# A lanthanum coordination polymer with 3,6-dichlorophthalate and 2,4-dichloro-6-(ethoxycarbonyl)benzoate as ligands

Christine Hénaff, Thierry Roisnel, Chloé Blais, Olivier Guillou, Carole Daiguebonne

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Christine Hénaff, Thierry Roisnel, Chloé Blais, Olivier Guillou, Carole Daiguebonne. A lanthanum coordination polymer with 3,6-dichlorophthalate and 2,4-dichloro-6-(ethoxycarbonyl)benzoate as ligands. Acta crystallographica Section E: Crystallographic communications [2015-..], 2025, 81 (12), pp.1106-1110. 10.1107/s2056989025009508. hal-05405286

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Distributed under a Creative Commons CC BY 4.0 - Attribution - International License
Acta Cryst.

E

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN 2056-9890

Received 10 September 2025

Accepted 29 October 2025

Edited by F. F. Ferreira, Universidade Federal do ABC, Brazil

**Keywords:** crystal structure; lanthanum; 3,6-dichlorophthalate; coordination polymer; luminescent marker.

CCDC reference: 2430840

**Supporting information:** this article has
supporting information at journals.iucr.org/e

# A lanthanum coordination polymer with 3,6-dichlorophthalate and 2,4-dichloro-6-(ethoxycarbonyl)benzoate as ligands

Christine Hénaff,ª* Thierry Roisnel,ᵇ Chloé Blais,ª Olivier Guillouª,ᶜ and Carole Daiguebonneª

A one-dimensional lanthanum-based coordination polymer based on 3,6-dichlorophthalate has been prepared and structurally described, namely, poly [[tetraaqu[a[2,4-dichloro-6-(ethoxycarbonyl)benzoato](μ₃⁻-3,6-dichlorophthalato)lanthanum(III)] monohydrate], [[La(C₈H₂Cl₂O₄)(C₁₀H₇Cl₂O₄)(H₂O)₄]⁻-H₂O]∞. Its crystal structure can be described based on molecular double chains in which lanthanum ions are linked to each other by ligands. There are several structural features that seem promising as far as luminescence properties are concerned, such as the presence of strong hydrogen bonds and of short halogen contacts, as well as quite long intermetallic distances. It is a pity that, to date, only a lanthanum-based compound has been obtained.

## 1. Chemical context

Materials traceability is an ongoing challenge. Indeed, the consumption of plastics is continuously growing worldwide, and their recycling is an environmental emergency. However, whatever the recycling process, homogeneous waste batches are required and marking plastics would enable rigorous waste sorting (Vollmer *et al.*, 2020). However, plastics must not only be marked according to the polymer matrix but also according to their complete formulation. Therefore, because of the wide variety of plastic formulations, marking them requires a large number of markers.

Our group was the first to design luminescent hetero-lanthanide coordination polymers (Kerbellec *et al.*, 2009) and to demonstrate that these compounds behave like true molecular alloys (Blais *et al.*, 2023; Ferlay & Hosseini, 2004; Haquin *et al.*, 2013). Luminescent markers based on lanthanide coordination polymers have proved their efficiency in the fight against counterfeiting (Guillou *et al.*, 2016). They could also be relevant for marking plastics to improve their recyclability (Daiguebonne *et al.*, 2025).

Recent studies strongly suggest that hetero-lanthanide coordination polymers with halogeno-derivatives of phthalic acid (Fig. 1) exhibit very promising luminescent properties and could be suitable for materials traceability (Blais *et al.*, 2025; Ngom *et al.*, 2024; Pointel, Suffren *et al.*, 2020; Pointel, Houard *et al.*, 2020; Hénaff *et al.*, 2026). There are several reasons that can explain such promising luminescent properties (Bünzli, 2010, 2015): (i) the adjacent positions of the two carboxylate functions enable the ligand to bridge several metal ions (Fig. 2), which can induce a fairly high rigidity of the molecular motif and therefore helps to limit non-radiative vibrational de-

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Published under a CC BY 4.0 licence

<footnote>ªUniv Rennes, INSA Rennes, CNRS UMR 6226 "Institut des Sciences Chimiques de Rennes", 35708 Rennes, France,</footnote>

<footnote>ᵇUniv Rennes, CNRS UMR 6226 "Institut des Sciences Chimiques de Rennes", 35042 Rennes, France, and cInstitut Universitaire de France, 1 rue Descartes, 75005 Paris, France. *Correspondence e-mail: christine.henaff@insa-rennes.fr</footnote>
<figure><img src="image_5.png" /><figcaption>**Figure 1**
Schematic representations of benzene-1,2-dicarboxylic or phthalic acid (a), 3,6-dichlorophthalic acid (b), 4,7-dichlorobenzofuran-1,3-dione (c) and 2,4-dichloro-6-(ethoxycarbonyl)benzoate (d).</figcaption></figure>

excitation; (ii) halogeno substituents can be involved in halogen-bond networks (Cavallo *et al.*, 2016; Fourmigué, 2009) that can keep molecular motifs away from each other and prevent π-stacking interactions, which is beneficial for reducing intermetallic energy transfers (Förster, 1960; Dexter, 1953; Blais *et al.*, 2022; Imbert *et al.*, 2003). The nature and the position of the halogeno substituents influence the energy of the first singlet and triplet excited states (Latva *et al.*, 1997; Steemers *et al.*, 1995), the photo-induced electron transfer (PET) mechanism (Freslon *et al.*, 2014) and the strength of the halogen interactions (Metrangolo *et al.*, 2008; Metrangolo & Resnati, 2001). However, contrary to halogenoterephthalate-based lanthanide coordination polymers (Smith *et al.*, 2024), halogenophthalate-based lanthanide coordination polymers have been little studied. So, for example, the only lanthanide coordination polymers based on dichlorophthalates described today are those involving 4,5-dichlorophthalate (Badiane *et al.*, 2018; Qiao *et al.*, 2018; He *et al.*, 2017) and, to the best of our knowledge, there is no example of lanthanide coordination polymers based on 3,6-dichlorophthalate (3,6-dcpa²⁻) in the literature.

We have thus undertaken a study of such compounds based on 3,6-dichlorophthalate. For reasons of commercial availability, and because anhydrides easily hydrolyse leading to the corresponding carboxylic acids, we have chosen to use 4,7-dichlorobenzofuran-1,3-dione as starting reactant. In the frame of this study, we have obtained a lanthanum coordination polymer with chemical formula $[La(3,6-dcpa)(C_{10}H_{7}Cl_{2}O_{4})(H_{2}O)_{4} \cdot H_{2}O]_{\infty}$. In this compound, as expected, 3,6-dichloro-phthalate comes from 4,7-dichlorobenzofuran-1,3-dione. Unexpectedly, a second ligand is also produced: 2,4-

dichloro-6-(ethoxycarbonyl)benzoate. This kind of re-organization of the ligand is commonly observed (Feng *et al.*, 2016; Abdallah *et al.*, 2020). To the best of our knowledge, this compound constitutes the first example of a lanthanide coordination polymer based on the 3,6-dcpa²⁻ ligand. Despite great synthetic effort, to date we have not not succeeded in synthesizing isomorphous compounds that involve luminescent lanthanide ions.

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## 2. Structural commentary

Microwave-assisted reaction in water between lanthanum chloride and 4,7-dichlorobenzofuran-1,3-dione leads to a coordination polymer with chemical formula $[La(3,6-dcpa)-

<figure><img src="image_7.png" /><figcaption>**Figure 3**
Projection view of an extended asymmetric unit with the numbering scheme of $[La(3,6-dcpa)(C_{10}H_{7}Cl_{2}O_{4})(H_{2}O)_{4} \cdot H_{2}O]_{\infty}$. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i) −1 + x, y, z; (ii) 1 − x, 1 − y, 2 − z]. The crystallization water molecule is omitted.</figcaption></figure>

<figure><img src="image_8.png" /><figcaption>**Figure 2**
Coordination modes observed in lanthanide coordination polymers based on a phthalate ligand.</figcaption></figure>
<figure><img src="image_9.png" /><figcaption>Figure 4</figcaption></figure>

Schematic representation of the neighbourhood of the $La^{3+}$ ion (left) and coordination modes of the 3,6-dcpa$^{2-}$ ligand (top right) and of the 2,4-dichloro-6-(ethoxycarbonyl)benzoate ligand (bottom right) of [La(3,6-dcpa)(C$_{10}$H$_7$Cl$_2$O$_4$)(H$_2$O)$_4$·H$_2$O]$_∞$.

$(C_{10}H_{7}Cl_{2}O_{4})(H_{2}O)_{4}·H_{2}O]_{∞}$ where 3,6-dcpa$^{2-}$ symbolizes 3,6-dichloropthalate (CCDC-2430840) (Fig. 3).

