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

Hénaff, C.; Roisnel, T.; Blais, C.; Guillou, O.; Daiguebonne, C.

doi:10.1107/S2056989025009508

research communications

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ISSN: 2056-9890

Volume 81| Part 12| December 2025| Pages 1106-1110

https://doi.org/10.1107/S2056989025009508

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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 Guillou ^a,^c and Carole Daiguebonne ^a

^aUniv Rennes, INSA Rennes, CNRS UMR 6226 "Institut des Sciences Chimiques de Rennes", 35708 Rennes, France, ^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: [email protected]

Edited by F. F. Ferreira, Universidade Federal do ABC, Brazil (Received 10 September 2025; accepted 29 October 2025; online 6 November 2025)

A one-dimensional lanthanum-based coordination polymer based on 3,6-dichlorophthalate has been prepared and structurally described, namely, poly[[tetraaqua[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.

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

CCDC reference: 2430840

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-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.

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).

Figure 2
Coordination modes observed in lanthanide coordination polymers based on a phthalate ligand.

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)(C₁₀H₇Cl₂O₄)(H₂O)₄·H₂O]_∞. 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.

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)(C₁₀H₇Cl₂O₄)(H₂O)₄·H₂O]_∞ where 3,6-dcpa²⁻ symbolizes 3,6-dichlorophtalate (CCDC-2430840) (Fig. 3).

Figure 3
Projection view of an extended asymmetric unit with the numbering scheme of [La(3,6-dcpa)(C₁₀H₇Cl₂O₄)(H₂O)₄·H₂O]_∞. 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.

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-dcpa²⁻ 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-dcpa²⁻ ligand and one independent 2,4-dichloro-6-(ethoxycarbonyl)benzoate ligand in the crystal structure. The former is μ₃(η₁η₁η₂) and the latter is μ₁(η₁) (Fig. 4) Finally, there is one crystallization water molecule (H13A–O13–H13B) in the crystal structure.

Figure 4
Schematic representation of the neighbourhood of the La³⁺ ion (left) and coordination modes of the 3,6-dcpa²⁻ ligand (top right) and of the 2,4-dichloro-6-(ethoxycarbonyl)benzoate ligand (bottom right) of [La(3,6-dcpa)(C₁₀H₇Cl₂O₄)(H₂O)₄·H₂O]_∞.

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 chains, lanthanum ions are linked to each other by 3,6-dcpa²⁻ 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).

Figure 5
Left: Projection view along the b axis of a molecular double chain of [La(3,6-dcpa)(C₁₀H₇Cl₂O₄)(H₂O)₄·H₂O]_∞. Shortest intermetallic distances are d(La—Laⁱ) = 6.8045 (8) Å, d(La—Laⁱⁱ) = 6.0680 (4) Å and d(Laⁱ—Laⁱⁱ) = 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.

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).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O13	0.84 (4)	2.00 (4)	2.787 (4)	155 (4)
O1—H1B⋯O10ⁱⁱⁱ	0.80 (4)	1.89 (5)	2.663 (4)	164 (4)
O2—H2A⋯O10ⁱⁱⁱ	0.77 (5)	2.28 (5)	2.972 (4)	150 (4)
O2—H2B⋯O1ⁱⁱⁱ	0.80 (5)	2.11 (5)	2.868 (4)	159 (4)
O3—H3A⋯O10ⁱⁱⁱ	0.82 (5)	2.10 (5)	2.850 (4)	152 (4)
O3—H3B⋯O13ⁱ	0.76 (5)	2.13 (5)	2.883 (4)	174 (5)
O6—H6A⋯O9^iv	0.78 (4)	2.10 (4)	2.864 (3)	166 (4)
O6—H6B⋯O8	0.85 (4)	1.92 (4)	2.772 (3)	175 (4)
O13—H13A⋯O11ⁱⁱⁱ	0.81 (5)	2.16 (5)	2.948 (4)	164 (5)
O13—H13B⋯O9^v	0.87 (5)	2.30 (5)	3.008 (4)	139 (4)
Symmetry codes: (i) ; (iii) ; (iv) ; (v) .

