.0273 (11)	0.0105 (9)	0.0020 (9)	0.0013 (8)	0.0001 (8)
O18	0.0200 (9)	0.0193 (9)	0.0106 (8)	0.0030 (7)	0.0021 (7)	0.0038 (7)
C19	0.0106 (11)	0.0197 (13)	0.0136 (12)	0.0040 (9)	0.0027 (9)	0.0028 (10)
O20	0.0234 (10)	0.0156 (9)	0.0168 (9)	0.0034 (7)	0.0048 (8)	0.0083 (7)
C21	0.0103 (11)	0.0133 (11)	0.0118 (11)	0.0031 (9)	0.0018 (9)	0.0036 (9)
C22	0.0155 (12)	0.0107 (11)	0.0146 (12)	0.0027 (9)	0.0023 (9)	0.0026 (9)
C23	0.0160 (12)	0.0117 (11)	0.0128 (12)	0.0033 (9)	0.0020 (9)	0.0001 (9)
C24	0.0086 (11)	0.0128 (11)	0.0109 (11)	0.0028 (9)	0.0021 (9)	0.0017 (9)
C25	0.0077 (10)	0.0130 (11)	0.0104 (11)	0.0034 (8)	0.0037 (8)	0.0011 (9)
C26	0.0069 (10)	0.0134 (11)	0.0115 (11)	0.0016 (9)	0.0015 (9)	−0.0001 (9)
C27	0.0071 (10)	0.0085 (10)	0.0118 (11)	−0.0003 (8)	0.0005 (9)	0.0019 (8)
O28	0.0125 (8)	0.0111 (8)	0.0122 (8)	0.0045 (6)	0.0017 (6)	0.0012 (6)
O29	0.0134 (8)	0.0134 (8)	0.0096 (8)	0.0024 (6)	0.0013 (6)	0.0006 (6)
O30	0.0164 (8)	0.0050 (7)	0.0139 (8)	−0.0016 (6)	−0.0012 (7)	0.0022 (6)
O31	0.0115 (8)	0.0110 (8)	0.0111 (8)	0.0002 (6)	0.0019 (6)	0.0035 (6)
C32	0.0067 (10)	0.0096 (11)	0.0140 (12)	0.0027 (8)	0.0040 (9)	0.0013 (9)
C33	0.0110 (11)	0.0078 (10)	0.0087 (11)	0.0000 (8)	0.0032 (9)	0.0003 (8)
C34	0.0098 (11)	0.0092 (11)	0.0119 (11)	−0.0016 (8)	0.0017 (9)	0.0008 (9)
C35	0.0099 (11)	0.0114 (11)	0.0103 (11)	0.0012 (9)	0.0005 (9)	0.0008 (9)
C36	0.0105 (11)	0.0085 (10)	0.0093 (11)	0.0012 (8)	0.0022 (9)	0.0022 (8)
C37	0.0112 (11)	0.0082 (11)	0.0074 (11)	0.0016 (8)	0.0028 (9)	0.0013 (8)
C38	0.0085 (10)	0.0093 (11)	0.0122 (11)	0.0000 (8)	0.0026 (9)	0.0014 (9)
O39	0.0125 (8)	0.0082 (8)	0.0122 (8)	0.0005 (6)	0.0013 (6)	0.0010 (6)
O40	0.0180 (9)	0.0104 (8)	0.0180 (9)	0.0045 (7)	−0.0053 (7)	0.0002 (7)
O41	0.0294 (10)	0.0129 (9)	0.0136 (9)	−0.0027 (7)	0.0033 (8)	−0.0007 (7)
O42	0.0213 (10)	0.0151 (9)	0.0198 (10)	0.0021 (7)	−0.0008 (8)	−0.0014 (7)

Geometric parameters (Å, º)

La1—O6	2.4948 (17)	O18—C19	1.377 (3)
La1—O9	2.5039 (16)	C19—O20	1.201 (3)
La1—O28^i	2.5138 (16)	C19—C21	1.475 (3)
La1—O5	2.5180 (17)	C21—C22	1.375 (3)
La1—O8	2.5491 (18)	C21—C26	1.421 (3)
La1—O7	2.6094 (17)	C22—C23	1.409 (3)
La1—O4	2.6136 (17)	C22—H22	0.9500
La1—O2	2.6212 (16)	C23—C24	1.384 (3)