There is one independent lanthanum ion in this crystal structure. It is ninefold coordinated by nine oxygen atoms. Four out of the nine are from four coordination water molecules (O1, O2, O3 and O6), four more (O4, O7i, O8ii and O9ii) are from carboxylate functions that belong to three different 3,6-dcpa$^{2-}$ ligands and the remaining one (O5) is from a carboxylate function that belongs to the 2,4-dichloro-6-(ethoxycarbonyl)benzoate ligand. They form a spherical capped square antiprism (Table S1) (Casanova et al., 2005; Alvarez et al., 2005). There is also one independent 3,6-dcpa$^{2-}$ ligand and one independent 2,4-dichloro-6-(ethoxycarbonyl) benzoate ligand in the crystal structure. The former is $μ_3(η_1η_1η_2)$ and the latter is $μ_1(η_1)$ (Fig. 4). Finally, there is one crystallization water molecule (H13A–O13–H13B) in the crystal structure.

The crystal structure is mono-dimensional and can be described based on molecular double chains that spread parallel to the *a* axis (Fig. 5). Inside these molecular double

<caption>Table 1</caption>

Hydrogen-bond geometry (Å, °).

<table><thead><tr><th>D–H···A</th><th>D–H</th><th>H···A</th><th>D···A</th><th>D–H···A</th></tr></thead><tbody><tr><td>O1–H1A···O13</td><td>0.84 (4)</td><td>2.00 (4)</td><td>2.787 (4)</td><td>155 (4)</td></tr><tr><td>O1–H1B···O10<sup>iii</sup></td><td>0.80 (4)</td><td>1.89 (5)</td><td>2.663 (4)</td><td>164 (4)</td></tr><tr><td>O2–H2A···O10<sup>iii</sup></td><td>0.77 (5)</td><td>2.28 (5)</td><td>2.972 (4)</td><td>150 (4)</td></tr><tr><td>O2–H2B···O1<sup>iii</sup></td><td>0.80 (5)</td><td>2.11 (5)</td><td>2.868 (4)</td><td>159 (4)</td></tr><tr><td>O3–H3A···O10<sup>iii</sup></td><td>0.82 (5)</td><td>2.10 (5)</td><td>2.850 (4)</td><td>152 (4)</td></tr><tr><td>O3–H3B···O13<sup>i</sup></td><td>0.76 (5)</td><td>2.13 (5)</td><td>2.883 (4)</td><td>174 (5)</td></tr><tr><td>O6–H6A···O9<sup>iv</sup></td><td>0.78 (4)</td><td>2.10 (4)</td><td>2.864 (3)</td><td>166 (4)</td></tr><tr><td>O6–H6B···O8</td><td>0.85 (4)</td><td>1.92 (4)</td><td>2.772 (3)</td><td>175 (4)</td></tr><tr><td>O13–H13A···O11<sup>iii</sup></td><td>0.81 (5)</td><td>2.16 (5)</td><td>2.948 (4)</td><td>164 (5)</td></tr><tr><td>O13–H13B···O9<sup>v</sup></td><td>0.87 (5)</td><td>2.30 (5)</td><td>3.008 (4)</td><td>139 (4)</td></tr></tbody></table>

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

<caption>Table 2</caption>

Selected interatomic distances (Å).

<table><tr><td>Cl2<sup>i</sup>···Cl3</td><td>3.4185 (16)</td><td>Cl3<sup>ii</sup>···Cl4</td><td>3.4645 (15)</td></tr><tr><td>Cl2···Cl3</td><td>3.4287 (15)</td><td></td><td></td></tr></table>

Symmetry codes: (i) $x + 1, y, z$; (ii) $x, -y + \frac{3}{2}, z + \frac{1}{2}$.

chains, lanthanum ions are linked to each other by 3,6-dcpa$^{2-}$ ligands while the ethyl groups of the 2,4-dichloro-6-(ethoxycarbonyl)benzoates point toward the intermolecular space. The shortest distances between lanthanide ions that belong to the same molecular motif are about 6 Å (Fig. 5).

It is noticeable that there is a dense network of strong intra- and inter-molecular hydrogen bonds (Fig. 5 and Table 1) in this crystal structure. Additionally, there are some weak $π-π$ interactions (shortest centroid–centroid distances are 3.7 Å).

### 3. Supramolecular features

The crystal structure can be described as a juxtaposition of molecular chains that spread along the *a*-axis direction. Beyond the network of strong hydrogen bonds, the cohesion of the crystal packing is reinforced by Cl···Cl interactions (Table 2). There are seven $La^{3+}$ ions closer than 10 Å from a given $La^{3+}$ ion (Table 3). All seven belong to two adjacent molecular motifs spreading parallel to the *ac* plane (Fig. 6).

<figure><img src="image_10.png" /><figcaption>Figure 5</figcaption></figure>

Left: Projection view along the *b* axis of a molecular double chain of [La(3,6-dcpa)(C$_{10}$H$_7$Cl$_2$O$_4$)(H$_2$O)$_4$·H$_2$O]$_∞$. Shortest intermetallic distances are $d(\text{La}–\text{La}^i) = 6.8045$ (8) Å, $d(\text{La}–\text{La}^{ii}) = 6.0680$ (4) Å and $d(\text{La}^i–\text{La}^{ii}) = 6.3651$ (3) Å. Symmetry codes: (i) $-1 + x, y, z$; (ii) $-x, 1 - y, 2 - z$. Right: Projection view along the *a* axis of two adjacent molecular motifs. Dotted blue lines indicate hydrogen bonds.

<figure><img src="image_11.png" /></figure>
<caption>**Table 3**</caption>

La···La distances (Å) shorter than 10 Å in [La(3,6-dcpa)(C₁₀H₇·Cl₂O₄)(H₂O)₄·H₂O]∞.

<table><thead><tr><th>Atom1</th><th>Atom2</th><th>Symmetry</th><th>Distance</th></tr></thead><tbody><tr><td rowspan="6">La1</td><td>La1</td><td>-x, 1 - y, 2 - z</td><td>6.0682 (6)</td></tr><tr><td>La1</td><td>-x, 1 - y, 1 - z</td><td>6.2554 (7)</td></tr><tr><td>La1</td><td>1 - x, 1 - y, 2 - z</td><td>6.3650 (6)</td></tr><tr><td>La1</td><td>1 + x, y, z</td><td>6.8044 (8)</td></tr><tr><td>La1</td><td>-1 + x, y, z</td><td>6.8046 (8)</td></tr><tr><td>La1</td><td>1 - x, 1 - y, 1 - z</td><td>8.5065 (8)</td></tr><tr><td>La1</td><td>-1 - x, 1 - y, 1 - z</td><td>9.9248 (9)</td></tr></tbody></table>

In conclusion, this crystal structure presents interesting features as far as luminescent properties are concerned. Indeed, the lanthanide ions are quite far from each other and the dense network of hydrogen and halogen bonds is expected to limit non-radiative vibrational de-excitation. The reproducibility of the synthesis was checked by reproducing it several times. Unfortunately, to date, we have not succeeded in synthesizing any iso-structural coordination polymer based on a luminescent lanthanide ion.

## 4. Database survey

A search of the Cambridge Structural Database was performed using ConQuest (version 2024.2.0, CSD version 5.45, updated September 2024; Groom et al., 2016). For lanthanide coordination polymers based on phthalate ligands, see: Li et al. (2009; CSD refcode KUGPUY); Meng et al. (2006; LEJPIA); Wan et al. (2002; WUJSID, WUJSOJ, WUJSUP, WUJTAW); Song et al. (2004, 2010; FIBWOD, YURGIC); Thirumurugan & Natarajan (2003; BEVPIC); Wang et al. (2008; FARJAL, KIWPOW) Pizon et al. (2010; IJEJOX); Luo et al. (2010; DUWRIX; Lush & Shen (2011; AZITOT); for 3,6-dichlorophthalate, see: Mattes & Dorau (1986; SAZQOZ); for lanthanide coordination polymers based on 4,5-dichloro-

<figure><img src="image_12.png" /><figcaption>**Figure 6**</figcaption></figure>

Projection view along the *b* axis of two adjacent molecular motifs. The dotted circle centred on the given La³⁺ ion (in yellow) has a 10 Å radius.

<caption>**Table 4**</caption>

Experimental details.