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 La³⁺ ions closer than 10 Å from a given La³⁺ ion (Table 3). All seven belong to two adjacent molecular motifs spreading parallel to the ac plane (Fig. 6).

Table 2
Selected interatomic distances (Å)

Cl2ⁱ⋯Cl3	3.4185 (16)	Cl3ⁱⁱ⋯Cl4	3.4645 (15)
Cl2⋯Cl3	3.4287 (15)
Symmetry codes: (i) ; (ii) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Table 3
La⋯La distances (Å) shorter than 10 Å in [La(3,6-dcpa)(C₁₀H₇Cl₂O₄)(H₂O)₄·H₂O]_∞

Atom1	Atom2	Symmetry	Distance
La1	La1	−x, 1 − y, 2 − z	6.0682 (6)
	La1	−x, 1 − y, 1 − z	6.2554 (7)
	La1	1 − x, 1 − y, 2 − z	6.3650 (6)
	La1	1 + x, y, z	6.8044 (8)
	La1	−1 + x, y, z	6.8046 (8)
	La1	1 − x, 1 − y, 1 − z	8.5065 (8)
	La1	−1 − x, 1 − y, 1 − z	9.9248 (9)

Figure 6
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.

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-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).

Table 4
Experimental details

Crystal data
Chemical formula	[La(C₈H₂Cl₂O₄)(C₁₀H₇Cl₂O₄)(H₂O)₄]·H₂O
M_r	724.04
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	150
a, b, c (Å)	6.8045 (7), 32.376 (3), 11.5188 (12)
β (°)	100.862 (4)
V (Å³)	2492.2 (4)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	2.21
Crystal size (mm)	0.44 × 0.07 × 0.03

Data collection
Diffractometer	D8 VENTURE Bruker AXS
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.777, 0.936
No. of measured, independent and observed [I > 2σ(I)] reflections	19761, 5674, 5503
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.068, 1.27
No. of reflections	5674
No. of parameters	355
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.72, −1.05
Computer programs: APEX3 (Bruker, 2015 ), SAINT (Bruker, 2014 ), SHELXT (Sheldrick, 2015a ), SHELXL2019/2 (Sheldrick, 2015b ), SXGRAPH (Farrugia, 1999 ), Mercury (Macrae et al., 2020 ) and CRYSCALC (T. Roisnel, local program, 2024).

Supporting information

CCDC reference: 2430840

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989025009508/ee2020sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989025009508/ee2020Isup3.hkl

checkCIF report

Computing details top

Poly[[tetraaqua[2,4-dichloro-6-(ethoxycarbonyl)benzoato](µ₃-3,6-dichlorophthalato)lanthanum(III)] monohydrate] top

Crystal data top

[La(C₈H₂Cl₂O₄)(C₁₀H₇Cl₂O₄)(H₂O)₄]·H₂O	F(000) = 1424
M_r = 724.04	D_x = 1.930 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 6.8045 (7) Å	Cell parameters from 9930 reflections
b = 32.376 (3) Å	θ = 2.6–27.5°
c = 11.5188 (12) Å	µ = 2.21 mm⁻¹
β = 100.862 (4)°	T = 150 K
V = 2492.2 (4) Å³	Stick, colourless
Z = 4	0.44 × 0.07 × 0.03 mm

Data collection top

D8 VENTURE Bruker AXS diffractometer	5674 independent reflections
Radiation source: Incoatec microfocus sealed tube	5503 reflections with I > 2σ(I)
Multilayer monochromator	R_int = 0.028
Detector resolution: 7.39 pixels mm^-1	θ_max = 27.5°, θ_min = 1.9°
rotation images scans	h = −8→8
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	k = −41→41
T_min = 0.777, T_max = 0.936	l = −14→14
19761 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.033	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.068	w = 1/[σ²(F_o²) + 7.126P] where P = (F_o² + 2F_c²)/3
S = 1.27	(Δ/σ)_max = 0.002
5674 reflections	Δρ_max = 0.72 e Å⁻³
355 parameters	Δρ_min = −1.05 e Å⁻³
0 restraints