La1—O3	2.6470 (17)	C23—H23	0.9500
O2—H2A	0.8990	C24—C25	1.430 (3)
O2—H2B	0.8969	C24—C27	1.521 (3)
O3—H3A	0.8984	C25—C26	1.427 (3)
O3—H3B	0.8981	C27—O29	1.258 (3)
O4—H4A	0.8982	C27—O28	1.258 (3)
O4—H4B	0.8976	O28—La1^ii	2.5138 (16)
O5—H5A	0.8983	O30—C32	1.298 (3)
O5—H5B	0.8978	O30—H30	0.9005
O6—H6A	0.8995	O31—C32	1.234 (3)
O6—H6B	0.8991	C32—C33	1.496 (3)
O7—H7A	0.8993	C33—C34	1.374 (3)
O7—H7B	0.8977	C33—C37^iii	1.435 (3)
O8—H8A	0.8982	C34—C35	1.402 (3)
O8—H8B	0.8989	C34—H34	0.9500
O9—C11	1.253 (3)	C35—C36	1.373 (3)
O10—C11	1.270 (3)	C35—H35	0.9500
C11—C12	1.513 (3)	C36—C37	1.437 (3)
C12—C13	1.376 (3)	C36—C38	1.504 (3)
C12—C25	1.430 (3)	C37—C37^iii	1.433 (4)
C13—C14	1.406 (3)	C37—C33^iii	1.435 (3)
C13—H13	0.9500	C38—O40	1.246 (3)
C14—C15	1.376 (4)	C38—O39	1.277 (3)
C14—H14	0.9500	O41—H41A	0.8983
C15—C26	1.421 (3)	O41—H41B	0.8983
C15—C16	1.469 (3)	O42—H42A	0.8982
C16—O17	1.191 (3)	O42—H42B	0.8979
C16—O18	1.406 (3)
O6—La1—O9	71.21 (6)	C25—C12—C11	122.3 (2)
O6—La1—O28^i	76.77 (6)	C12—C13—C14	121.4 (2)
O9—La1—O28^i	102.95 (5)	C12—C13—H13	119.3
O6—La1—O5	115.52 (6)	C14—C13—H13	119.3
O9—La1—O5	130.79 (6)	C15—C14—C13	119.2 (2)
O28^i—La1—O5	126.24 (5)	C15—C14—H14	120.4
O6—La1—O8	136.76 (6)	C13—C14—H14	120.4
O9—La1—O8	72.32 (6)	C14—C15—C26	120.8 (2)
O28^i—La1—O8	134.23 (6)	C14—C15—C16	118.8 (2)
O5—La1—O8	73.74 (6)	C26—C15—C16	120.4 (2)
O6—La1—O7	71.37 (6)	O17—C16—O18	116.2 (2)
O9—La1—O7	142.55 (6)	O17—C16—C15	126.5 (2)
O28^i—La1—O7	69.73 (5)	O18—C16—C15	117.3 (2)
O5—La1—O7	66.64 (5)	C19—O18—C16	124.4 (2)
O8—La1—O7	139.56 (6)	O20—C19—O18	116.8 (2)
O6—La1—O4	73.26 (6)	O20—C19—C21	125.0 (2)
O9—La1—O4	71.28 (5)	O18—C19—C21	118.2 (2)
O28^i—La1—O4	149.74 (5)	C22—C21—C26	120.6 (2)
O5—La1—O4	65.63 (5)	C22—C21—C19	119.5 (2)
O8—La1—O4	73.66 (6)	C26—C21—C19	119.9 (2)
O7—La1—O4	96.40 (5)	C21—C22—C23	119.6 (2)
O6—La1—O2	141.89 (6)	C21—C22—H22	120.2
O9—La1—O2	138.29 (5)	C23—C22—H22	120.2
O28^i—La1—O2	73.20 (5)	C24—C23—C22	121.4 (2)
O5—La1—O2	67.45 (5)	C24—C23—H23	119.3
O8—La1—O2	81.35 (6)	C22—C23—H23	119.3
O7—La1—O2	76.52 (6)	C23—C24—C25	120.1 (2)
O4—La1—O2	131.23 (5)	C23—C24—C27	116.7 (2)
O6—La1—O3	115.97 (6)	C25—C24—C27	122.5 (2)
O9—La1—O3	68.28 (5)	C26—C25—C12	117.1 (2)
