Syntheses and crystal structures of the cerium-based coordination polymers poly[(acetic acid)bis­(μ-5-carb­oxy­thio­phene-2-carboxyl­ato)bis­(μ-thio­phene-2,5-di­carboxyl­ato)dicerium(III)] and poly[(μ-acetato)­aqua­(μ4-thio­phene-2,5-di­carboxyl­ato)cerium(III)]

Ruser, N.; Näther, C.; Stock, N.

doi:10.1107/S2056989025000210

research communications

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 81| Part 2| February 2025| Pages 153-159

https://doi.org/10.1107/S2056989025000210

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Syntheses and crystal structures of the cerium-based coordination polymers poly[(acetic acid)bis(μ-5-carboxythiophene-2-carboxylato)bis(μ-thiophene-2,5-dicarboxylato)dicerium(III)] and poly[(μ-acetato)aqua(μ₄-thiophene-2,5-dicarboxylato)cerium(III)]

Niklas Ruser,^a Christian Näther ^a and Norbert Stock ^a ^*

^aInstitute of Inorganic Chemistry, Kiel University, Max-Eyth-Str. 2, 24118 Kiel, Germany
^*Correspondence e-mail: stock@ac.uni-kiel.de

Edited by X. Hao, Institute of Chemistry, Chinese Academy of Sciences (Received 16 December 2024; accepted 9 January 2025; online 17 January 2025)

The title compounds, [Ce₂(C₆H₃SO₄)₂(C₆H₂SO₄)₂(CH₃COOH)]_n (1) and [Ce(CH₃COO)(C₆H₂SO₄)(H₂O)]_n (2) were synthesized by solvothermal reaction of Ce(NO₃)₃·6H₂O with 2,5-thiophenedicarboxylic acid (H₂TDC, C₆H₄SO₄) and acetic acid in acetonitrile or ethanol/water, respectively. These compounds were obtained as single crystals among other crystalline phases. Both compounds belong to the family of three-dimensional coordination polymers. The asymmetric unit of 1 consists of two Ce^III cations, two TDC²⁻ dianions, two HTDC⁻ anions and one acetic acid ligand, all of them located in general positions. The two Ce^III cations are each coordinated by eight oxygen atoms in the form of distorted square antiprisms. These are bridged by carboxylate and carboxylic acid groups, forming mono-periodic hybrid inorganic building units (IBUs), which are connected into a three-dimensional network by the TDC²⁻ and HTDC⁻ ligands. Compound 2 has an asymmetric unit composed of one Ce^III cation, one TDC²⁻ dianion, one acetate anion and one water molecule in general positions. The cerium atom is eightfold coordinated by oxygen atoms. Edge-sharing CeO₈ polyhedra form a dinuclear IBU (Ce₂O₁₄). This IBU is bridged by six TDC²⁻ linkers to nine other IBUs, forming a three-dimensional framework. Both title compounds exhibit additional O—H⋯O hydrogen bonds. Powder X-ray diffraction shows that both compounds were not obtained as pure phases.

Keywords: synthesis; crystal structure; solvothermal reaction; coordination polymer.

CCDC references: 2415947; 2415946

1. Chemical context

The search for new coordination polymers (CPs) (Batten et al., 2009 ), especially metal–organic frameworks (MOFs) (Rowsell & Yaghi, 2004 ; Long & Yaghi, 2009 ) is still a very active field of research. As a result of the variety of possible metals, as well as inorganic and organic linker molecules, there are many opportunities to discover new compounds and to modify properties and structural behaviors of existing ones. CPs contain metal atoms/ions linked by ligands that extend in one, two or three dimensions. MOFs are a subclass of CPs that exclusively contain organic ligands, called linkers, that lead to the formation of two- or three-periodic networks. In addition, MOFs have potential pores (Batten et al., 2013 ). As a result of their porosity and large specific surface areas, MOFs have potential applications in areas such as catalysis (Hu et al., 2018 ; Li, 2018 ; Lammert et al., 2015 ), gas storage (Li et al., 2019 ; Sahayaraj et al., 2023 ) and sensing (Shekhah et al., 2011 ; Wang et al., 2018 ). The properties of MOFs can often be tuned by the selection of metal ions and organic linkers (Sahayaraj et al., 2023). In the case of cerium MOFs, their redox properties can be exploited in catalytic applications (Lammert et al., 2015; Smolders et al., 2018 , 2020 ).

The variety of possible reactants is matched by the variety of synthesis conditions under which these compounds can be obtained. Therefore, there are multidimensional parameter spaces to explore, which could lead to the discovery of an enormous number of new compounds. A very useful tool for the screening of large parameter spaces is high-throughput methods (Stock, 2010 ). High-throughput methods make use of the concepts of automation, parallelization and miniaturization. Many syntheses can be carried out under the same temperature-time program, while the influence of molar ratios of starting materials, solvent mixtures, concentration, etc. on the product formation can be studied simultaneously. Phase mixtures are often observed and high-throughput methods can also be used to optimize reaction conditions. In a systematic study of the chemical system Ce^III/2,5-thiophenedicarboxylic acid (H₂TDC) in different solvents two new CPs were discovered and structurally characterized by single crystal X-ray diffraction.

2. Structural commentary

Crystal structure of 1

The asymmetric unit of [Ce₂(C₆H₃SO₄)₂(C₆H₂SO₄)₂(CH₃COOH)]_n (1) contains two Ce^III cations, two HTDC⁻ anions, two TDC²⁻ dianions and one acetic acid molecule, all located in general positions (Fig. 1). Both Ce^III cations (Ce1 and Ce2) are coordinated by eight oxygen atoms, forming distorted square antiprisms. These oxygen atoms coordinating Ce1 belong to four TDC²⁻ dianions, three HTDC⁻ anions and one acetic acid molecule. For Ce2, the oxygen atoms originate from four TDC²⁻ dianions and four HTDC⁻ anions. While the binding mode of the carboxylate groups is exclusively bridging μ₂-(O,O′), the binding modes of the carboxylic acid groups of HTDC⁻ are monodentate μ₁-(O) and bridging μ₂-(O,O′). The carboxylic acid group of acetic acid exhibits the monodentate μ₁-(O) binding mode. The Ce—O distances are in the range 2.259 (5)–2.555 (4) Å (Table 1). The binding modes of the ligands lead to an IBU consisting of CeO₈ polyhedra, which are bridged by carboxylate and carboxylic acid groups of TDC²⁻ and HTDC⁻ anions, forming a monoperiodic chain extending along the crystallographic a-axis direction (Fig. 2). Each chain is interconnected to six other chains by TDC²⁻ and HTDC⁻ anions (Fig. 3), resulting in a hexagonal arrangement of the chains (Fig. 4). This gives rise to a CP with a three-dimensional network. The acetic acid does not participate in the formation of the network but completes the coordination sphere of Ce1.

Table 1
Selected bond lengths (Å) for 1

Ce1—O1	2.437 (5)	Ce2—O2^iv	2.481 (5)
Ce1—O4ⁱ	2.259 (5)	Ce2—O3ⁱⁱ	2.527 (5)
Ce1—O11	2.278 (4)	Ce2—O12^iv	2.518 (4)
Ce1—O13ⁱⁱ	2.389 (4)	Ce2—O14^v	2.538 (4)
Ce1—O21	2.344 (5)	Ce2—O22^vi	2.502 (5)
Ce1—O32ⁱⁱⁱ	2.288 (4)	Ce2—O23	2.555 (4)
Ce1—O34ⁱⁱ	2.360 (5)	Ce2—O31	2.342 (5)
Ce1—O41	2.549 (5)	Ce2—O33^v	2.376 (5)
Symmetry codes: (i) $[-x+1, -y+2, z-{\script{1\over 2}}]$ ; (ii) $[-x+1, -y+1, z-{\script{1\over 2}}]$ ; (iii) ; (iv) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z]$ ; (v) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (vi) .