Special details top

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-K_α 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 (R_int=0.0280; R_sigma=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 F² (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 F² with 5674 unique intensities and 355 parameters converged at ωR(F²)=0.0678 (R_F = 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 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 > 2sigma(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 (Å²) top

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

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
La1	0.00833 (9)	0.01307 (9)	0.01034 (8)	−0.00037 (7)	0.00073 (6)	−0.00107 (7)
Cl1	0.0187 (4)	0.0346 (5)	0.0126 (3)	0.0022 (3)	0.0016 (3)	0.0008 (3)
Cl2	0.0370 (5)	0.0243 (4)	0.0304 (5)	−0.0050 (4)	0.0029 (4)	−0.0104 (4)
Cl3	0.0349 (5)	0.0384 (5)	0.0217 (4)	−0.0004 (4)	0.0030 (4)	−0.0065 (4)
Cl4	0.0657 (8)	0.0160 (4)	0.0377 (5)	−0.0049 (5)	0.0063 (5)	0.0054 (4)
O1	0.0181 (12)	0.0223 (13)	0.0159 (11)	−0.0045 (10)	0.0018 (9)	−0.0044 (10)
O2	0.0268 (13)	0.0183 (13)	0.0158 (12)	−0.0007 (11)	0.0057 (10)	−0.0012 (10)
O3	0.0206 (13)	0.0244 (13)	0.0177 (12)	0.0044 (11)	−0.0003 (10)	−0.0039 (10)
O4	0.0123 (11)	0.0225 (12)	0.0204 (11)	−0.0030 (10)	0.0023 (9)	−0.0013 (10)
O5	0.0223 (12)	0.0144 (11)	0.0197 (11)	0.0004 (10)	0.0046 (10)	0.0012 (9)
O6	0.0098 (11)	0.0244 (13)	0.0144 (11)	0.0002 (10)	0.0024 (9)	−0.0049 (9)
O7	0.0120 (11)	0.0191 (12)	0.0216 (11)	0.0032 (9)	0.0039 (9)	0.0006 (10)
O8	0.0115 (11)	0.0222 (12)	0.0133 (10)	−0.0031 (9)	−0.0001 (8)	0.0017 (9)
O9	0.0108 (10)	0.0227 (12)	0.0148 (11)	0.0010 (9)	0.0009 (9)	0.0008 (9)
O10	0.0220 (12)	0.0208 (12)	0.0163 (11)	0.0026 (10)	−0.0007 (9)	−0.0006 (9)
O11	0.0485 (18)	0.0363 (16)	0.0247 (14)	−0.0026 (14)	0.0189 (13)	0.0013 (12)
O12	0.0415 (17)	0.0302 (15)	0.0211 (13)	0.0112 (13)	−0.0028 (12)	0.0021 (11)
O13	0.0266 (15)	0.0311 (15)	0.0281 (15)	−0.0008 (12)	0.0054 (12)	−0.0013 (12)
C1	0.0136 (15)	0.0200 (16)	0.0089 (13)	−0.0008 (12)	0.0040 (11)	−0.0007 (12)
C2	0.0081 (13)	0.0184 (15)	0.0148 (14)	0.0017 (12)	0.0039 (11)	0.0001 (12)
C3	0.0109 (14)	0.0231 (17)	0.0138 (14)	0.0035 (13)	0.0034 (12)	0.0009 (12)
C4	0.0173 (16)	0.0215 (17)	0.0248 (17)	0.0072 (14)	0.0073 (14)	0.0098 (14)
C5	0.0194 (17)	0.0165 (16)	0.0293 (18)	0.0016 (14)	0.0065 (14)	0.0035 (14)
C6	0.0167 (16)	0.0195 (17)	0.0213 (16)	−0.0018 (13)	0.0034 (13)	−0.0037 (13)
C7	0.0105 (14)	0.0173 (15)	0.0142 (14)	0.0004 (12)	0.0041 (11)	0.0019 (12)
C8	0.0153 (15)	0.0129 (14)	0.0100 (13)	0.0010 (12)	0.0022 (11)	−0.0010 (11)
C9	0.0112 (14)	0.0148 (15)	0.0172 (15)	−0.0007 (12)	0.0058 (12)	−0.0017 (12)
C10	0.0152 (15)	0.0146 (15)	0.0177 (15)	0.0006 (12)	0.0069 (12)	−0.0011 (12)
C11	0.0159 (15)	0.0167 (15)	0.0172 (15)	−0.0009 (13)	0.0058 (12)	0.0012 (12)
C12	0.0174 (16)	0.0247 (18)	0.0151 (15)	0.0001 (14)	0.0024 (12)	−0.0034 (13)
C13	0.0258 (18)	0.0191 (17)	0.0254 (18)	−0.0032 (15)	0.0039 (15)	−0.0057 (14)
C14	0.0292 (19)	0.0148 (16)	0.0252 (18)	0.0003 (14)	0.0078 (15)	0.0024 (14)
C15	0.0190 (16)	0.0192 (16)	0.0175 (16)	0.0013 (13)	0.0050 (13)	0.0019 (13)
C16	0.035 (2)	0.0151 (16)	0.0211 (17)	0.0008 (15)	0.0069 (15)	0.0030 (13)
C17	0.071 (4)	0.046 (3)	0.023 (2)	0.011 (3)	−0.013 (2)	0.0057 (19)
C18	0.065 (4)	0.086 (5)	0.063 (4)	0.016 (4)	−0.022 (3)	0.019 (4)