O28^i—La1—O3	66.90 (5)	C26—C25—C24	117.7 (2)
O5—La1—O3	128.51 (5)	C12—C25—C24	125.2 (2)
O8—La1—O3	69.43 (6)	C15—C26—C21	119.8 (2)
O7—La1—O3	132.11 (5)	C15—C26—C25	120.1 (2)
O4—La1—O3	131.47 (5)	C21—C26—C25	120.1 (2)
O2—La1—O3	72.45 (5)	O29—C27—O28	125.5 (2)
La1—O2—H2A	116.2	O29—C27—C24	118.6 (2)
La1—O2—H2B	122.7	O28—C27—C24	115.8 (2)
H2A—O2—H2B	105.5	C27—O28—La1^ii	146.54 (15)
La1—O3—H3A	112.7	C32—O30—H30	110.6
La1—O3—H3B	110.9	O31—C32—O30	123.9 (2)
H3A—O3—H3B	105.2	O31—C32—C33	121.2 (2)
La1—O4—H4A	124.5	O30—C32—C33	114.6 (2)
La1—O4—H4B	113.1	C34—C33—C37^iii	120.6 (2)
H4A—O4—H4B	110.0	C34—C33—C32	116.0 (2)
La1—O5—H5A	127.7	C37^iii—C33—C32	122.8 (2)
La1—O5—H5B	125.9	C33—C34—C35	120.5 (2)
H5A—O5—H5B	102.8	C33—C34—H34	119.7
La1—O6—H6A	114.9	C35—C34—H34	119.7
La1—O6—H6B	136.0	C36—C35—C34	121.0 (2)
H6A—O6—H6B	108.4	C36—C35—H35	119.5
La1—O7—H7A	132.8	C34—C35—H35	119.5
La1—O7—H7B	115.0	C35—C36—C37	120.0 (2)
H7A—O7—H7B	106.0	C35—C36—C38	116.8 (2)
La1—O8—H8A	131.4	C37—C36—C38	122.9 (2)
La1—O8—H8B	116.9	C37^iii—C37—C33^iii	118.2 (3)
H8A—O8—H8B	108.1	C37^iii—C37—C36	118.9 (3)
C11—O9—La1	148.13 (15)	C33^iii—C37—C36	122.9 (2)
O9—C11—O10	125.7 (2)	O40—C38—O39	124.5 (2)
O9—C11—C12	116.8 (2)	O40—C38—C36	118.4 (2)
O10—C11—C12	117.4 (2)	O39—C38—C36	117.1 (2)
C13—C12—C25	120.7 (2)	H41A—O41—H41B	108.9
C13—C12—C11	116.6 (2)	H42A—O42—H42B	106.1

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2B···O41	0.90	1.93	2.822 (2)	176
O2—H2A···O10^i	0.90	1.77	2.653 (2)	166
O3—H3A···O20^iv	0.90	1.97	2.857 (2)	167
O3—H3B···O10^i	0.90	1.99	2.862 (2)	165
O4—H4A···O30^v	0.90	2.02	2.919 (2)	173
O4—H4B···O2^ii	0.90	2.09	2.984 (2)	178
O5—H5A···O31	0.90	1.89	2.751 (2)	161
O5—H5B···O40^vi	0.90	1.82	2.705 (2)	167
O6—H6A···O29	0.90	1.88	2.777 (2)	175
O6—H6B···O42^vii	0.90	1.86	2.749 (3)	169
O7—H7A···O39^vii	0.90	2.04	2.902 (2)	160
O7—H7B···O29^i	0.90	1.97	2.810 (2)	155
O8—H8A···O42	0.90	1.86	2.723 (3)	160
O8—H8B···O10	0.90	2.27	3.027 (3)	141
O30—H30···O39^vii	0.90	1.60	2.494 (2)	171
O41—H41A···O29^viii	0.90	1.93	2.776 (2)	157
O41—H41B···O31	0.90	1.90	2.708 (2)	149
O42—H42A···O40^vi	0.90	1.85	2.720 (3)	164
O42—H42B···O41	0.90	1.90	2.795 (3)	174

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