Figure 1
Crystal structure of compound 1 with atom labeling and displacement ellipsoids drawn at the 50% probability level. The HTDC⁻ and TDC²⁻ fragments belonging to the oxygen atoms created by symmetry operations are omitted for clarity. Symmetry codes: (i) −x + 1, −y + 2, z − $[{1\over 2}]$ ; (ii) −x + 1, −y + 1, z − $[{1\over 2}]$ ; (iii) x, y + 1, z; (iv) x − $[{1\over 2}]$ , −y + $[{1\over 2}]$ , z; (v) −x + $[{1\over 2}]$ , y − $[{1\over 2}]$ , z − $[{1\over 2}]$ ; (vi) x, y − 1, z.

Figure 2
Monoperiodic chain of 1 composed of Ce^III cations, carboxylate groups and carboxylic acid groups.

Figure 3
Connection of the monoperiodic chains of 1 by the TDC²⁻ and HTDC⁻ anions.

Figure 4
Crystal structure of 1 along the crystallographic a-axis. The CeO₈ units are represented by polyhedra.

Crystal structure of 2

The asymmetric unit of [Ce(C₆H₂SO₄)(CH₃COO)(H₂O)]_n contains one Ce^III cation, one CH₃COO⁻ anion, one TDC²⁻ dianion and one water molecule, all of which are located in general positions (Fig. 5). The Ce^III cation is eightfold coordinated by oxygen atoms that originate from four TDC²⁻ dianions, two acetate ions and one water molecule, forming a distorted square antiprism. The carboxylate groups of the TDC²⁻ dianions coordinate the Ce^III cations exclusively in the bridging μ₂-(O,O′) binding mode, while for the acetate ions the bridging chelate μ₂-(O,O′,O′) binding mode is observed. The Ce—O distances are in the range 2.406 (2)–2.621 (2) Å (Table 2). Edge-sharing of the CeO₈ polyhedra leads to a dinuclear Ce₂O₁₄ IBU. Each IBU is surrounded by six TDC²⁻ ligands (Fig. 6), which connect it to nine other IBUs, while each linker bridges three IBUs (Fig. 7). This gives rise to a CP with a three-dimensional network (Fig. 8).

Table 2
Selected bond lengths (Å) for 2

Ce1—O1	2.422 (3)	Ce1—O5	2.621 (2)
Ce1—O2ⁱ	2.428 (3)	Ce1—O5ⁱ	2.466 (2)
Ce1—O3ⁱⁱ	2.406 (2)	Ce1—O6	2.551 (3)
Ce1—O4ⁱⁱⁱ	2.443 (2)	Ce1—O7	2.503 (3)
Symmetry codes: (i) ; (ii) ; (iii) $[x-1, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

Figure 5
Crystal structure of compound 2 with atom labeling and displacement ellipsoids drawn at the 50% probability level. Symmetry codes: (i) −x + 1, −y + 1, −z + 1; (ii) x − 1, y, z − 1; (iii) x − 1, −y + $[{3\over 2}]$ , z − $[{1\over 2}]$ .

Figure 6
Connection of the CeO₈ polyhedra and the coordination of the linker molecules to the Ce₂O₁₄ IBU of 2.

Figure 7
Bridging of three Ce₂O₁₄ IBUs by one TDC²⁻ dianion in 2.

Figure 8
Crystal structure of 2 along the crystallographic c-axis. The Ce₂O₁₄ IBUs are represented by polyhedra.

3. Supramolecular features

Supramolecular features of 1

Additionally, 1 exhibits hydrogen bonds (O—H⋯O) between HTDC⁻ and TDC²⁻ anions (O33—H33⋯O22 and O24—H24⋯O14) as well as acetic acid and TDC²⁻ (O42—H42⋯O1, Fig. 9). The H⋯O distances and O–H⋯O angles (Table 3) indicate the presence of strong hydrogen bonds (1.5–2.2 Å, 130–180°; Desiraju & Steiner, 1999 ). In addition, C—H⋯O hydrogen bonds are found, indicating the presence of weak hydrogen bonds.

Table 3
Hydrogen-bond geometry (Å, °) for 1

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12⋯O21	0.95	2.55	3.283 (8)	134
C12—H12⋯O32ⁱⁱⁱ	0.95	2.55	3.329 (9)	140
O24—H24⋯O14^v	0.84	1.77	2.599 (7)	168
O33—H33⋯O22^vii	0.85 (3)	2.06 (5)	2.871 (7)	159 (11)
C32—H32⋯O12^iv	0.95	2.55	3.449 (8)	158
O42—H42⋯O1	0.84	1.89	2.671 (8)	155
Symmetry codes: (iii) ; (iv) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z]$ ; (v) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (vii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Figure 9
Hydrogen bonds in 1. The carboxylic acid groups and carboxylate are related to HTDC⁻ anions and TDC²⁻ dianions, which are not shown completely for the sake of clarity. The hydrogen bonding is shown with dashed lines.

Supramolecular features of 2

In 2, hydrogen bonds (O—H⋯O) are present between the hydrogen atoms of the water molecules and the TDC²⁻ (O7—H4A⋯O4) and the acetate anions (O7—H4B⋯O6). The presence of these hydrogen bonds leads to the stabilization of the network through the connection with two adjacent IBUs (Fig. 10). The H⋯O distances and O—H⋯O angles (Table 4) indicate the presence of strong hydrogen bonds (1.5–2.2 Å, 130–180°; Desiraju & Steiner, 1999). For C—H⋯O hydrogen bonds, only weak interactions can be assumed.

Table 4
Hydrogen-bond geometry (Å, °) for 2

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8B⋯O3^iv	0.98	2.65	3.497 (5)	145
O7—H7A⋯O4ⁱⁱ	0.86 (2)	2.02 (2)	2.829 (4)	156 (4)
O7—H7B⋯O6^v	0.85 (2)	1.95 (2)	2.795 (4)	168 (5)
Symmetry codes: (ii) ; (iv) ; (v) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Figure 10
Hydrogen bonds in 2. The bridging carboxylate group is related to a TDC²⁻ dianion, which was omitted for clarity. The hydrogen bonding is shown with dashed lines.

4. Database survey

A search for crystal structures containing Ce and TDC²⁻ anions in the Cambridge Structural Database (CSD version 5.45, last update September 2024; Groom et al., 2016 ) revealed two structures containing Ce^III cations, namely [Ce₆(TDC)₉(N,N-diethylformamide)₅(H₂O)₃]_n (refcode UMEKUU; Yawer et al., 2016 ) and [Ce₂(TDC)₃(N,N′-dimethylacetamide)₂(H₂O)]_n (VUZNEM; Kumar et al., 2020 ). Extending the search to any lanthanide cation except Ce results in 150 hits. Restricting the search to the cell parameters of 1 (reduced cell, 5% tolerance) yields nine hits with eight unique compounds, none of which is isostructural to 1. Restricting the search to the cell parameters of 2 (reduced cell, 5% tolerance) gives 24 hits with 16 unique compounds. Eight of the compounds have the composition [Ln(TDC)(CH₃COO)(H₂O)]_n (Ln = Pr, Nd, Eu, Gd, Tb, Dy) (refcodes: KILCAL, KILCEP, KILCIT, KILCOZ, KILCUF, KILDAM (Ren et al., 2012 ), KILCUF01 (Yuan et al., 2022 ) (deposited without coordinates) and KILCUF02 (Han et al., 2024 )], which are isostructural to 2. Another six results are published as [Ln(TDC)(CH₃COO)(H₂O)]_n (Ln = Sm, Eu, Gd, Tb, Dy) and are also isostructural to 2 [refcodes: FEFXEF, FEFWIZ, FEFWUL, FEFWOF, FEFXAS (Han et al., 2017 ) and FEFWIZ01 (Han et al., 2020 )]. Another ten results are for compounds structurally related to 2 with acetate anions being replaced by nitrate anions [Ln(TDC)(NO₃)(H₂O)]_n (Ln = Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb) [refcodes: ICOREZ, ICORID, ICOROJ, ICORUP, ICOSAW, ICOSEA, ICOSIE, ICOSOK, ICOSUQ (Sun et al., 2011) and ICOROJ01 (Adcock et al., 2018 )].