<table><tbody><tr><td colspan="2">Crystal data</td></tr><tr><td>Chemical formula</td><td>[La(C₈H₂Cl₂O₄)-<br>(C₁₀H₇Cl₂O₄)(H₂O)₄]·H₂O</td></tr><tr><td>M<sub>r</sub></td><td>724.04</td></tr><tr><td>Crystal system, space group</td><td>Monoclinic, P2<sub>1</sub>/c</td></tr><tr><td>Temperature (K)</td><td>150</td></tr><tr><td>a, b, c (Å)</td><td>6.8045 (7), 32.376 (3), 11.5188 (12)</td></tr><tr><td>β (°)</td><td>100.862 (4)</td></tr><tr><td>V (Å<sup>3</sup>)</td><td>2492.2 (4)</td></tr><tr><td>Z</td><td>4</td></tr><tr><td>Radiation type</td><td>Mo Kα</td></tr><tr><td>μ (mm<sup>-1</sup>)</td><td>2.21</td></tr><tr><td>Crystal size (mm)</td><td>0.44 × 0.07 × 0.03</td></tr><tr><td colspan="2">Data collection</td></tr><tr><td>Diffractometer</td><td>D8 VENTURE Bruker AXS</td></tr><tr><td>Absorption correction</td><td>Multi-scan (SADABS; Krause et al., 2015)</td></tr><tr><td>T<sub>min</sub>, T<sub>max</sub></td><td>0.777, 0.936</td></tr><tr><td>No. of measured, independent and<br>observed [I > 2σ(I)] reflections</td><td>19761, 5674, 5503</td></tr><tr><td>R<sub>int</sub></td><td>0.028</td></tr><tr><td>(sin θ/λ)<sub>max</sub> (Å<sup>-1</sup>)</td><td>0.650</td></tr><tr><td colspan="2">Refinement</td></tr><tr><td>R[F<sup>2</sup> > 2σ(F<sup>2</sup>)], wR(F<sup>2</sup>), S</td><td>0.033, 0.068, 1.27</td></tr><tr><td>No. of reflections</td><td>5674</td></tr><tr><td>No. of parameters</td><td>355</td></tr><tr><td>H-atom treatment</td><td>H atoms treated by a mixture of<br>independent and constrained<br>refinement</td></tr><tr><td>Δρ<sub>max</sub>, Δρ<sub>min</sub> (e Å<sup>-3</sup>)</td><td>0.72, -1.05</td></tr></tbody></table>

Computer programs: APEX3 (Bruker, 2015), SAINT (Bruker, 2014), SHELXT (Sheldrick, 2015a), SHELXL20192 (Sheldrick, 2015b), SXGRAPH (Farrugia, 1999), Mercury (Macrae et al., 2020) and CRYSCALC (T. Roisnel, local program, 2024).

hthalates, see: Badiane et al. (2018; BETYOR); Qiao et al. (2018; GIQCIV, GIQCOB, GIQCUH, GIQDAO, MICCEJ); He et al. (2017; DEJGAD). For a structural comparison between these crystal structures, see: Hénaff et al. (2026).

## 5. Synthesis and crystallization

Lanthanum oxide (4N) was purchased from Ampère. Hydrated lanthanum chloride [LaCl₃(H₂O)₆] was prepared according to established procedures (Desreux, 1989). 4,7-Dichlorobenzofuran-1,3-dione (C₈H₂Cl₂O₃, 98%) was purchased from BDLpharm and used without further purification. 0.5 mmol (185.6 mg) of LaCl₃(H₂O)₆, 0.75 mmol (162.7 mg) of C₈H₂Cl₂O₃, 1.5 mL of a solution of sodium hydroxide (1 mol L⁻¹) and 3.5 mL of deionized water were put in a 10 mL sealed Pyrex test tube in a CEM Discover microwave oven and maintained for 10 min under stirring (T = 403 K; P = 2.5 bar). Single crystals suitable for X-ray diffraction were obtained after slow evaporation of the supernatant solution extracted after the synthesis.

## 6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 4. Except for O-bound H atoms that were introduced in the structural model through
Fourier difference map analysis, H atoms were finally included in their calculated positions (C–H = 0.95–0.98 Å) and treated as riding on their parent atom with $U_{iso}(H) = 1.2–1.5U_{eq}(C)$.

## Acknowledgements

The CDifX (Centre de Diffractométrie X) of ISCR is acknowledged for X-ray diffraction data collection.

## Funding information

Funding for this research was provided by: Région Bretagne (grant No. ARED-COH24014).

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supporting information

Acta Cryst. (2025). E81, 1106-1110 [https://doi.org/10.1107/S2056989025009508]

# A lanthanum coordination polymer with 3,6-dichlorophthalate and 2,4-dichloro-6-(ethoxycarbonyl)benzoate as ligands

Christine Hénaff, Thierry Roisnel, Chloé Blais, Olivier Guillou and Carole Daiguebonne

## Computing details

Poly[[tetraqua[2,4-dichloro-6-(ethoxycarbonyl)benzoate](μ₃-3,6-dichlorophthalato)lanthanum(III)] monohydrate]

### Crystal data

[La(C₈H₂Cl₂O₄)(C₁₀H₇Cl₂O₄)(H₂O)₄]·H₂O

$M_r = 724.04$

Monoclinic, P2₁/c

$a = 6.8045 (7) Å$

$b = 32.376 (3) Å$

$c = 11.5188 (12) Å$

$\beta = 100.862 (4)°$

$V = 2492.2 (4) Å³$

$Z = 4$

$F(000) = 1424$

$D_x = 1.930 \text{ Mg m}^{-3}$

Mo Kα radiation, $\lambda = 0.71073$ Å

Cell parameters from 9930 reflections

$\theta = 2.6–27.5°$

$\mu = 2.21 \text{ mm}^{-1}$

$T = 150$ K

Stick, colourless

$0.44 \times 0.07 \times 0.03 \text{ mm}$

### Data collection

D8 VENTURE Bruker AXS
diffractometer

Radiation source: Incoatec microfocus sealed
tube

Multilayer monochromator

Detector resolution: 7.39 pixels mm⁻¹

rotation images scans

Absorption correction: multi-scan
(SADABS; Krause et al., 2015)

$T_{min} = 0.777, T_{max} = 0.936$

19761 measured reflections

5674 independent reflections

5503 reflections with $I > 2\sigma(I)$

$R_{int} = 0.028$

$\theta_{max} = 27.5°, \theta_{min} = 1.9°$

$h = -8 \rightarrow 8$

$k = -41 \rightarrow 41$

$l = -14 \rightarrow 14$

### Refinement

Refinement on $F^2$

Least-squares matrix: full

$R[F^2 > 2\sigma(F^2)] = 0.033$

$wR(F^2) = 0.068$

$S = 1.27$

5674 reflections

355 parameters

0 restraints

Primary atom site location: dual

Hydrogen site location: mixed

H atoms treated by a mixture of independent
and constrained refinement

$w = 1/[\sigma^2(F_o^2) + 7.126P]$  
where $P = (F_o^2 + 2F_c^2)/3$

($\Delta/\sigma)_{max} = 0.002$

$\Delta\rho_{max} = 0.72 \text{ e Å}^{-3}$

$\Delta\rho_{min} = -1.05 \text{ e Å}^{-3}$
Special details

**Experimental.** A suitable crystal for X-ray diffraction single crystal experiment (colourless stick, dimensions = 0.030 x 0.070 x 0.440 mm) was selected and mounted with a cryoloop on the goniometer head of a D8 Venture (Bruker-AXS) diffractometer equipped with a CMOS-PHOTON70 detector, using Mo-Kα radiation (λ = 0.71073 Å, multilayer monochromator) at T = 150 (2) K. Crystal structure has been described in monoclinic symmetry and *P* 2₁/c (I.T.#14) centric space group (Rint=0.0280; Rsigma=0.0262). Cell parameters have been refined as follows: *a* = 6.8045 (7) Å, *b* = 32.376 (3) Å, *c*=11.5188 (12) Å, β = 100.862 (4) °, *V* = 2492.2 (4) Å³. Number of formula unit Z is equal to 4 and calculated density *d* and absorption coefficient *μ* values are 1.930 g.cm⁻³ and 2.207mm⁻¹ respectively. Crystal structure was solved by dual-space algorithm using *SHELXT* program and then refined with full-matrix least-squares methods based on *F*² (*SHELXL* program). All non-Hydrogen atoms were refined with anisotropic atomic displacement parameters. Except Hydrogen atoms linked to Oxygen atoms that were introduced in the structural model through Fourier difference maps analysis, H atoms were finally included in their calculated positions and treated as riding on their parent atom with constrained thermal parameters. A final refinement on *F*² with 5674 unique intensities and 355 parameters converged at ωR(*F*²)=0.0678 (Rf = 0.0325) for 5503 observed reflections with *I* > 2σ.

**Geometry.** All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

**Refinement.** Refinement of *F*² against ALL reflections. The weighted R-factor *wR* and goodness of fit *S* are based on *F*², conventional R-factors *R* are based on *F*, with *F* set to zero for negative *F*². The threshold expression of *F*² > 2*sigma*(*F*²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on *F*² are statistically about twice as large as those based on *F*, and R-factors based on ALL data will be even larger.