Geometric parameters (Å, º) top

La1—O4	2.422 (2)	O12—C17	1.454 (5)
La1—O5	2.448 (2)	O13—H13A	0.81 (5)
La1—O7ⁱ	2.488 (2)	O13—H13B	0.87 (5)
La1—O6	2.537 (2)	C1—C2	1.518 (5)
La1—O2	2.570 (2)	C2—C3	1.390 (4)
La1—O1	2.584 (2)	C2—C7	1.398 (4)
La1—O8ⁱⁱ	2.595 (2)	C3—C4	1.385 (5)
La1—O3	2.651 (3)	C4—C5	1.379 (5)
La1—O9ⁱⁱ	2.684 (2)	C4—H4	0.9500
La1—C8ⁱⁱ	3.004 (3)	C5—C6	1.385 (5)
Cl1—C3	1.737 (3)	C5—H5	0.9500
Cl2—C6	1.740 (4)	C6—C7	1.383 (5)
Cl3—C12	1.729 (3)	C7—C8	1.511 (4)
Cl4—C14	1.733 (4)	C9—C10	1.507 (4)
O1—H1A	0.84 (4)	C10—C11	1.390 (5)
O1—H1B	0.80 (4)	C10—C15	1.398 (5)
O2—H2A	0.77 (5)	C11—C12	1.381 (5)
O2—H2B	0.80 (5)	C11—H11	0.9500
O3—H3A	0.82 (5)	C12—C13	1.379 (5)
O3—H3B	0.76 (5)	C13—C14	1.388 (5)
O4—C1	1.247 (4)	C13—H13	0.9500
O5—C9	1.251 (4)	C14—C15	1.391 (5)
O6—H6A	0.78 (4)	C15—C16	1.504 (5)
O6—H6B	0.85 (4)	C17—C18	1.455 (8)
O7—C1	1.252 (4)	C17—H17A	0.9900
O8—C8	1.255 (4)	C17—H17B	0.9900
O9—C8	1.263 (4)	C18—H18A	0.9800
O10—C9	1.257 (4)	C18—H18B	0.9800
O11—C16	1.210 (5)	C18—H18C	0.9800
O12—C16	1.313 (5)

Cl2ⁱⁱⁱ···Cl3	3.4185 (16)	Cl3^iv···Cl4	3.4645 (15)
Cl2···Cl3	3.4287 (15)