5. Synthesis and crystallization

Synthesis of 1

Single crystals of the title compound were obtained by applying the high-throughput method as described in the literature with our custom-made high-throughput setup (Radke et al., 2023 ) and were placed in a Memmert UFP400 oven. 36.7 mg (0.21332 mmol) of H₂TDC (abcr, 97%) were inserted into a 2 mL Teflon vial. 80 µL (0.0640 mmol) of Ce(NO₃)₃·6H₂O [abcr, 99.9% Ce (REO)] in acetonitrile (c = 0.1333 mol L⁻¹), 320 µL of acetonitrile and 610 µL of acetic acid were added. The reactor was sealed, placed in an oven and heated to 423 K within 1 h. This temperature was held for 3 h and afterwards the reactor was cooled down to room temperature within 1 h. The reaction mixture was filtered off and washed three times with 3 mL of acetonitrile and dried under air. Comparison of the experimental powder pattern of 1 with that calculated from single crystal data reveal that this batch is contaminated with a very small amount of an unknown crystalline phase (Fig. 11).

Figure 11
Comparison of the calculated (black) PXRD pattern with the measured one (red) of 1.

Synthesis of 2

Single crystals of the title compound were obtained by applying the high-throughput method mentioned above. Different amounts of H₂O, EtOH and acetic acid were used to synthesize single crystals suitable for single-crystal X-ray diffraction (sample A) and the product containing larger amounts of 2 (sample B). In both syntheses, 9.2 mg (0.0533 mmol) of H₂TDC (abcr, 97%) were inserted into a 2 mL Teflon vial and 400 µL (0.0533 mmol) of Ce(NO₃)₃·6H₂O [abcr, 99.9% Ce (REO)] in H₂O/EtOH (68:32) (c = 0.1333 mol L⁻¹) were used. For sample A, 131 µL of H₂O/EtOH (68:32) and 469 µL of acetic acid, and for sample B, 470 µL of H₂O/EtOH (68:32) and 130 µL of acetic acid were added. The reactor was sealed, placed in an oven and heated to 423 K within 24 h. This temperature was held for 192 h and afterwards the reactor was cooled down to room temperature within 48 h. The reaction mixture was filtered off and washed with H₂O/EtOH (68:32) and dried in air. Compound 2 was not obtained phase pure, as demonstrated by powder X-ray diffraction (Fig. 12). While sample A contained single crystals with large amounts of unidentified byproduct, the majority of sample B can be assigned to microcrystalline 2.

Figure 12
Comparison of the calculated (black) PXRD pattern with the measured ones from sample A (red) and sample B (blue) of 2.

Experimental details

The powder X-ray diffraction patterns were collected on a Stoe Stadi P with a MYTHEN2 1K detector and Cu Kα1 radiation.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 5.

Table 5
Experimental details

	1	2
Crystal data
Chemical formula	[Ce₂(C₆H₃O₄S)₂(C₆H₂OS)₂(C₂H₄O₂)]	[Ce(C₂H₃O₂)(C₆H₂O₄S)(H₂O)]
M_r	1022.85	387.32
Crystal system, space group	Orthorhombic, Pna2₁	Monoclinic, P2₁/c
Temperature (K)	100	100
a, b, c (Å)	17.91596 (13), 11.08917 (9), 17.25666 (13)	10.0310 (1), 14.6755 (1), 7.6765 (1)
α, β, γ (°)	90, 90, 90	90, 102.354 (1), 90
V (Å³)	3428.43 (5)	1103.89 (2)
Z	4	4
Radiation type	Cu Kα	Cu Kα
μ (mm⁻¹)	23.23	33.89
Crystal size (mm)	0.08 × 0.08 × 0.03	0.12 × 0.10 × 0.08

Data collection
Diffractometer	XtaLAB Synergy, Dualflex, HyPix	XtaLAB Synergy, Dualflex, HyPix
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2023 $[Rigaku OD (2023). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )	Multi-scan (CrysAlis PRO; Rigaku OD, 2023 $[Rigaku OD (2023). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )
T_min, T_max	0.601, 1.000	0.301, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	29513, 7126, 7101	13515, 2360, 2349
R_int	0.022	0.025
(sin θ/λ)_max (Å⁻¹)	0.637	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.024, 0.067, 1.05	0.027, 0.077, 1.15
No. of reflections	7126	2360
No. of parameters	458	162
No. of restraints	2	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.43, −1.05	1.43, −1.30
Absolute structure	Refined as an inversion twin	–
Absolute structure parameter	0.491 (4)	–
Computer programs: CrysAlis PRO (Rigaku OD, 2023 $[Rigaku OD (2023). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ), SHELXT2014/4 (Sheldrick, 2015a ), SHELXL2016/6 (Sheldrick, 2015b ), DIAMOND (Brandenburg & Putz, 1999 ), XP in SHELXTL-PC (Sheldrick, 2008 ) and publCIF (Westrip, 2010 ).

Refinement of 1

The C—H H atoms were located in difference maps but were positioned with idealized geometry (methyl H atoms allowed to rotate but not to tip) and were refined isotropically with U_iso(H) = 1.2U_eq(C) (1.5 for methyl H atoms) using a riding model. The O—H H atoms at O24 and O42 were clearly located in difference maps but were finally positioned with idealized geometry, allowed to rotate but not to tip and were refined with U_iso(H) = 1.5U_eq(O) using a riding model. It is noted that some electron density is also found close to O1, which make a hydrogen bond to O42. Because the O⋯O distance between O42 and O1 is relatively short and the C—O distances C41—O42 and C5—O1 are clearly elongated, it cannot be excluded that the H atom is disordered over both sites. Considering these two H atoms, one must assume that compound 1 is a mixed-valance compound, consisting of Ce^III and Ce^IV, but bond-valence calculations using PLATON (Spek, 2009 ) leads to very similar values for both Ce centers, which deviate only slightly from that expected for Ce^III. Moreover, because this compound was not obtained as a pure phase, this cannot experimentally proven. Therefore, we assumed that the oxidation state is retained during the synthesis and in this case, one O—H H atom is missing for charge balance. In this context, it is noted that no reasonable electron density was found close to O atoms for carboxylate groups where the C—O distances are slightly different, but for one carboxylate group that shows comparable C—O bond lengths, a reasonable electron density maxima is observed at O33, which would make a hydrogen bond to O22. If an H atom is assigned to this maximum, the corresponding H atom can be refined isotropically, leading to a reasonable temperature factor. This leads to an elongated O—H distance, which indicates that the situation is similar to that between O1 and O42, where the H atom might be disordered. Therefore, the H atom at O33 (H33) was refined with restraints. Finally, it is noted that all carboxylate O atoms except O24 and O42 are coordinated to Ce cations, which might be responsible for the fact that in this case the C—O bond lengths are slightly elongated and not very different. This might also be responsible for the problems in the location of the final H atom and it can also not be excluded that the H atoms are disordered over at least two different sites.

The crystal is twinned by inversion and therefore, a twin-refinement was performed [BASF parameter: 0.491 (4)].