<table><caption>Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²)</caption><thead><tr><th></th><th>x</th><th>y</th><th>z</th><th>U<sub>iso</sub>*/U<sub>eq</sub></th></tr></thead><tbody><tr><td>La1</td><td>0.15728 (3)</td><td>0.49053 (2)</td><td>0.77186 (2)</td><td>0.01071 (6)</td></tr><tr><td>Cl1</td><td>0.52632 (12)</td><td>0.57653 (3)</td><td>0.57191 (7)</td><td>0.02214 (17)</td></tr><tr><td>Cl2</td><td>0.86113 (15)</td><td>0.66386 (3)</td><td>1.04825 (9)</td><td>0.0310 (2)</td></tr><tr><td>Cl3</td><td>0.35058 (15)</td><td>0.65895 (3)</td><td>1.01756 (8)</td><td>0.0320 (2)</td></tr><tr><td>Cl4</td><td>0.1852 (2)</td><td>0.74928 (3)</td><td>0.62045 (10)</td><td>0.0402 (3)</td></tr><tr><td>O1</td><td>-0.1375 (4)</td><td>0.45586 (8)</td><td>0.6315 (2)</td><td>0.0190 (5)</td></tr><tr><td>H1A</td><td>-0.216 (7)</td><td>0.4425 (13)</td><td>0.666 (4)</td><td>0.023*</td></tr><tr><td>H1B</td><td>-0.111 (6)</td><td>0.4389 (13)</td><td>0.586 (4)</td><td>0.023*</td></tr><tr><td>O2</td><td>0.2230 (4)</td><td>0.48617 (8)</td><td>0.5597 (2)</td><td>0.0201 (5)</td></tr><tr><td>H2A</td><td>0.195 (7)</td><td>0.4665 (14)</td><td>0.522 (4)</td><td>0.024*</td></tr><tr><td>H2B</td><td>0.227 (6)</td><td>0.5050 (14)</td><td>0.515 (4)</td><td>0.024*</td></tr><tr><td>O3</td><td>0.2806 (4)</td><td>0.41711 (8)</td><td>0.7131 (2)</td><td>0.0214 (5)</td></tr><tr><td>H3A</td><td>0.234 (7)</td><td>0.4074 (13)</td><td>0.648 (4)</td><td>0.026*</td></tr><tr><td>H3B</td><td>0.390 (7)</td><td>0.4112 (14)</td><td>0.728 (4)</td><td>0.026*</td></tr><tr><td>O4</td><td>0.5011 (3)</td><td>0.51206 (7)</td><td>0.7824 (2)</td><td>0.0185 (5)</td></tr><tr><td>O5</td><td>0.0711 (4)</td><td>0.55684 (7)</td><td>0.6732 (2)</td><td>0.0187 (5)</td></tr><tr><td>O6</td><td>0.2443 (4)</td><td>0.53789 (8)</td><td>0.9496 (2)</td><td>0.0162 (5)</td></tr><tr><td>H6A</td><td>0.172 (6)</td><td>0.5421 (13)</td><td>0.994 (4)</td><td>0.019*</td></tr><tr><td>H6B</td><td>0.365 (7)</td><td>0.5414 (13)</td><td>0.985 (4)</td><td>0.019*</td></tr><tr><td>O7</td><td>0.8332 (3)</td><td>0.51060 (7)</td><td>0.8259 (2)</td><td>0.0175 (5)</td></tr><tr><td>O8</td><td>0.6424 (3)</td><td>0.55065 (7)</td><td>1.05147 (19)</td><td>0.0160 (5)</td></tr><tr><td>O9</td><td>0.9632 (3)</td><td>0.56660 (7)</td><td>1.08782 (19)</td><td>0.0163 (5)</td></tr><tr><td>O10</td><td>-0.0218 (4)</td><td>0.59396 (8)</td><td>0.5099 (2)</td><td>0.0203 (5)</td></tr></tbody></table>
<table><tr><td>O11</td><td>0.1928 (5)</td><td>0.66501 (9)</td><td>0.4265 (2)</td><td>0.0350 (7)</td></tr><tr><td>O12</td><td>-0.1099 (4)</td><td>0.68329 (9)</td><td>0.4598 (2)</td><td>0.0321 (6)</td></tr><tr><td>O13</td><td>-0.3045 (4)</td><td>0.39310 (9)</td><td>0.7472 (3)</td><td>0.0286 (6)</td></tr><tr><td>H13A</td><td>-0.272 (7)</td><td>0.3738 (15)</td><td>0.711 (4)</td><td>0.034*</td></tr><tr><td>H13B</td><td>-0.220 (7)</td><td>0.3931 (15)</td><td>0.814 (4)</td><td>0.034*</td></tr><tr><td>C1</td><td>0.6686 (5)</td><td>0.52900 (10)</td><td>0.8040 (3)</td><td>0.0139 (6)</td></tr><tr><td>C2</td><td>0.6774 (4)</td><td>0.57584 (10)</td><td>0.8076 (3)</td><td>0.0135 (6)</td></tr><tr><td>C3</td><td>0.6275 (5)</td><td>0.59966 (11)</td><td>0.7059 (3)</td><td>0.0158 (6)</td></tr><tr><td>C4</td><td>0.6544 (5)</td><td>0.64206 (11)</td><td>0.7079 (3)</td><td>0.0208 (7)</td></tr><tr><td>H4</td><td>0.622165</td><td>0.657699</td><td>0.637085</td><td>0.025*</td></tr><tr><td>C5</td><td>0.7287 (5)</td><td>0.66131 (11)</td><td>0.8138 (3)</td><td>0.0215 (7)</td></tr><tr><td>H5</td><td>0.747350</td><td>0.690401</td><td>0.816744</td><td>0.026*</td></tr><tr><td>C6</td><td>0.7758 (5)</td><td>0.63795 (11)</td><td>0.9160 (3)</td><td>0.0192 (7)</td></tr><tr><td>C7</td><td>0.7527 (5)</td><td>0.59551 (10)</td><td>0.9149 (3)</td><td>0.0138 (6)</td></tr><tr><td>C8</td><td>0.7894 (5)</td><td>0.56959 (9)</td><td>1.0260 (3)</td><td>0.0128 (6)</td></tr><tr><td>C9</td><td>0.0562 (5)</td><td>0.59016 (10)</td><td>0.6172 (3)</td><td>0.0140 (6)</td></tr><tr><td>C10</td><td>0.1326 (5)</td><td>0.62886 (10)</td><td>0.6833 (3)</td><td>0.0153 (6)</td></tr><tr><td>C11</td><td>0.1994 (5)</td><td>0.62682 (10)</td><td>0.8049 (3)</td><td>0.0163 (6)</td></tr><tr><td>H11</td><td>0.203366</td><td>0.601080</td><td>0.844882</td><td>0.020*</td></tr><tr><td>C12</td><td>0.2599 (5)</td><td>0.66250 (11)</td><td>0.8673 (3)</td><td>0.0192 (7)</td></tr><tr><td>C13</td><td>0.2529 (6)</td><td>0.70049 (11)</td><td>0.8124 (3)</td><td>0.0235 (7)</td></tr><tr><td>H13</td><td>0.290133</td><td>0.724962</td><td>0.856623</td><td>0.028*</td></tr><tr><td>C14</td><td>0.1899 (6)</td><td>0.70185 (11)</td><td>0.6906 (3)</td><td>0.0227 (7)</td></tr><tr><td>C15</td><td>0.1311 (5)</td><td>0.66659 (11)</td><td>0.6241 (3)</td><td>0.0184 (7)</td></tr><tr><td>C16</td><td>0.0752 (6)</td><td>0.67031 (11)</td><td>0.4919 (3)</td><td>0.0235 (7)</td></tr><tr><td>C17</td><td>-0.1740 (9)</td><td>0.69157 (16)</td><td>0.3343 (4)</td><td>0.0497 (13)</td></tr><tr><td>H17A</td><td>-0.180144</td><td>0.665521</td><td>0.288787</td><td>0.060*</td></tr><tr><td>H17B</td><td>-0.078142</td><td>0.710400</td><td>0.306355</td><td>0.060*</td></tr><tr><td>C18</td><td>-0.3711 (10)</td><td>0.7106 (2)</td><td>0.3177 (6)</td><td>0.076 (2)</td></tr><tr><td>H18A</td><td>-0.418000</td><td>0.716488</td><td>0.233614</td><td>0.114*</td></tr><tr><td>H18B</td><td>-0.464813</td><td>0.691644</td><td>0.345401</td><td>0.114*</td></tr><tr><td>H18C</td><td>-0.363204</td><td>0.736350</td><td>0.362901</td><td>0.114*</td></tr></table>

Atomic displacement parameters (Å²)