O4—La1—O5	85.14 (8)	O4—C1—O7	125.5 (3)
O4—La1—O7ⁱ	143.67 (8)	O4—C1—C2	118.4 (3)
O5—La1—O7ⁱ	75.00 (8)	O7—C1—C2	116.1 (3)
O4—La1—O6	73.11 (8)	C3—C2—C7	118.9 (3)
O5—La1—O6	81.00 (8)	C3—C2—C1	121.9 (3)
O7ⁱ—La1—O6	73.93 (8)	C7—C2—C1	119.0 (3)
O4—La1—O2	73.96 (8)	C4—C3—C2	121.7 (3)
O5—La1—O2	71.11 (8)	C4—C3—Cl1	118.1 (3)
O7ⁱ—La1—O2	125.01 (8)	C2—C3—Cl1	120.2 (3)
O6—La1—O2	138.13 (8)	C5—C4—C3	119.2 (3)
O4—La1—O1	141.71 (8)	C5—C4—H4	120.4
O5—La1—O1	90.05 (8)	C3—C4—H4	120.4
O7ⁱ—La1—O1	69.51 (8)	C4—C5—C6	119.5 (3)
O6—La1—O1	143.43 (8)	C4—C5—H5	120.2
O2—La1—O1	68.58 (8)	C6—C5—H5	120.2
O4—La1—O8ⁱⁱ	75.46 (7)	C7—C6—C5	121.8 (3)
O5—La1—O8ⁱⁱ	149.22 (8)	C7—C6—Cl2	120.4 (3)
O7ⁱ—La1—O8ⁱⁱ	107.29 (7)	C5—C6—Cl2	117.8 (3)
O6—La1—O8ⁱⁱ	70.69 (8)	C6—C7—C2	118.9 (3)
O2—La1—O8ⁱⁱ	123.90 (8)	C6—C7—C8	122.9 (3)
O1—La1—O8ⁱⁱ	119.92 (8)	C2—C7—C8	118.0 (3)
O4—La1—O3	85.50 (8)	O8—C8—O9	122.2 (3)
O5—La1—O3	136.70 (8)	O8—C8—C7	117.2 (3)
O7ⁱ—La1—O3	129.51 (8)	O9—C8—C7	120.5 (3)
O6—La1—O3	135.31 (8)	O8—C8—La1ⁱⁱ	59.15 (16)
O2—La1—O3	65.67 (8)	O9—C8—La1ⁱⁱ	63.26 (16)
O1—La1—O3	72.34 (8)	C7—C8—La1ⁱⁱ	173.1 (2)
O8ⁱⁱ—La1—O3	66.07 (8)	O5—C9—O10	124.8 (3)
O4—La1—O9ⁱⁱ	124.74 (7)	O5—C9—C10	118.0 (3)
O5—La1—O9ⁱⁱ	144.12 (7)	O10—C9—C10	117.2 (3)
O7ⁱ—La1—O9ⁱⁱ	69.12 (7)	C11—C10—C15	120.2 (3)
O6—La1—O9ⁱⁱ	88.95 (7)	C11—C10—C9	119.1 (3)
O2—La1—O9ⁱⁱ	131.49 (8)	C15—C10—C9	120.7 (3)
O1—La1—O9ⁱⁱ	77.78 (7)	C12—C11—C10	119.5 (3)
O8ⁱⁱ—La1—O9ⁱⁱ	49.35 (7)	C12—C11—H11	120.2
O3—La1—O9ⁱⁱ	71.52 (7)	C10—C11—H11	120.2
O4—La1—C8ⁱⁱ	99.99 (8)	C13—C12—C11	121.8 (3)
O5—La1—C8ⁱⁱ	155.69 (8)	C13—C12—Cl3	119.5 (3)
O7ⁱ—La1—C8ⁱⁱ	87.61 (8)	C11—C12—Cl3	118.7 (3)
O6—La1—C8ⁱⁱ	77.89 (8)	C12—C13—C14	117.9 (3)
O2—La1—C8ⁱⁱ	133.19 (8)	C12—C13—H13	121.0
O1—La1—C8ⁱⁱ	99.77 (8)	C14—C13—H13	121.0
O8ⁱⁱ—La1—C8ⁱⁱ	24.53 (8)	C13—C14—C15	122.2 (3)
O3—La1—C8ⁱⁱ	67.60 (8)	C13—C14—Cl4	118.3 (3)
O9ⁱⁱ—La1—C8ⁱⁱ	24.86 (8)	C15—C14—Cl4	119.5 (3)
La1—O1—H1A	114 (3)	C14—C15—C10	118.3 (3)
La1—O1—H1B	118 (3)	C14—C15—C16	118.9 (3)
H1A—O1—H1B	101 (4)	C10—C15—C16	122.7 (3)
La1—O2—H2A	120 (3)	O11—C16—O12	125.6 (4)
La1—O2—H2B	127 (3)	O11—C16—C15	123.2 (4)
H2A—O2—H2B	108 (4)	O12—C16—C15	110.9 (3)
La1—O3—H3A	120 (3)	O12—C17—C18	107.8 (5)
La1—O3—H3B	121 (3)	O12—C17—H17A	110.2
H3A—O3—H3B	107 (4)	C18—C17—H17A	110.2
C1—O4—La1	167.0 (2)	O12—C17—H17B	110.2
C9—O5—La1	169.9 (2)	C18—C17—H17B	110.2
La1—O6—H6A	123 (3)	H17A—C17—H17B	108.5
La1—O6—H6B	122 (3)	C17—C18—H18A	109.5
H6A—O6—H6B	109 (4)	C17—C18—H18B	109.5
C1—O7—La1ⁱⁱⁱ	151.1 (2)	H18A—C18—H18B	109.5
C8—O8—La1ⁱⁱ	96.32 (18)	C17—C18—H18C	109.5
C8—O9—La1ⁱⁱ	91.88 (18)	H18A—C18—H18C	109.5
C16—O12—C17	115.5 (3)	H18B—C18—H18C	109.5
H13A—O13—H13B	105 (5)