Refinement of 2

The C—H H atoms were positioned with idealized geometry (methyl H atoms allowed to rotate but not to tip) and were refined isotropically with U_iso(H) = 1.2U_eq(C) (1.5 for methyl H atoms) using a riding model. The O—H H atoms were located in difference maps and were refined isotropically with U_iso(H) = 1.5U_eq(O) using restraints.

Supporting information

CCDC references: 2415947; 2415946

Crystal structure: contains datablocks 1, 2. DOI: https://doi.org/10.1107/S2056989025000210/nx2017sup1.cif

Structure factors: contains datablock 1. DOI: https://doi.org/10.1107/S2056989025000210/nx20171sup2.hkl

Structure factors: contains datablock 2. DOI: https://doi.org/10.1107/S2056989025000210/nx20172sup3.hkl

checkCIF report

Computing details top

Poly[(acetic acid)bis(µ-5-carboxythiophene-2-carboxylato)bis(µ-thiophene-2,5-dicarboxylato)dicerium(III)] (1) top

Crystal data top

[Ce₂(C₆H₃O₄S)₂(C₆H₂OS)₂(C₂H₄O₂)]	D_x = 1.982 Mg m⁻³
M_r = 1022.85	Cu Kα radiation, λ = 1.54184 Å
Orthorhombic, Pna2₁	Cell parameters from 25594 reflections
a = 17.91596 (13) Å	θ = 2.5–78.6°
b = 11.08917 (9) Å	µ = 23.23 mm⁻¹
c = 17.25666 (13) Å	T = 100 K
V = 3428.43 (5) Å³	Block, red
Z = 4	0.08 × 0.08 × 0.03 mm
F(000) = 1976

Data collection top

XtaLAB Synergy, Dualflex, HyPix diffractometer	7126 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Cu) X-ray Source	7101 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.022
Detector resolution: 10.0000 pixels mm^-1	θ_max = 79.4°, θ_min = 4.7°
ω scans	h = −12→20
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2023)	k = −13→14
T_min = 0.601, T_max = 1.000	l = −21→21
29513 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.024	w = 1/[σ²(F_o²) + (0.049P)² + 4.6448P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.067	(Δ/σ)_max = 0.001
S = 1.05	Δρ_max = 1.43 e Å⁻³
7126 reflections	Δρ_min = −1.05 e Å⁻³
458 parameters	Absolute structure: Refined as an inversion twin
2 restraints	Absolute structure parameter: 0.491 (4)
Primary atom site location: dual