<table><thead><tr><th></th><th>U<sup>11</sup></th><th>U<sup>22</sup></th><th>U<sup>33</sup></th><th>U<sup>12</sup></th><th>U<sup>13</sup></th><th>U<sup>23</sup></th></tr></thead><tbody><tr><td>La1</td><td>0.00833 (9)</td><td>0.01307 (9)</td><td>0.01034 (8)</td><td>-0.00037 (7)</td><td>0.00073 (6)</td><td>-0.00107 (7)</td></tr><tr><td>Cl1</td><td>0.0187 (4)</td><td>0.0346 (5)</td><td>0.0126 (3)</td><td>0.0022 (3)</td><td>0.0016 (3)</td><td>0.0008 (3)</td></tr><tr><td>Cl2</td><td>0.0370 (5)</td><td>0.0243 (4)</td><td>0.0304 (5)</td><td>-0.0050 (4)</td><td>0.0029 (4)</td><td>-0.0104 (4)</td></tr><tr><td>Cl3</td><td>0.0349 (5)</td><td>0.0384 (5)</td><td>0.0217 (4)</td><td>-0.0004 (4)</td><td>0.0030 (4)</td><td>-0.0065 (4)</td></tr><tr><td>Cl4</td><td>0.0657 (8)</td><td>0.0160 (4)</td><td>0.0377 (5)</td><td>-0.0049 (5)</td><td>0.0063 (5)</td><td>0.0054 (4)</td></tr><tr><td>O1</td><td>0.0181 (12)</td><td>0.0223 (13)</td><td>0.0159 (11)</td><td>-0.0045 (10)</td><td>0.0018 (9)</td><td>-0.0044 (10)</td></tr><tr><td>O2</td><td>0.0268 (13)</td><td>0.0183 (13)</td><td>0.0158 (12)</td><td>-0.0007 (11)</td><td>0.0057 (10)</td><td>-0.0012 (10)</td></tr><tr><td>O3</td><td>0.0206 (13)</td><td>0.0244 (13)</td><td>0.0177 (12)</td><td>0.0044 (11)</td><td>-0.0003 (10)</td><td>-0.0039 (10)</td></tr><tr><td>O4</td><td>0.0123 (11)</td><td>0.0225 (12)</td><td>0.0204 (11)</td><td>-0.0030 (10)</td><td>0.0023 (9)</td><td>-0.0013 (10)</td></tr><tr><td>O5</td><td>0.0223 (12)</td><td>0.0144 (11)</td><td>0.0197 (11)</td><td>0.0004 (10)</td><td>0.0046 (10)</td><td>0.0012 (9)</td></tr><tr><td>O6</td><td>0.0098 (11)</td><td>0.0244 (13)</td><td>0.0144 (11)</td><td>0.0002 (10)</td><td>0.0024 (9)</td><td>-0.0049 (9)</td></tr><tr><td>O7</td><td>0.0120 (11)</td><td>0.0191 (12)</td><td>0.0216 (11)</td><td>0.0032 (9)</td><td>0.0039 (9)</td><td>0.0006 (10)</td></tr></tbody></table>
<table><tr><td>O8</td><td>0.0115 (11)</td><td>0.0222 (12)</td><td>0.0133 (10)</td><td>-0.0031 (9)</td><td>-0.0001 (8)</td><td>0.0017 (9)</td></tr><tr><td>O9</td><td>0.0108 (10)</td><td>0.0227 (12)</td><td>0.0148 (11)</td><td>0.0010 (9)</td><td>0.0009 (9)</td><td>0.0008 (9)</td></tr><tr><td>O10</td><td>0.0220 (12)</td><td>0.0208 (12)</td><td>0.0163 (11)</td><td>0.0026 (10)</td><td>-0.0007 (9)</td><td>-0.0006 (9)</td></tr><tr><td>O11</td><td>0.0485 (18)</td><td>0.0363 (16)</td><td>0.0247 (14)</td><td>-0.0026 (14)</td><td>0.0189 (13)</td><td>0.0013 (12)</td></tr><tr><td>O12</td><td>0.0415 (17)</td><td>0.0302 (15)</td><td>0.0211 (13)</td><td>0.0112 (13)</td><td>-0.0028 (12)</td><td>0.0021 (11)</td></tr><tr><td>O13</td><td>0.0266 (15)</td><td>0.0311 (15)</td><td>0.0281 (15)</td><td>-0.0008 (12)</td><td>0.0054 (12)</td><td>-0.0013 (12)</td></tr><tr><td>C1</td><td>0.0136 (15)</td><td>0.0200 (16)</td><td>0.0089 (13)</td><td>-0.0008 (12)</td><td>0.0040 (11)</td><td>-0.0007 (12)</td></tr><tr><td>C2</td><td>0.0081 (13)</td><td>0.0184 (15)</td><td>0.0148 (14)</td><td>0.0017 (12)</td><td>0.0039 (11)</td><td>0.0001 (12)</td></tr><tr><td>C3</td><td>0.0109 (14)</td><td>0.0231 (17)</td><td>0.0138 (14)</td><td>0.0035 (13)</td><td>0.0034 (12)</td><td>0.0009 (12)</td></tr><tr><td>C4</td><td>0.0173 (16)</td><td>0.0215 (17)</td><td>0.0248 (17)</td><td>0.0072 (14)</td><td>0.0073 (14)</td><td>0.0098 (14)</td></tr><tr><td>C5</td><td>0.0194 (17)</td><td>0.0165 (16)</td><td>0.0293 (18)</td><td>0.0016 (14)</td><td>0.0065 (14)</td><td>0.0035 (14)</td></tr><tr><td>C6</td><td>0.0167 (16)</td><td>0.0195 (17)</td><td>0.0213 (16)</td><td>-0.0018 (13)</td><td>0.0034 (13)</td><td>-0.0037 (13)</td></tr><tr><td>C7</td><td>0.0105 (14)</td><td>0.0173 (15)</td><td>0.0142 (14)</td><td>0.0004 (12)</td><td>0.0041 (11)</td><td>0.0019 (12)</td></tr><tr><td>C8</td><td>0.0153 (15)</td><td>0.0129 (14)</td><td>0.0100 (13)</td><td>0.0010 (12)</td><td>0.0022 (11)</td><td>-0.0010 (11)</td></tr><tr><td>C9</td><td>0.0112 (14)</td><td>0.0148 (15)</td><td>0.0172 (15)</td><td>-0.0007 (12)</td><td>0.0058 (12)</td><td>-0.0017 (12)</td></tr><tr><td>C10</td><td>0.0152 (15)</td><td>0.0146 (15)</td><td>0.0177 (15)</td><td>0.0006 (12)</td><td>0.0069 (12)</td><td>-0.0011 (12)</td></tr><tr><td>C11</td><td>0.0159 (15)</td><td>0.0167 (15)</td><td>0.0172 (15)</td><td>-0.0009 (13)</td><td>0.0058 (12)</td><td>0.0012 (12)</td></tr><tr><td>C12</td><td>0.0174 (16)</td><td>0.0247 (18)</td><td>0.0151 (15)</td><td>0.0001 (14)</td><td>0.0024 (12)</td><td>-0.0034 (13)</td></tr><tr><td>C13</td><td>0.0258 (18)</td><td>0.0191 (17)</td><td>0.0254 (18)</td><td>-0.0032 (15)</td><td>0.0039 (15)</td><td>-0.0057 (14)</td></tr><tr><td>C14</td><td>0.0292 (19)</td><td>0.0148 (16)</td><td>0.0252 (18)</td><td>0.0003 (14)</td><td>0.0078 (15)</td><td>0.0024 (14)</td></tr><tr><td>C15</td><td>0.0190 (16)</td><td>0.0192 (16)</td><td>0.0175 (16)</td><td>0.0013 (13)</td><td>0.0050 (13)</td><td>0.0019 (13)</td></tr><tr><td>C16</td><td>0.035 (2)</td><td>0.0151 (16)</td><td>0.0211 (17)</td><td>0.0008 (15)</td><td>0.0069 (15)</td><td>0.0030 (13)</td></tr><tr><td>C17</td><td>0.071 (4)</td><td>0.046 (3)</td><td>0.023 (2)</td><td>0.011 (3)</td><td>-0.013 (2)</td><td>0.0057 (19)</td></tr><tr><td>C18</td><td>0.065 (4)</td><td>0.086 (5)</td><td>0.063 (4)</td><td>0.016 (4)</td><td>-0.022 (3)</td><td>0.019 (4)</td></tr></table>

Geometric parameters (Å, °)