La1—O4—C1—O7	133.7 (9)	C6—C7—C8—O9	−65.7 (4)
La1—O4—C1—C2	−44.7 (11)	C2—C7—C8—O9	119.3 (3)
La1ⁱⁱⁱ—O7—C1—O4	111.9 (4)	La1—O5—C9—O10	90.4 (13)
La1ⁱⁱⁱ—O7—C1—C2	−69.7 (5)	La1—O5—C9—C10	−91.1 (13)
O4—C1—C2—C3	−70.8 (4)	O5—C9—C10—C11	−5.8 (4)
O7—C1—C2—C3	110.6 (3)	O10—C9—C10—C11	172.9 (3)
O4—C1—C2—C7	114.2 (3)	O5—C9—C10—C15	176.1 (3)
O7—C1—C2—C7	−64.3 (4)	O10—C9—C10—C15	−5.2 (4)
C7—C2—C3—C4	1.4 (5)	C15—C10—C11—C12	1.5 (5)
C1—C2—C3—C4	−173.6 (3)	C9—C10—C11—C12	−176.6 (3)
C7—C2—C3—Cl1	−178.0 (2)	C10—C11—C12—C13	1.1 (5)
C1—C2—C3—Cl1	7.0 (4)	C10—C11—C12—Cl3	−177.7 (2)
C2—C3—C4—C5	−1.4 (5)	C11—C12—C13—C14	−2.4 (5)
Cl1—C3—C4—C5	178.0 (3)	Cl3—C12—C13—C14	176.4 (3)
C3—C4—C5—C6	0.3 (5)	C12—C13—C14—C15	1.2 (6)
C4—C5—C6—C7	0.8 (5)	C12—C13—C14—Cl4	−178.8 (3)
C4—C5—C6—Cl2	−177.9 (3)	C13—C14—C15—C10	1.2 (5)
C5—C6—C7—C2	−0.8 (5)	Cl4—C14—C15—C10	−178.7 (3)
Cl2—C6—C7—C2	177.9 (2)	C13—C14—C15—C16	−176.8 (3)
C5—C6—C7—C8	−175.7 (3)	Cl4—C14—C15—C16	3.2 (5)
Cl2—C6—C7—C8	3.0 (4)	C11—C10—C15—C14	−2.6 (5)
C3—C2—C7—C6	−0.3 (4)	C9—C10—C15—C14	175.5 (3)
C1—C2—C7—C6	174.8 (3)	C11—C10—C15—C16	175.4 (3)
C3—C2—C7—C8	174.9 (3)	C9—C10—C15—C16	−6.5 (5)
C1—C2—C7—C8	−10.0 (4)	C17—O12—C16—O11	0.2 (6)
La1ⁱⁱ—O8—C8—O9	−4.8 (3)	C17—O12—C16—C15	174.7 (3)
La1ⁱⁱ—O8—C8—C7	173.3 (2)	C14—C15—C16—O11	93.0 (5)
La1ⁱⁱ—O9—C8—O8	4.7 (3)	C10—C15—C16—O11	−85.0 (5)
La1ⁱⁱ—O9—C8—C7	−173.4 (2)	C14—C15—C16—O12	−81.6 (4)
C6—C7—C8—O8	116.1 (3)	C10—C15—C16—O12	100.4 (4)
C2—C7—C8—O8	−58.8 (4)	C16—O12—C17—C18	−172.7 (4)