Special details top

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. Refined as a 2-component inversion twin.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Ce1	0.46380 (2)	0.80027 (2)	0.28586 (2)	0.01453 (8)
Ce2	0.18976 (2)	−0.15909 (3)	0.29904 (2)	0.01616 (8)
O1	0.5601 (3)	0.9287 (4)	0.3419 (3)	0.0244 (9)
O2	0.6600 (3)	0.8289 (4)	0.3874 (3)	0.0262 (10)
O3	0.7403 (3)	1.0927 (5)	0.6792 (3)	0.0284 (10)
O4	0.6311 (3)	1.1855 (5)	0.7001 (3)	0.0324 (11)
S1	0.68606 (9)	0.97752 (15)	0.52658 (9)	0.0247 (3)
C1	0.6206 (3)	0.9991 (6)	0.4542 (4)	0.0213 (12)
C2	0.5756 (4)	1.0967 (6)	0.4703 (4)	0.0273 (14)
H2	0.537576	1.124358	0.436258	0.033*
C3	0.5914 (4)	1.1509 (6)	0.5416 (4)	0.0257 (13)
H3	0.564755	1.218090	0.561729	0.031*
C4	0.6500 (4)	1.0959 (6)	0.5794 (4)	0.0229 (13)
C5	0.6152 (4)	0.9125 (6)	0.3899 (4)	0.0231 (12)
C6	0.6772 (4)	1.1245 (6)	0.6581 (4)	0.0210 (12)
O11	0.5337 (2)	0.6800 (4)	0.3645 (3)	0.0192 (9)
O12	0.6233 (2)	0.5628 (4)	0.4117 (3)	0.0242 (9)
O13	0.5094 (2)	0.3635 (4)	0.7003 (3)	0.0215 (9)
O14	0.4058 (2)	0.4679 (4)	0.7275 (2)	0.0200 (8)
S11	0.54976 (8)	0.49323 (13)	0.55758 (8)	0.0202 (3)
C11	0.5132 (4)	0.5817 (6)	0.4845 (4)	0.0218 (12)
C12	0.4420 (4)	0.6152 (7)	0.4994 (4)	0.0299 (14)
H12	0.412376	0.661448	0.464759	0.036*
C13	0.4165 (4)	0.5740 (7)	0.5722 (4)	0.0301 (15)
H13	0.368422	0.591469	0.592429	0.036*
C14	0.4687 (3)	0.5061 (6)	0.6106 (4)	0.0198 (12)
C15	0.5601 (4)	0.6078 (5)	0.4161 (3)	0.0197 (12)
C16	0.4612 (3)	0.4414 (6)	0.6848 (4)	0.0172 (12)
O21	0.3820 (3)	0.6444 (4)	0.3206 (3)	0.0239 (10)
O22	0.2682 (3)	0.6609 (4)	0.2674 (3)	0.0276 (11)
O23	0.2292 (3)	0.0610 (4)	0.3147 (3)	0.0299 (11)
O24	0.1564 (4)	0.1784 (5)	0.2421 (4)	0.0438 (15)
H24	0.130628	0.115383	0.238411	0.066*
S21	0.23213 (9)	0.40527 (14)	0.26857 (10)	0.0277 (3)
C21	0.3077 (4)	0.4717 (6)	0.3126 (4)	0.0276 (14)
C22	0.3471 (5)	0.3929 (7)	0.3566 (6)	0.044 (2)
H22	0.390305	0.414617	0.385313	0.053*
C23	0.3170 (5)	0.2748 (7)	0.3551 (6)	0.044 (2)
H23	0.337410	0.208507	0.382821	0.053*
C24	0.2546 (4)	0.2677 (6)	0.3087 (4)	0.0303 (14)
C25	0.3202 (3)	0.6025 (5)	0.2991 (4)	0.0219 (11)
C26	0.2124 (4)	0.1592 (5)	0.2890 (5)	0.0287 (14)
O31	0.2886 (3)	−0.1471 (4)	0.3875 (3)	0.0289 (11)
O32	0.4117 (3)	−0.1330 (4)	0.3991 (3)	0.0252 (9)
O33	0.3789 (3)	0.2171 (4)	0.7121 (3)	0.0297 (11)
H33	0.334 (2)	0.193 (9)	0.717 (7)	0.044*
O34	0.4761 (3)	0.1068 (5)	0.6798 (3)	0.0279 (10)
S31	0.41620 (8)	−0.01107 (14)	0.54570 (9)	0.0223 (3)
C31	0.3376 (3)	−0.0379 (6)	0.4919 (3)	0.0182 (11)
C32	0.2764 (4)	0.0208 (7)	0.5203 (4)	0.0271 (14)
H32	0.227951	0.015883	0.498103	0.032*
C33	0.2940 (4)	0.0900 (6)	0.5868 (4)	0.0265 (14)
H33A	0.258660	0.137317	0.614346	0.032*
C34	0.3674 (4)	0.0811 (6)	0.6069 (3)	0.0209 (12)
C35	0.3462 (4)	−0.1112 (5)	0.4215 (4)	0.0194 (12)
C36	0.4093 (4)	0.1370 (6)	0.6702 (4)	0.0247 (13)
O41	0.4239 (3)	1.0183 (5)	0.2643 (3)	0.0365 (12)
O42	0.5238 (4)	1.1350 (6)	0.2716 (5)	0.0552 (18)
H42	0.535686	1.084306	0.305602	0.083*
C41	0.4562 (5)	1.1099 (7)	0.2450 (5)	0.0397 (19)
C42	0.4262 (6)	1.2017 (9)	0.1916 (7)	0.056 (3)
H42A	0.460229	1.211191	0.147552	0.084*
H42B	0.421445	1.278750	0.218924	0.084*
H42C	0.377096	1.176024	0.172853	0.084*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ce1	0.02098 (15)	0.01503 (14)	0.00758 (14)	0.00154 (9)	0.00108 (12)	0.00061 (11)
Ce2	0.02058 (15)	0.01835 (14)	0.00956 (14)	−0.00248 (10)	−0.00244 (13)	0.00005 (11)
O1	0.030 (2)	0.025 (2)	0.018 (2)	−0.0008 (18)	−0.0033 (18)	0.0006 (18)
O2	0.032 (3)	0.023 (2)	0.024 (3)	0.0029 (19)	−0.003 (2)	−0.0046 (18)
O3	0.031 (3)	0.033 (2)	0.021 (2)	0.001 (2)	−0.0032 (19)	−0.0059 (19)
O4	0.035 (3)	0.040 (3)	0.022 (3)	0.006 (2)	0.003 (2)	−0.013 (2)
S1	0.0263 (8)	0.0282 (7)	0.0195 (7)	0.0050 (6)	−0.0035 (6)	−0.0081 (6)
C1	0.021 (3)	0.027 (3)	0.015 (3)	−0.002 (2)	0.000 (2)	−0.006 (2)
C2	0.027 (3)	0.030 (3)	0.025 (3)	0.004 (3)	0.001 (3)	−0.003 (3)
C3	0.029 (3)	0.023 (3)	0.025 (3)	0.004 (2)	0.001 (3)	−0.006 (2)
C4	0.025 (3)	0.024 (3)	0.019 (3)	−0.002 (2)	0.003 (2)	−0.005 (2)
C5	0.029 (3)	0.025 (3)	0.015 (3)	−0.007 (3)	0.001 (2)	−0.001 (2)
C6	0.024 (3)	0.021 (3)	0.017 (3)	−0.002 (2)	−0.001 (2)	−0.004 (2)
O11	0.028 (2)	0.0177 (18)	0.012 (2)	0.0019 (16)	0.0016 (17)	0.0038 (17)
O12	0.020 (2)	0.030 (2)	0.022 (2)	0.0043 (18)	0.0020 (16)	0.0052 (18)
O13	0.022 (2)	0.026 (2)	0.016 (2)	0.0053 (18)	0.0021 (17)	0.0087 (17)
O14	0.024 (2)	0.0199 (19)	0.0166 (19)	0.0025 (16)	0.0033 (17)	0.0037 (17)
S11	0.0190 (6)	0.0258 (7)	0.0158 (7)	0.0035 (5)	0.0021 (5)	0.0087 (6)
C11	0.026 (3)	0.023 (3)	0.017 (3)	0.001 (2)	0.006 (2)	0.007 (2)
C12	0.026 (3)	0.039 (4)	0.025 (3)	0.004 (3)	0.003 (3)	0.015 (3)
C13	0.026 (3)	0.042 (4)	0.022 (3)	0.009 (3)	0.006 (3)	0.012 (3)
C14	0.017 (3)	0.027 (3)	0.015 (3)	−0.001 (2)	0.001 (2)	0.010 (2)
C15	0.028 (3)	0.018 (3)	0.014 (3)	−0.004 (2)	0.004 (2)	0.001 (2)
C16	0.017 (3)	0.019 (3)	0.016 (3)	−0.002 (2)	−0.0022 (19)	0.006 (2)
O21	0.026 (2)	0.025 (2)	0.020 (2)	0.0007 (16)	−0.0014 (17)	−0.0063 (17)
O22	0.036 (3)	0.021 (2)	0.025 (3)	−0.0049 (17)	−0.009 (2)	0.0027 (17)
O23	0.034 (2)	0.022 (2)	0.033 (3)	−0.0054 (18)	−0.006 (2)	0.0018 (19)
O24	0.044 (3)	0.022 (2)	0.065 (4)	−0.006 (2)	−0.024 (3)	0.006 (2)
S21	0.0290 (8)	0.0203 (6)	0.0338 (9)	−0.0040 (5)	−0.0056 (6)	0.0016 (6)
C21	0.027 (3)	0.022 (3)	0.033 (4)	0.001 (2)	−0.002 (2)	−0.001 (3)
C22	0.044 (4)	0.024 (3)	0.064 (6)	−0.007 (3)	−0.022 (4)	0.003 (3)
C23	0.049 (5)	0.023 (3)	0.060 (6)	−0.005 (3)	−0.017 (4)	0.005 (4)
C24	0.033 (3)	0.026 (3)	0.032 (4)	−0.003 (3)	−0.002 (3)	−0.001 (3)
C25	0.025 (3)	0.021 (3)	0.020 (3)	−0.002 (2)	0.000 (2)	−0.003 (3)
C26	0.030 (3)	0.025 (3)	0.032 (4)	−0.003 (2)	0.000 (3)	0.000 (3)
O31	0.028 (2)	0.032 (3)	0.027 (3)	0.0014 (19)	−0.011 (2)	−0.013 (2)
O32	0.028 (2)	0.029 (2)	0.018 (2)	−0.0017 (19)	0.0069 (18)	−0.0082 (19)
O33	0.042 (3)	0.027 (2)	0.020 (2)	−0.008 (2)	0.012 (2)	−0.0117 (19)
O34	0.027 (2)	0.036 (3)	0.021 (2)	−0.005 (2)	−0.0036 (18)	−0.007 (2)
S31	0.0204 (7)	0.0285 (7)	0.0178 (7)	0.0003 (5)	−0.0019 (5)	−0.0110 (6)
C31	0.020 (3)	0.023 (3)	0.012 (3)	−0.001 (2)	0.000 (2)	−0.005 (2)
C32	0.019 (3)	0.041 (4)	0.021 (3)	0.001 (3)	−0.004 (2)	−0.013 (3)
C33	0.029 (3)	0.027 (3)	0.023 (3)	0.004 (3)	0.005 (3)	−0.014 (3)
C34	0.026 (3)	0.024 (3)	0.013 (3)	0.000 (2)	0.000 (2)	−0.009 (2)
C35	0.024 (3)	0.019 (3)	0.016 (3)	0.001 (2)	−0.005 (2)	−0.001 (2)
C36	0.033 (4)	0.025 (3)	0.015 (3)	−0.003 (3)	0.002 (3)	−0.008 (2)
O41	0.035 (3)	0.033 (3)	0.042 (3)	0.005 (2)	−0.001 (2)	−0.001 (2)
O42	0.061 (4)	0.038 (3)	0.067 (5)	−0.013 (3)	−0.015 (3)	0.012 (3)
C41	0.050 (5)	0.030 (4)	0.039 (5)	0.000 (3)	−0.009 (3)	−0.001 (3)
C42	0.069 (7)	0.040 (5)	0.060 (7)	0.006 (4)	−0.001 (5)	0.015 (4)