<table><tr><td>La1—O4</td><td>2.422 (2)</td><td>O12—C17</td><td>1.454 (5)</td></tr><tr><td>La1—O5</td><td>2.448 (2)</td><td>O13—H13A</td><td>0.81 (5)</td></tr><tr><td>La1—O7<sup>i</sup></td><td>2.488 (2)</td><td>O13—H13B</td><td>0.87 (5)</td></tr><tr><td>La1—O6</td><td>2.537 (2)</td><td>C1—C2</td><td>1.518 (5)</td></tr><tr><td>La1—O2</td><td>2.570 (2)</td><td>C2—C3</td><td>1.390 (4)</td></tr><tr><td>La1—O1</td><td>2.584 (2)</td><td>C2—C7</td><td>1.398 (4)</td></tr><tr><td>La1—O8<sup>ii</sup></td><td>2.595 (2)</td><td>C3—C4</td><td>1.385 (5)</td></tr><tr><td>La1—O3</td><td>2.651 (3)</td><td>C4—C5</td><td>1.379 (5)</td></tr><tr><td>La1—O9<sup>ii</sup></td><td>2.684 (2)</td><td>C4—H4</td><td>0.9500</td></tr><tr><td>La1—C8<sup>ii</sup></td><td>3.004 (3)</td><td>C5—C6</td><td>1.385 (5)</td></tr><tr><td>Cl1—C3</td><td>1.737 (3)</td><td>C5—H5</td><td>0.9500</td></tr><tr><td>Cl2—C6</td><td>1.740 (4)</td><td>C6—C7</td><td>1.383 (5)</td></tr><tr><td>Cl3—C12</td><td>1.729 (3)</td><td>C7—C8</td><td>1.511 (4)</td></tr><tr><td>Cl4—C14</td><td>1.733 (4)</td><td>C9—C10</td><td>1.507 (4)</td></tr><tr><td>O1—H1A</td><td>0.84 (4)</td><td>C10—C11</td><td>1.390 (5)</td></tr><tr><td>O1—H1B</td><td>0.80 (4)</td><td>C10—C15</td><td>1.398 (5)</td></tr><tr><td>O2—H2A</td><td>0.77 (5)</td><td>C11—C12</td><td>1.381 (5)</td></tr><tr><td>O2—H2B</td><td>0.80 (5)</td><td>C11—H11</td><td>0.9500</td></tr><tr><td>O3—H3A</td><td>0.82 (5)</td><td>C12—C13</td><td>1.379 (5)</td></tr><tr><td>O3—H3B</td><td>0.76 (5)</td><td>C13—C14</td><td>1.388 (5)</td></tr><tr><td>O4—C1</td><td>1.247 (4)</td><td>C13—H13</td><td>0.9500</td></tr></table>
<table>
  <tbody>
    <tr>
      <td>O5—C9</td>
      <td>1.251 (4)</td>
      <td>C14—C15</td>
      <td>1.391 (5)</td>
    </tr>
    <tr>
      <td>O6—H6A</td>
      <td>0.78 (4)</td>
      <td>C15—C16</td>
      <td>1.504 (5)</td>
    </tr>
    <tr>
      <td>O6—H6B</td>
      <td>0.85 (4)</td>
      <td>C17—C18</td>
      <td>1.455 (8)</td>
    </tr>
    <tr>
      <td>O7—C1</td>
      <td>1.252 (4)</td>
      <td>C17—H17A</td>
      <td>0.9900</td>
    </tr>
    <tr>
      <td>O8—C8</td>
      <td>1.255 (4)</td>
      <td>C17—H17B</td>
      <td>0.9900</td>
    </tr>
    <tr>
      <td>O9—C8</td>
      <td>1.263 (4)</td>
      <td>C18—H18A</td>
      <td>0.9800</td>
    </tr>
    <tr>
      <td>O10—C9</td>
      <td>1.257 (4)</td>
      <td>C18—H18B</td>
      <td>0.9800</td>
    </tr>
    <tr>
      <td>O11—C16</td>
      <td>1.210 (5)</td>
      <td>C18—H18C</td>
      <td>0.9800</td>
    </tr>
    <tr>
      <td>O12—C16</td>
      <td>1.313 (5)</td>
      <td></td>
      <td></td>
    </tr>
    <tr>
      <td>Cl2<sup>iii</sup>...Cl3</td>
      <td>3.4185 (16)</td>
      <td>Cl3<sup>iv</sup>...Cl4</td>
      <td>3.4645 (15)</td>
    </tr>
    <tr>
      <td>Cl2...Cl3</td>
      <td>3.4287 (15)</td>
      <td></td>
      <td></td>
    </tr>
    <tr>
      <td>O4—La1—O5</td>
      <td>85.14 (8)</td>
      <td>O4—C1—O7</td>
      <td>125.5 (3)</td>
    </tr>
    <tr>
      <td>O4—La1—O7<sup>i</sup></td>
      <td>143.67 (8)</td>
      <td>O4—C1—C2</td>
      <td>118.4 (3)</td>
    </tr>
    <tr>
      <td>O5—La1—O7<sup>i</sup></td>
      <td>75.00 (8)</td>
      <td>O7—C1—C2</td>
      <td>116.1 (3)</td>
    </tr>
    <tr>
      <td>O4—La1—O6</td>
      <td>73.11 (8)</td>
      <td>C3—C2—C7</td>
      <td>118.9 (3)</td>
    </tr>
    <tr>
      <td>O5—La1—O6</td>
      <td>81.00 (8)</td>
      <td>C3—C2—C1</td>
      <td>121.9 (3)</td>
    </tr>
    <tr>
      <td>O7<sup>i</sup>—La1—O6</td>
      <td>73.93 (8)</td>
      <td>C7—C2—C1</td>
      <td>119.0 (3)</td>
    </tr>
    <tr>
      <td>O4—La1—O2</td>
      <td>73.96 (8)</td>
      <td>C4—C3—C2</td>
      <td>121.7 (3)</td>
    </tr>
    <tr>
      <td>O5—La1—O2</td>
      <td>71.11 (8)</td>
      <td>C4—C3—Cl1</td>
      <td>118.1 (3)</td>
    </tr>
    <tr>
      <td>O7<sup>i</sup>—La1—O2</td>
      <td>125.01 (8)</td>
      <td>C2—C3—Cl1</td>
      <td>120.2 (3)</td>
    </tr>
    <tr>
      <td>O6—La1—O2</td>
      <td>138.13 (8)</td>
      <td>C5—C4—C3</td>
      <td>119.2 (3)</td>
    </tr>
    <tr>
      <td>O4—La1—O1</td>
      <td>141.71 (8)</td>
      <td>C5—C4—H4</td>
      <td>120.4</td>
    </tr>
    <tr>
      <td>O5—La1—O1</td>
      <td>90.05 (8)</td>
      <td>C3—C4—H4</td>
      <td>120.4</td>
    </tr>
    <tr>
      <td>O7<sup>i</sup>—La1—O1</td>
      <td>69.51 (8)</td>
      <td>C4—C5—C6</td>
      <td>119.5 (3)</td>
    </tr>
    <tr>
      <td>O6—La1—O1</td>
      <td>143.43 (8)</td>
      <td>C4—C5—H5</td>
      <td>120.2</td>
    </tr>
    <tr>
      <td>O2—La1—O1</td>
      <td>68.58 (8)</td>
      <td>C6—C5—H5</td>
      <td>120.2</td>
    </tr>
    <tr>
      <td>O4—La1—O8<sup>ii</sup></td>
      <td>75.46 (7)</td>
      <td>C7—C6—C5</td>
      <td>121.8 (3)</td>
    </tr>
    <tr>
      <td>O5—La1—O8<sup>ii</sup></td>
      <td>149.22 (8)</td>
      <td>C7—C6—Cl2</td>
      <td>120.4 (3)</td>
    </tr>
    <tr>
      <td>O7<sup>i</sup>—La1—O8<sup>ii</sup></td>
      <td>107.29 (7)</td>
      <td>C5—C6—Cl2</td>
      <td>117.8 (3)</td>
    </tr>
    <tr>
      <td>O6—La1—O8<sup>ii</sup></td>
      <td>70.69 (8)</td>
      <td>C6—C7—C2</td>
      <td>118.9 (3)</td>
    </tr>
    <tr>
      <td>O2—La1—O8<sup>ii</sup></td>
      <td>123.90 (8)</td>
      <td>C6—C7—C8</td>
      <td>122.9 (3)</td>
    </tr>
    <tr>
      <td>O1—La1—O8<sup>ii</sup></td>
      <td>119.92 (8)</td>
      <td>C2—C7—C8</td>
      <td>118.0 (3)</td>
    </tr>
    <tr>
      <td>O4—La1—O3</td>
      <td>85.50 (8)</td>
      <td>O8—C8—O9</td>
      <td>122.2 (3)</td>
    </tr>
    <tr>
      <td>O5—La1—O3</td>
      <td>136.70 (8)</td>
      <td>O8—C8—C7</td>
      <td>117.2 (3)</td>
    </tr>
    <tr>
      <td>O7<sup>i</sup>—La1—O3</td>
      <td>129.51 (8)</td>
      <td>O9—C8—C7</td>
      <td>120.5 (3)</td>
    </tr>
    <tr>
      <td>O6—La1—O3</td>
      <td>135.31 (8)</td>
      <td>O8—C8—La1<sup>ii</sup></td>
      <td>59.15 (16)</td>
    </tr>
    <tr>
      <td>O2—La1—O3</td>
      <td>65.67 (8)</td>
      <td>O9—C8—La1<sup>ii</sup></td>
      <td>63.26 (16)</td>
    </tr>
    <tr>
      <td>O1—La1—O3</td>
      <td>72.34 (8)</td>
      <td>C7—C8—La1<sup>ii</sup></td>
      <td>173.1 (2)</td>
    </tr>
    <tr>
      <td>O8<sup>ii</sup>—La1—O3</td>
      <td>66.07 (8)</td>
      <td>O5—C9—O10</td>
      <td>124.8 (3)</td>
    </tr>
    <tr>
      <td>O4—La1—O9<sup>ii</sup></td>
      <td>124.74 (7)</td>
      <td>O5—C9—C10</td>
      <td>118.0 (3)</td>
    </tr>
    <tr>
      <td>O5—La1—O9<sup>ii</sup></td>
      <td>144.12 (7)</td>
      <td>O10—C9—C10</td>
      <td>117.2 (3)</td>
    </tr>
    <tr>
      <td>O7<sup>i</sup>—La1—O9<sup>ii</sup></td>
      <td>69.12 (7)</td>
      <td>C11—C10—C15</td>
      <td>120.2 (3)</td>
    </tr>
    <tr>
      <td>O6—La1—O9<sup>ii</sup></td>
      <td>88.95 (7)</td>
      <td>C11—C10—C9</td>
      <td>119.1 (3)</td>
    </tr>
    <tr>
      <td>O2—La1—O9<sup>ii</sup></td>
      <td>131.49 (8)</td>
      <td>C15—C10—C9</td>
      <td>120.7 (3)</td>
    </tr>
    <tr>
      <td>O1—La1—O9<sup>ii</sup></td>
      <td>77.78 (7)</td>
      <td>C12—C11—C10</td>
      <td>119.5 (3)</td>
    </tr>
    <tr>
      <td>O8<sup>ii</sup>—La1—O9<sup>ii</sup></td>
      <td>49.35 (7)</td>
      <td>C12—C11—H11</td>
      <td>120.2</td>
    </tr>
  </tbody>
</table>
<table>
  <tbody>
    <tr>
      <td>O3—La1—O9<sup>ii</sup></td>
      <td>71.52 (7)</td>
    </tr>
    <tr>
      <td>O4—La1—C8<sup>ii</sup></td>
      <td>99.99 (8)</td>
    </tr>
    <tr>
      <td>O5—La1—C8<sup>ii</sup></td>
      <td>155.69 (8)</td>
    </tr>
    <tr>
      <td>O7<sup>i</sup>—La1—C8<sup>ii</sup></td>
      <td>87.61 (8)</td>
    </tr>
    <tr>
      <td>O6—La1—C8<sup>ii</sup></td>
      <td>77.89 (8)</td>
    </tr>
    <tr>
      <td>O2—La1—C8<sup>ii</sup></td>
      <td>133.19 (8)</td>
    </tr>
    <tr>
      <td>O1—La1—C8<sup>ii</sup></td>
      <td>99.77 (8)</td>
    </tr>
    <tr>
      <td>O8<sup>ii</sup>—La1—C8<sup>ii</sup></td>
      <td>24.53 (8)</td>
    </tr>
    <tr>
      <td>O3—La1—C8<sup>ii</sup></td>
      <td>67.60 (8)</td>
    </tr>
    <tr>
      <td>O9<sup>ii</sup>—La1—C8<sup>ii</sup></td>
      <td>24.86 (8)</td>
    </tr>
    <tr>
      <td>La1—O1—H1A</td>
      <td>114 (3)</td>
    </tr>
    <tr>
      <td>La1—O1—H1B</td>
      <td>118 (3)</td>
    </tr>
    <tr>
      <td>H1A—O1—H1B</td>
      <td>101 (4)</td>
    </tr>
    <tr>
      <td>La1—O2—H2A</td>
      <td>120 (3)</td>
    </tr>
    <tr>
      <td>La1—O2—H2B</td>
      <td>127 (3)</td>
    </tr>
    <tr>
      <td>H2A—O2—H2B</td>
      <td>108 (4)</td>
    </tr>
    <tr>
      <td>La1—O3—H3A</td>
      <td>120 (3)</td>
    </tr>
    <tr>
      <td>La1—O3—H3B</td>
      <td>121 (3)</td>
    </tr>
    <tr>
      <td>H3A—O3—H3B</td>
      <td>107 (4)</td>
    </tr>
    <tr>
      <td>C1—O4—La1</td>
      <td>167.0 (2)</td>
    </tr>
    <tr>
      <td>C9—O5—La1</td>
      <td>169.9 (2)</td>
    </tr>
    <tr>
      <td>La1—O6—H6A</td>
      <td>123 (3)</td>
    </tr>
    <tr>
      <td>La1—O6—H6B</td>
      <td>122 (3)</td>
    </tr>
    <tr>
      <td>H6A—O6—H6B</td>
      <td>109 (4)</td>
    </tr>
    <tr>
      <td>C1—O7—La1<sup>iii</sup></td>
      <td>151.1 (2)</td>
    </tr>
    <tr>
      <td>C8—O8—La1<sup>ii</sup></td>
      <td>96.32 (18)</td>
    </tr>
    <tr>
      <td>C8—O9—La1<sup>ii</sup></td>
      <td>91.88 (18)</td>
    </tr>
    <tr>
      <td>C16—O12—C17</td>
      <td>115.5 (3)</td>
    </tr>
    <tr>
      <td>H13A—O13—H13B</td>
      <td>105 (5)</td>
    </tr>
  </tbody>
</table>