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.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O13	0.84 (4)	2.00 (4)	2.787 (4)	155 (4)
O1—H1B···O10^v	0.80 (4)	1.89 (5)	2.663 (4)	164 (4)
O2—H2A···O10^v	0.77 (5)	2.28 (5)	2.972 (4)	150 (4)
O2—H2B···O1^v	0.80 (5)	2.11 (5)	2.868 (4)	159 (4)
O3—H3A···O10^v	0.82 (5)	2.10 (5)	2.850 (4)	152 (4)
O3—H3B···O13ⁱⁱⁱ	0.76 (5)	2.13 (5)	2.883 (4)	174 (5)
O6—H6A···O9ⁱ	0.78 (4)	2.10 (4)	2.864 (3)	166 (4)
O6—H6B···O8	0.85 (4)	1.92 (4)	2.772 (3)	175 (4)
O13—H13A···O11^v	0.81 (5)	2.16 (5)	2.948 (4)	164 (5)
O13—H13B···O9ⁱⁱ	0.87 (5)	2.30 (5)	3.008 (4)	139 (4)

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

La···La distances (Å) shorter than 10 Å in [La(3,6-dcpa)(C₁₀H₇Cl₂O₄)(H₂O)₄.H₂O]_∞ top

Atom1	Atom2	Symmetry	Distance
La1	La1	-x, 1 - y, 2 - z	6.0682 (6)
	La1	-x, 1 - y, 1 - z	6.2554 (7)
	La1	1 - x, 1 - y, 2-z	6.3650 (6)
	La1	1 + x, y, z	6.8044 (8)
	La1	-1 + x, y, z	6.8046 (8)
	La1	1 - x, 1 - y, 1 - z	8.5065 (8)
	La1	-1 - x, 1 - y, 1 - z	9.9248 (9)

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. top

[ML9]	EP-9	OPY-9	HBPY-9	JTC-9	JCCU-9	CCU-9	JCSAPR-9	CSAPR-9	JTCTPR-9	TCTPR-9	JTDIC-9	HH-9	MFF-9
La	35.863	21.416	20.115	15.640	11.075	9.311	2.176	1.059	2.715	1.073	13.106	10.786	1.588

EP-9 ≡D₉_h-Enneagon; OPY-9 ≡ C₈_v-Octagonal pyramid; HBPY-9 ≡D₇_h-Heptagonal bipyramid; JTC-9≡ C₃_v-Johnson triangular cupola J3; JCCU-9 ≡C₄_v-Capped cube J8; CCU-9 ≡ C₄_v-Spherical-relaxed capped cube; JCSAPR-9 C₄_v-Capped square antiprism J10; CSAPR-9 ≡C₄_v-Spherical capped square antiprism; JTCTPR-9 ≡D₃_h-Tricapped trigonal prism J51; TCTPR-9 ≡ D₃_h Spherical tricapped trigonal prism; JTDIC-9 ≡ C₃_v-Tridiminished icosahedron J63; HH-9 ≡ C₂_v-Hula-hoop; MFF-9 ≡C_s-Muffin.

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).

References

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