Geometric parameters (Å, º) top

Ce1—O1	2.437 (5)	C13—H13	0.9500
Ce1—O4ⁱ	2.259 (5)	C13—C14	1.371 (9)
Ce1—O11	2.278 (4)	C14—C16	1.474 (8)
Ce1—O13ⁱⁱ	2.389 (4)	O21—C25	1.257 (7)
Ce1—O21	2.344 (5)	O22—C25	1.259 (8)
Ce1—O32ⁱⁱⁱ	2.288 (4)	O23—C26	1.214 (8)
Ce1—O34ⁱⁱ	2.360 (5)	O24—H24	0.8400
Ce1—O41	2.549 (5)	O24—C26	1.306 (9)
Ce2—O2^iv	2.481 (5)	S21—C21	1.718 (7)
Ce2—O3ⁱⁱ	2.527 (5)	S21—C24	1.723 (7)
Ce2—O12^iv	2.518 (4)	C21—C22	1.356 (11)
Ce2—O14^v	2.538 (4)	C21—C25	1.486 (8)
Ce2—O22^vi	2.502 (5)	C22—H22	0.9500
Ce2—O23	2.555 (4)	C22—C23	1.416 (10)
Ce2—O31	2.342 (5)	C23—H23	0.9500
Ce2—O33^v	2.376 (5)	C23—C24	1.378 (11)
O1—C5	1.301 (8)	C24—C26	1.462 (9)
O2—C5	1.226 (8)	O31—C35	1.252 (8)
O3—C6	1.240 (8)	O32—C35	1.260 (8)
O4—C6	1.290 (8)	O33—H33	0.85 (3)
S1—C1	1.730 (6)	O33—C36	1.268 (8)
S1—C4	1.724 (6)	O34—C36	1.255 (9)
C1—C2	1.377 (9)	S31—C31	1.713 (6)
C1—C5	1.470 (8)	S31—C34	1.710 (6)
C2—H2	0.9500	C31—C32	1.366 (9)
C2—C3	1.400 (9)	C31—C35	1.469 (8)
C3—H3	0.9500	C32—H32	0.9500
C3—C4	1.378 (10)	C32—C33	1.417 (9)
C4—C6	1.478 (9)	C33—H33A	0.9500
O11—C15	1.287 (8)	C33—C34	1.363 (10)
O12—C15	1.239 (8)	C34—C36	1.463 (8)
O13—C16	1.249 (7)	O41—C41	1.215 (10)
O14—C16	1.270 (7)	O42—H42	0.8400
S11—C11	1.727 (6)	O42—C41	1.324 (10)
S11—C14	1.722 (6)	C41—C42	1.475 (12)
C11—C12	1.354 (10)	C42—H42A	0.9800
C11—C15	1.478 (8)	C42—H42B	0.9800
C12—H12	0.9500	C42—H42C	0.9800
C12—C13	1.412 (9)

O1—Ce1—O41	72.69 (16)	C16—O13—Ce1^viii	142.8 (4)
O4ⁱ—Ce1—O1	138.75 (17)	C16—O14—Ce2^x	132.9 (4)
O4ⁱ—Ce1—O11	147.65 (18)	C14—S11—C11	91.2 (3)
O4ⁱ—Ce1—O13ⁱⁱ	78.45 (19)	C12—C11—S11	112.0 (5)
O4ⁱ—Ce1—O21	75.46 (18)	C12—C11—C15	129.4 (6)
O4ⁱ—Ce1—O32ⁱⁱⁱ	103.31 (19)	C15—C11—S11	118.6 (5)
O4ⁱ—Ce1—O34ⁱⁱ	78.76 (18)	C11—C12—H12	123.7
O4ⁱ—Ce1—O41	68.09 (19)	C11—C12—C13	112.6 (6)
O11—Ce1—O1	73.52 (16)	C13—C12—H12	123.7
O11—Ce1—O13ⁱⁱ	79.19 (16)	C12—C13—H13	123.6
O11—Ce1—O21	76.09 (16)	C14—C13—C12	112.8 (6)
O11—Ce1—O32ⁱⁱⁱ	84.53 (17)	C14—C13—H13	123.6
O11—Ce1—O34ⁱⁱ	117.81 (16)	C13—C14—S11	111.3 (5)
O11—Ce1—O41	142.83 (17)	C13—C14—C16	128.7 (5)
O13ⁱⁱ—Ce1—O1	123.16 (16)	C16—C14—S11	119.9 (4)
O13ⁱⁱ—Ce1—O41	133.41 (17)	O11—C15—C11	117.7 (6)
O21—Ce1—O1	140.50 (16)	O12—C15—O11	123.0 (6)
O21—Ce1—O13ⁱⁱ	73.96 (16)	O12—C15—C11	119.3 (5)
O21—Ce1—O34ⁱⁱ	143.69 (17)	O13—C16—O14	125.1 (6)
O21—Ce1—O41	124.15 (16)	O13—C16—C14	117.4 (5)
O32ⁱⁱⁱ—Ce1—O1	76.14 (16)	O14—C16—C14	117.5 (5)
O32ⁱⁱⁱ—Ce1—O13ⁱⁱ	148.81 (17)	C25—O21—Ce1	138.4 (4)
O32ⁱⁱⁱ—Ce1—O21	76.40 (16)	C25—O22—Ce2ⁱⁱⁱ	136.9 (4)
O32ⁱⁱⁱ—Ce1—O34ⁱⁱ	134.98 (18)	C26—O23—Ce2	138.5 (5)
O32ⁱⁱⁱ—Ce1—O41	72.77 (18)	C26—O24—H24	109.5
O34ⁱⁱ—Ce1—O1	74.31 (16)	C21—S21—C24	91.0 (3)
O34ⁱⁱ—Ce1—O13ⁱⁱ	76.18 (17)	C22—C21—S21	112.4 (5)
O34ⁱⁱ—Ce1—O41	66.45 (18)	C22—C21—C25	129.7 (7)
O2^iv—Ce2—O3ⁱⁱ	146.16 (16)	C25—C21—S21	117.9 (5)
O2^iv—Ce2—O12^iv	75.25 (16)	C21—C22—H22	123.6
O2^iv—Ce2—O14^v	125.11 (15)	C21—C22—C23	112.8 (7)
O2^iv—Ce2—O22^vi	69.48 (17)	C23—C22—H22	123.6
O2^iv—Ce2—O23	136.00 (16)	C22—C23—H23	124.1
O3ⁱⁱ—Ce2—O14^v	76.98 (15)	C24—C23—C22	111.8 (7)
O3ⁱⁱ—Ce2—O23	70.81 (17)	C24—C23—H23	124.1
O12^iv—Ce2—O3ⁱⁱ	137.97 (16)	C23—C24—S21	111.9 (5)
O12^iv—Ce2—O14^v	79.70 (15)	C23—C24—C26	127.0 (7)
O12^iv—Ce2—O23	69.15 (16)	C26—C24—S21	120.9 (5)
O14^v—Ce2—O23	73.03 (14)	O21—C25—O22	126.2 (5)
O22^vi—Ce2—O3ⁱⁱ	77.01 (16)	O21—C25—C21	116.5 (6)
O22^vi—Ce2—O12^iv	140.61 (16)	O22—C25—C21	117.3 (5)
O22^vi—Ce2—O14^v	135.69 (15)	O23—C26—O24	124.3 (6)
O22^vi—Ce2—O23	129.04 (15)	O23—C26—C24	121.6 (7)
O31—Ce2—O2^iv	78.76 (18)	O24—C26—C24	114.0 (6)
O31—Ce2—O3ⁱⁱ	98.17 (17)	C35—O31—Ce2	161.2 (5)
O31—Ce2—O12^iv	80.23 (17)	C35—O32—Ce1^vi	134.8 (4)
O31—Ce2—O14^v	142.75 (15)	Ce2^x—O33—H33	68 (7)
O31—Ce2—O22^vi	76.28 (16)	C36—O33—Ce2^x	170.6 (5)
O31—Ce2—O23	70.59 (16)	C36—O33—H33	104 (7)
O31—Ce2—O33^v	146.68 (17)	C36—O34—Ce1^viii	114.9 (4)
O33^v—Ce2—O2^iv	80.68 (18)	C34—S31—C31	91.0 (3)
O33^v—Ce2—O3ⁱⁱ	84.75 (18)	C32—C31—S31	112.5 (5)
O33^v—Ce2—O12^iv	119.17 (16)	C32—C31—C35	130.1 (6)
O33^v—Ce2—O14^v	70.38 (15)	C35—C31—S31	117.2 (5)
O33^v—Ce2—O22^vi	72.06 (16)	C31—C32—H32	124.1
O33^v—Ce2—O23	139.62 (16)	C31—C32—C33	111.7 (6)
C5—O1—Ce1	135.2 (4)	C33—C32—H32	124.1
C5—O2—Ce2^vii	137.4 (5)	C32—C33—H33A	123.8
C6—O3—Ce2^viii	127.5 (4)	C34—C33—C32	112.5 (6)
C6—O4—Ce1^ix	152.4 (5)	C34—C33—H33A	123.8
C4—S1—C1	91.3 (3)	C33—C34—S31	112.3 (5)
C2—C1—S1	111.1 (5)	C33—C34—C36	130.8 (6)
C2—C1—C5	128.8 (6)	C36—C34—S31	116.9 (5)
C5—C1—S1	119.9 (5)	O31—C35—O32	124.2 (6)
C1—C2—H2	123.3	O31—C35—C31	118.5 (6)
C1—C2—C3	113.4 (6)	O32—C35—C31	117.3 (6)
C3—C2—H2	123.3	O33—C36—C34	120.2 (6)
C2—C3—H3	123.8	O34—C36—O33	121.4 (6)
C4—C3—C2	112.3 (6)	O34—C36—C34	118.3 (6)
C4—C3—H3	123.8	C41—O41—Ce1	134.3 (5)
C3—C4—S1	111.9 (5)	C41—O42—H42	109.5
C3—C4—C6	126.2 (6)	O41—C41—O42	121.1 (8)
C6—C4—S1	121.7 (5)	O41—C41—C42	125.0 (8)
O1—C5—C1	116.1 (6)	O42—C41—C42	113.8 (8)
O2—C5—O1	125.3 (6)	C41—C42—H42A	109.5
O2—C5—C1	118.5 (6)	C41—C42—H42B	109.5
O3—C6—O4	124.7 (6)	C41—C42—H42C	109.5
O3—C6—C4	120.6 (6)	H42A—C42—H42B	109.5
O4—C6—C4	114.7 (6)	H42A—C42—H42C	109.5
C15—O11—Ce1	168.0 (4)	H42B—C42—H42C	109.5
C15—O12—Ce2^vii	107.9 (4)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···O21	0.95	2.55	3.283 (8)	134
C12—H12···O32ⁱⁱⁱ	0.95	2.55	3.329 (9)	140
O24—H24···O14^v	0.84	1.77	2.599 (7)	168
O33—H33···O22^xi	0.85 (3)	2.06 (5)	2.871 (7)	159 (11)
C32—H32···O12^iv	0.95	2.55	3.449 (8)	158
O42—H42···O1	0.84	1.89	2.671 (8)	155