<table>
  <tbody>
    <tr>
      <td>La1—O4—C1—O7</td>
      <td>133.7 (9)</td>
    </tr>
    <tr>
      <td>La1—O4—C1—C2</td>
      <td>-44.7 (11)</td>
    </tr>
    <tr>
      <td>La1<sup>iii</sup>—O7—C1—O4</td>
      <td>111.9 (4)</td>
    </tr>
    <tr>
      <td>La1<sup>iii</sup>—O7—C1—C2</td>
      <td>-69.7 (5)</td>
    </tr>
    <tr>
      <td>O4—C1—C2—C3</td>
      <td>-70.8 (4)</td>
    </tr>
    <tr>
      <td>O7—C1—C2—C3</td>
      <td>110.6 (3)</td>
    </tr>
    <tr>
      <td>O4—C1—C2—C7</td>
      <td>114.2 (3)</td>
    </tr>
    <tr>
      <td>O7—C1—C2—C7</td>
      <td>-64.3 (4)</td>
    </tr>
    <tr>
      <td>C7—C2—C3—C4</td>
      <td>1.4 (5)</td>
    </tr>
    <tr>
      <td>C1—C2—C3—C4</td>
      <td>-173.6 (3)</td>
    </tr>
    <tr>
      <td>C7—C2—C3—C11</td>
      <td>-178.0 (2)</td>
    </tr>
    <tr>
      <td>C1—C2—C3—C11</td>
      <td>7.0 (4)</td>
    </tr>
    <tr>
      <td>C2—C3—C4—C5</td>
      <td>-1.4 (5)</td>
    </tr>
    <tr>
      <td>C11—C3—C4—C5</td>
      <td>178.0 (3)</td>
    </tr>
    <tr>
      <td>C3—C4—C5—C6</td>
      <td>0.3 (5)</td>
    </tr>
    <tr>
      <td>C4—C5—C6—C7</td>
      <td>0.8 (5)</td>
    </tr>
    <tr>
      <td>C4—C5—C6—C12</td>
      <td>-177.9 (3)</td>
    </tr>
    <tr>
      <td>C5—C6—C7—C2</td>
      <td>-0.8 (5)</td>
    </tr>
  </tbody>
</table>

<table>
  <tbody>
    <tr>
      <td>C10—C11—H11</td>
      <td>120.2</td>
    </tr>
    <tr>
      <td>C13—C12—C11</td>
      <td>121.8 (3)</td>
    </tr>
    <tr>
      <td>C13—C12—Cl3</td>
      <td>119.5 (3)</td>
    </tr>
    <tr>
      <td>C11—C12—Cl3</td>
      <td>118.7 (3)</td>
    </tr>
    <tr>
      <td>C12—C13—C14</td>
      <td>117.9 (3)</td>
    </tr>
    <tr>
      <td>C12—C13—H13</td>
      <td>121.0</td>
    </tr>
    <tr>
      <td>C14—C13—H13</td>
      <td>121.0</td>
    </tr>
    <tr>
      <td>C13—C14—C15</td>
      <td>122.2 (3)</td>
    </tr>
    <tr>
      <td>C13—C14—Cl4</td>
      <td>118.3 (3)</td>
    </tr>
    <tr>
      <td>C15—C14—Cl4</td>
      <td>119.5 (3)</td>
    </tr>
    <tr>
      <td>C14—C15—C10</td>
      <td>118.3 (3)</td>
    </tr>
    <tr>
      <td>C14—C15—C16</td>
      <td>118.9 (3)</td>
    </tr>
    <tr>
      <td>C10—C15—C16</td>
      <td>122.7 (3)</td>
    </tr>
    <tr>
      <td>O11—C16—O12</td>
      <td>125.6 (4)</td>
    </tr>
    <tr>
      <td>O11—C16—C15</td>
      <td>123.2 (4)</td>
    </tr>
    <tr>
      <td>O12—C16—C15</td>
      <td>110.9 (3)</td>
    </tr>
    <tr>
      <td>O12—C17—C18</td>
      <td>107.8 (5)</td>
    </tr>
    <tr>
      <td>O12—C17—H17A</td>
      <td>110.2</td>
    </tr>
    <tr>
      <td>C18—C17—H17A</td>
      <td>110.2</td>
    </tr>
    <tr>
      <td>O12—C17—H17B</td>
      <td>110.2</td>
    </tr>
    <tr>
      <td>C18—C17—H17B</td>
      <td>110.2</td>
    </tr>
    <tr>
      <td>H17A—C17—H17B</td>
      <td>108.5</td>
    </tr>
    <tr>
      <td>C17—C18—H18A</td>
      <td>109.5</td>
    </tr>
    <tr>
      <td>C17—C18—H18B</td>
      <td>109.5</td>
    </tr>
    <tr>
      <td>H18A—C18—H18B</td>
      <td>109.5</td>
    </tr>
    <tr>
      <td>C17—C18—H18C</td>
      <td>109.5</td>
    </tr>
    <tr>
      <td>H18A—C18—H18C</td>
      <td>109.5</td>
    </tr>
    <tr>
      <td>H18B—C18—H18C</td>
      <td>109.5</td>
    </tr>
  </tbody>
</table>