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

Poly[(µ-acetato)aqua(µ₄-thiophene-2,5-dicarboxylato)cerium(III)] (2) top

Crystal data top

[Ce(C₂H₃O₂)(C₆H₂O₄S)(H₂O)]	F(000) = 740
M_r = 387.32	D_x = 2.330 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54184 Å
a = 10.0310 (1) Å	Cell parameters from 10498 reflections
b = 14.6755 (1) Å	θ = 3.1–79.9°
c = 7.6765 (1) Å	µ = 33.89 mm⁻¹
β = 102.354 (1)°	T = 100 K
V = 1103.89 (2) Å³	Block, colorless
Z = 4	0.12 × 0.10 × 0.08 mm

Data collection top

XtaLAB Synergy, Dualflex, HyPix diffractometer	2360 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Cu) X-ray Source	2349 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.025
Detector resolution: 10.0000 pixels mm^-1	θ_max = 80.3°, θ_min = 4.5°
ω scans	h = −12→10
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2023)	k = −18→18
T_min = 0.301, T_max = 1.000	l = −9→9
13515 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.027	w = 1/[σ²(F_o²) + (0.0508P)² + 2.3818P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.077	(Δ/σ)_max = 0.002
S = 1.15	Δρ_max = 1.43 e Å⁻³
2360 reflections	Δρ_min = −1.30 e Å⁻³
162 parameters	Extinction correction: SHELXL2016/6 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
3 restraints	Extinction coefficient: 0.00097 (10)
Primary atom site location: dual

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Ce1	0.39777 (2)	0.61197 (2)	0.39322 (2)	0.00537 (11)
S1	0.97823 (9)	0.62456 (6)	0.89764 (12)	0.00924 (18)
C1	0.8335 (3)	0.6693 (2)	0.7640 (5)	0.0091 (7)
C2	0.8385 (4)	0.7628 (3)	0.7551 (5)	0.0120 (7)
H2	0.766359	0.799189	0.690202	0.014*
C3	0.9626 (4)	0.7987 (2)	0.8530 (5)	0.0123 (7)
H3	0.984488	0.861789	0.859212	0.015*
C4	1.0481 (3)	0.7316 (2)	0.9386 (5)	0.0081 (6)
C5	0.7227 (4)	0.6083 (2)	0.6703 (5)	0.0102 (7)
O1	0.6225 (3)	0.64614 (19)	0.5702 (4)	0.0139 (5)
O2	0.7387 (3)	0.52357 (18)	0.6960 (4)	0.0140 (5)
C6	1.1848 (3)	0.7417 (2)	1.0561 (4)	0.0068 (6)
O3	1.2357 (2)	0.67297 (17)	1.1434 (3)	0.0102 (5)
O4	1.2436 (2)	0.81927 (17)	1.0629 (3)	0.0095 (5)
O5	0.5659 (3)	0.48401 (17)	0.3371 (3)	0.0110 (5)
O6	0.5347 (3)	0.59880 (18)	0.1501 (4)	0.0122 (5)
C7	0.6028 (3)	0.5302 (2)	0.2133 (5)	0.0077 (6)
C8	0.7282 (4)	0.5017 (3)	0.1529 (5)	0.0136 (7)
H8A	0.743427	0.542620	0.058242	0.016*
H8B	0.716894	0.439144	0.107223	0.016*
H8C	0.806844	0.504409	0.253655	0.016*
O7	0.4453 (3)	0.77851 (18)	0.3711 (3)	0.0121 (5)
H7A	0.387 (4)	0.807 (3)	0.291 (5)	0.018*
H7B	0.484 (5)	0.816 (3)	0.452 (5)	0.018*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ce1	0.00288 (14)	0.00494 (15)	0.00770 (14)	0.00049 (5)	−0.00018 (9)	0.00042 (5)
S1	0.0047 (4)	0.0073 (4)	0.0142 (4)	−0.0007 (3)	−0.0013 (3)	0.0008 (3)
C1	0.0040 (15)	0.0136 (17)	0.0087 (15)	−0.0003 (12)	−0.0006 (12)	−0.0001 (12)
C2	0.0061 (16)	0.0130 (18)	0.0149 (18)	0.0005 (12)	−0.0021 (13)	0.0017 (13)
C3	0.0088 (15)	0.0073 (16)	0.0182 (17)	0.0007 (12)	−0.0025 (13)	0.0023 (13)
C4	0.0050 (15)	0.0097 (16)	0.0086 (15)	−0.0022 (12)	−0.0008 (12)	0.0006 (12)
C5	0.0076 (17)	0.0100 (18)	0.0129 (18)	−0.0026 (11)	0.0019 (14)	−0.0007 (12)
O1	0.0087 (11)	0.0122 (13)	0.0177 (13)	−0.0028 (10)	−0.0041 (10)	0.0027 (11)
O2	0.0095 (12)	0.0116 (13)	0.0173 (13)	−0.0013 (9)	−0.0051 (10)	0.0021 (10)
C6	0.0038 (15)	0.0112 (16)	0.0052 (15)	−0.0005 (12)	0.0006 (12)	−0.0011 (12)
O3	0.0071 (11)	0.0121 (12)	0.0091 (11)	0.0001 (9)	−0.0030 (9)	0.0018 (9)
O4	0.0071 (11)	0.0082 (12)	0.0122 (11)	−0.0025 (9)	0.0000 (9)	−0.0007 (9)
O5	0.0106 (12)	0.0126 (12)	0.0107 (11)	0.0020 (9)	0.0039 (9)	0.0030 (9)
O6	0.0123 (13)	0.0101 (11)	0.0148 (13)	0.0026 (10)	0.0046 (10)	0.0033 (10)
C7	0.0074 (15)	0.0065 (15)	0.0086 (14)	−0.0010 (12)	0.0006 (12)	0.0023 (12)
C8	0.0126 (17)	0.0115 (17)	0.0195 (17)	−0.0005 (13)	0.0093 (14)	−0.0016 (14)
O7	0.0131 (13)	0.0106 (12)	0.0102 (12)	−0.0024 (10)	−0.0030 (10)	−0.0006 (9)