<table>
  <tbody>
    <tr>
      <td>C6—C7—C8—O9</td>
      <td>-65.7 (4)</td>
    </tr>
    <tr>
      <td>C2—C7—C8—O9</td>
      <td>119.3 (3)</td>
    </tr>
    <tr>
      <td>La1—O5—C9—O10</td>
      <td>90.4 (13)</td>
    </tr>
    <tr>
      <td>La1—O5—C9—C10</td>
      <td>-91.1 (13)</td>
    </tr>
    <tr>
      <td>O5—C9—C10—C11</td>
      <td>-5.8 (4)</td>
    </tr>
    <tr>
      <td>O10—C9—C10—C11</td>
      <td>172.9 (3)</td>
    </tr>
    <tr>
      <td>O5—C9—C10—C15</td>
      <td>176.1 (3)</td>
    </tr>
    <tr>
      <td>O10—C9—C10—C15</td>
      <td>-5.2 (4)</td>
    </tr>
    <tr>
      <td>C15—C10—C11—C12</td>
      <td>1.5 (5)</td>
    </tr>
    <tr>
      <td>C9—C10—C11—C12</td>
      <td>-176.6 (3)</td>
    </tr>
    <tr>
      <td>C10—C11—C12—C13</td>
      <td>1.1 (5)</td>
    </tr>
    <tr>
      <td>C10—C11—C12—Cl3</td>
      <td>-177.7 (2)</td>
    </tr>
    <tr>
      <td>C11—C12—C13—C14</td>
      <td>-2.4 (5)</td>
    </tr>
    <tr>
      <td>Cl3—C12—C13—C14</td>
      <td>176.4 (3)</td>
    </tr>
    <tr>
      <td>C12—C13—C14—C15</td>
      <td>1.2 (6)</td>
    </tr>
    <tr>
      <td>C12—C13—C14—Cl4</td>
      <td>-178.8 (3)</td>
    </tr>
    <tr>
      <td>C13—C14—C15—C10</td>
      <td>1.2 (5)</td>
    </tr>
    <tr>
      <td>Cl4—C14—C15—C10</td>
      <td>-178.7 (3)</td>
    </tr>
  </tbody>
</table>
<table><tr><td>Cl2—C6—C7—C2</td><td>177.9 (2)</td><td>C13—C14—C15—C16</td><td>-176.8 (3)</td></tr><tr><td>C5—C6—C7—C8</td><td>-175.7 (3)</td><td>C14—C14—C15—C16</td><td>3.2 (5)</td></tr><tr><td>Cl2—C6—C7—C8</td><td>3.0 (4)</td><td>C11—C10—C15—C14</td><td>-2.6 (5)</td></tr><tr><td>C3—C2—C7—C6</td><td>-0.3 (4)</td><td>C9—C10—C15—C14</td><td>175.5 (3)</td></tr><tr><td>C1—C2—C7—C6</td><td>174.8 (3)</td><td>C11—C10—C15—C16</td><td>175.4 (3)</td></tr><tr><td>C3—C2—C7—C8</td><td>174.9 (3)</td><td>C9—C10—C15—C16</td><td>-6.5 (5)</td></tr><tr><td>C1—C2—C7—C8</td><td>-10.0 (4)</td><td>C17—O12—C16—O11</td><td>0.2 (6)</td></tr><tr><td>La1<sup>ii</sup>—O8—C8—O9</td><td>-4.8 (3)</td><td>C17—O12—C16—C15</td><td>174.7 (3)</td></tr><tr><td>La1<sup>ii</sup>—O8—C8—C7</td><td>173.3 (2)</td><td>C14—C15—C16—O11</td><td>93.0 (5)</td></tr><tr><td>La1<sup>ii</sup>—O9—C8—O8</td><td>4.7 (3)</td><td>C10—C15—C16—O11</td><td>-85.0 (5)</td></tr><tr><td>La1<sup>ii</sup>—O9—C8—C7</td><td>-173.4 (2)</td><td>C14—C15—C16—O12</td><td>-81.6 (4)</td></tr><tr><td>C6—C7—C8—O8</td><td>116.1 (3)</td><td>C10—C15—C16—O12</td><td>100.4 (4)</td></tr><tr><td>C2—C7—C8—O8</td><td>-58.8 (4)</td><td>C16—O12—C17—C18</td><td>-172.7 (4)</td></tr></table>

Symmetry codes: (i) $x-1, y, z$; (ii) $-x+1, -y+1, -z+2$; (iii) $x+1, y, z$; (iv) $x, -y+3/2, z+1/2$.

<table><caption>Hydrogen-bond geometry (Å, °)</caption><thead><tr><th>D—H···A</th><th>D—H</th><th>H···A</th><th>D···A</th><th>D—H···A</th></tr></thead><tbody><tr><td>O1—H1A···O13</td><td>0.84 (4)</td><td>2.00 (4)</td><td>2.787 (4)</td><td>155 (4)</td></tr><tr><td>O1—H1B···O10<sup>v</sup></td><td>0.80 (4)</td><td>1.89 (5)</td><td>2.663 (4)</td><td>164 (4)</td></tr><tr><td>O2—H2A···O10<sup>v</sup></td><td>0.77 (5)</td><td>2.28 (5)</td><td>2.972 (4)</td><td>150 (4)</td></tr><tr><td>O2—H2B···O1<sup>v</sup></td><td>0.80 (5)</td><td>2.11 (5)</td><td>2.868 (4)</td><td>159 (4)</td></tr><tr><td>O3—H3A···O10<sup>v</sup></td><td>0.82 (5)</td><td>2.10 (5)</td><td>2.850 (4)</td><td>152 (4)</td></tr><tr><td>O3—H3B···O13<sup>iii</sup></td><td>0.76 (5)</td><td>2.13 (5)</td><td>2.883 (4)</td><td>174 (5)</td></tr><tr><td>O6—H6A···O9<sup>i</sup></td><td>0.78 (4)</td><td>2.10 (4)</td><td>2.864 (3)</td><td>166 (4)</td></tr><tr><td>O6—H6B···O8</td><td>0.85 (4)</td><td>1.92 (4)</td><td>2.772 (3)</td><td>175 (4)</td></tr><tr><td>O13—H13A···O11<sup>v</sup></td><td>0.81 (5)</td><td>2.16 (5)</td><td>2.948 (4)</td><td>164 (5)</td></tr><tr><td>O13—H13B···O9<sup>ii</sup></td><td>0.87 (5)</td><td>2.30 (5)</td><td>3.008 (4)</td><td>139 (4)</td></tr></tbody></table>

Symmetry codes: (i) $x-1, y, z$; (ii) $-x+1, -y+1, -z+2$; (iii) $x+1, y, z$; (iv) $x, -y+1, -z+1$.

Continuous Shape Measurements (CShM) for [La(3,6-dcpa)(C₁₀H₇Cl₂O₄)(H₂O)₄·H₂O]∞. The lower is the CShM value, the better is the agreement with the given coordination polyhedron.

<table><tr><td>[ML9]</td><td>EP-9</td><td>OPY-9</td><td>HBPY-9</td><td>JTC-9</td><td>JCCU-9</td><td>CCU-9</td><td>JCSAPR-9</td><td>CSAPR-9</td><td>JTCTPR-9</td><td>TCTPR-9</td><td>JTDIC-9</td><td>HH-9</td><td>MFF-9</td></tr><tr><td>La</td><td>35.863</td><td>21.416</td><td>20.115</td><td>15.640</td><td>11.075</td><td>9.311</td><td>2.176</td><td><b>1.059</b></td><td>2.715</td><td>1.073</td><td>13.106</td><td>10.7861</td><td>1.588</td></tr></table>

EP-9 ≡ D<sub>9h</sub>-Enneagon; OPY-9 ≡ C<sub>8v</sub>-Octagonal pyramid; HBPY-9 ≡ D<sub>7h</sub>-Heptagonal bipyramid; JTC-9 ≡ C<sub>3v</sub>-Johnson triangular cupola J3; JCCU-9 ≡ C<sub>4v</sub>-Capped cube J8; CCU-9 ≡ C<sub>4v</sub>-Spherical-relaxed capped cube; JCSAPR-9 C<sub>4v</sub>-Capped square antiprism J10; CSAPR-9 ≡ C<sub>4v</sub>-Spherical capped square antiprism; JTCTPR-9 ≡ D<sub>3h</sub>-Tricapped trigonal prism J51; TCTPR-9 ≡ D<sub>3h</sub>-Spherical tricapped trigonal prism; JTDIC-9 ≡ C<sub>3v</sub>-Tridiminished icosahedron J63; HH-9 ≡ C<sub>2v</sub>-Hula-hoop; MFF-9 ≡ C<sub>4v</sub>-Muffin.