Geometric parameters (Å, º) top

Ce1—Ce1ⁱ	4.0320 (3)	C3—H3	0.9500
Ce1—O1	2.422 (3)	C3—C4	1.377 (5)
Ce1—O2ⁱ	2.428 (3)	C4—C6	1.479 (4)
Ce1—O3ⁱⁱ	2.406 (2)	C5—O1	1.257 (5)
Ce1—O4ⁱⁱⁱ	2.443 (2)	C5—O2	1.263 (4)
Ce1—O5	2.621 (2)	C6—O3	1.258 (4)
Ce1—O5ⁱ	2.466 (2)	C6—O4	1.277 (4)
Ce1—O6	2.551 (3)	O5—C7	1.285 (4)
Ce1—C7	2.965 (4)	O6—C7	1.254 (4)
Ce1—O7	2.503 (3)	C7—C8	1.491 (5)
S1—C1	1.719 (3)	C8—H8A	0.9800
S1—C4	1.722 (4)	C8—H8B	0.9800
C1—C2	1.375 (5)	C8—H8C	0.9800
C1—C5	1.488 (5)	O7—H7A	0.861 (19)
C2—H2	0.9500	O7—H7B	0.854 (19)
C2—C3	1.411 (5)

O1—Ce1—Ce1ⁱ	67.00 (6)	O7—Ce1—C7	101.68 (9)
O1—Ce1—O2ⁱ	136.75 (9)	C1—S1—C4	91.09 (17)
O1—Ce1—O4ⁱⁱⁱ	103.58 (9)	C2—C1—S1	112.1 (3)
O1—Ce1—O5	71.71 (9)	C2—C1—C5	127.4 (3)
O1—Ce1—O5ⁱ	72.22 (9)	C5—C1—S1	120.4 (3)
O1—Ce1—O6	81.02 (10)	C1—C2—H2	123.7
O1—Ce1—C7	71.95 (10)	C1—C2—C3	112.5 (3)
O1—Ce1—O7	70.61 (9)	C3—C2—H2	123.7
O2ⁱ—Ce1—Ce1ⁱ	69.76 (6)	C2—C3—H3	124.0
O2ⁱ—Ce1—O4ⁱⁱⁱ	96.07 (9)	C4—C3—C2	112.0 (3)
O2ⁱ—Ce1—O5ⁱ	75.06 (9)	C4—C3—H3	124.0
O2ⁱ—Ce1—O5	73.16 (8)	C3—C4—S1	112.2 (3)
O2ⁱ—Ce1—O6	95.20 (9)	C3—C4—C6	128.4 (3)
O2ⁱ—Ce1—C7	86.69 (9)	C6—C4—S1	119.4 (3)
O2ⁱ—Ce1—O7	152.22 (8)	O1—C5—C1	116.5 (3)
O3ⁱⁱ—Ce1—Ce1ⁱ	145.65 (6)	O1—C5—O2	126.1 (3)
O3ⁱⁱ—Ce1—O1	139.39 (9)	O2—C5—C1	117.4 (3)
O3ⁱⁱ—Ce1—O2ⁱ	80.56 (8)	C5—O1—Ce1	141.1 (2)
O3ⁱⁱ—Ce1—O4ⁱⁱⁱ	82.77 (8)	C5—O2—Ce1ⁱ	135.8 (2)
O3ⁱⁱ—Ce1—O5ⁱ	146.62 (8)	O3—C6—C4	117.5 (3)
O3ⁱⁱ—Ce1—O5	118.98 (8)	O3—C6—O4	124.2 (3)
O3ⁱⁱ—Ce1—O6	79.80 (9)	O4—C6—C4	118.3 (3)
O3ⁱⁱ—Ce1—C7	101.36 (9)	C6—O3—Ce1^iv	148.4 (2)
O3ⁱⁱ—Ce1—O7	71.86 (8)	C6—O4—Ce1^v	133.3 (2)
O4ⁱⁱⁱ—Ce1—Ce1ⁱ	116.42 (6)	Ce1ⁱ—O5—Ce1	104.82 (9)
O4ⁱⁱⁱ—Ce1—O5	152.47 (8)	C7—O5—Ce1ⁱ	155.3 (2)
O4ⁱⁱⁱ—Ce1—O5ⁱ	77.58 (8)	C7—O5—Ce1	92.3 (2)
O4ⁱⁱⁱ—Ce1—O6	157.36 (8)	C7—O6—Ce1	96.4 (2)
O4ⁱⁱⁱ—Ce1—C7	175.38 (9)	O5—C7—Ce1	62.02 (18)
O4ⁱⁱⁱ—Ce1—O7	77.54 (9)	O5—C7—C8	118.5 (3)
O5ⁱ—Ce1—Ce1ⁱ	38.93 (6)	O6—C7—Ce1	58.74 (19)
O5—Ce1—Ce1ⁱ	36.25 (5)	O6—C7—O5	119.4 (3)
O5ⁱ—Ce1—O5	75.18 (9)	O6—C7—C8	122.1 (3)
O5ⁱ—Ce1—O6	124.42 (8)	C8—C7—Ce1	166.9 (2)
O5—Ce1—C7	25.65 (9)	C7—C8—H8A	109.5
O5ⁱ—Ce1—C7	99.64 (9)	C7—C8—H8B	109.5
O5ⁱ—Ce1—O7	128.22 (8)	C7—C8—H8C	109.5
O6—Ce1—Ce1ⁱ	85.93 (6)	H8A—C8—H8B	109.5
O6—Ce1—O5	50.13 (8)	H8A—C8—H8C	109.5
O6—Ce1—C7	24.85 (9)	H8B—C8—H8C	109.5
C7—Ce1—Ce1ⁱ	61.08 (6)	Ce1—O7—H7A	114 (3)
O7—Ce1—Ce1ⁱ	137.38 (6)	Ce1—O7—H7B	129 (3)
O7—Ce1—O5	123.36 (8)	H7A—O7—H7B	111 (4)
O7—Ce1—O6	83.35 (9)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8B···O3^vi	0.98	2.65	3.497 (5)	145
O7—H7A···O4ⁱⁱ	0.86 (2)	2.02 (2)	2.829 (4)	156 (4)
O7—H7B···O6^vii	0.85 (2)	1.95 (2)	2.795 (4)	168 (5)

Symmetry codes: (ii) x−1, y, z−1; (vi) −x+2, −y+1, −z+1; (vii) x, −y+3/2, z+1/2.

Acknowledgements

The authors thank the state of Schleswig-Holstein for the financial support. NR and NS acknowledge support by the Deutsche Forschungsgemeinschaft (STO-643/15–1).

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