Crystal structure of poly[μ3-acetato-di­aqua-μ3-sulfato-cerium(III)]: serendipitous synthesis of a layered coordination polymer exhibiting inter­layer O—H⋯O hydrogen bonding

Ruser, N.; Näther, C.; Stock, N.

doi:10.1107/S2056989024012313

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ISSN: 2056-9890

Volume 81| Part 2| February 2025| Pages 104-108

https://doi.org/10.1107/S2056989024012313

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Crystal structure of poly[μ₃-acetato-diaqua-μ₃-sulfato-cerium(III)]: serendipitous synthesis of a layered coordination polymer exhibiting interlayer O—H⋯O hydrogen bonding

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 W. T. A. Harrison, University of Aberdeen, United Kingdom (Received 17 December 2024; accepted 20 December 2024; online 10 January 2025)

Single crystals of the title compound, [Ce(CH₃COO)(SO₄)(H₂O)₂]_n, were obtained serendipitously by the reaction of Ce(NO₃)₃·6H₂O with 2,5-thiophenedicarboxylic acid (H₂TDC) and acetic acid in a mixture of ethanol and water, where it is assumed that the sulfate ions leached from the Teflon reactor, which was treated with peroxymonosulfuric acid prior to its use. Its asymmetric unit consists of one Ce^III cation, one sulfate dianion, one acetate anion and two crystallographically independent water molecules, all of them located in general positions. The cerium cations are coordinated by three acetate anions (one O,O-chelating) and three sulfate dianions that are related by symmetry as well as two independent water molecules within an irregular CeO₉ coordination geometry. The Ce^III cations are linked by the acetate ions into [010] chains, which are further connected into (001) layers by the sulfate dianions. Intralayer and interlayer O—H⋯O hydrogen bonds are observed. Powder X-ray diffraction shows that only traces of the title compound have formed together with a large amount of an unknown crystalline phase. Attempts to prepare the title compound in larger amounts and as a pure phase were unsuccessful.

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

CCDC reference: 2411959

1. Chemical context

In the search for new coordination polymers (CPs) (Batten et al., 2009 ) or metal–organic frameworks (MOFs) (Rowsell & Yaghi, 2004 ; Long & Yaghi, 2009 ), many inorganic and organic building blocks have been used to construct such materials. Consisting of repeating units of metal atoms or ions bridged by coordinating ligands, the resulting frameworks of CPs extend in up to three dimensions. MOFs, on the other hand, are a subclass of CPs and contain only organic ligands, called linkers, and extend in two or three dimensions. Another requirement is the presence of potential pores (Batten et al., 2013 ), which generate large specific surface areas that can be used for applications 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 ). Depending on the metal ions and organic linkers used, the properties of MOFs can often be tailored (Sahayaraj et al., 2023). For example, by using a metal such as cerium, its ability to change its oxidation state between +III and +IV can be exploited in catalysis (Lammert et al., 2015; Smolders et al., 2018 , 2020 ).

There are as many different building blocks as there are reaction conditions to synthesize such materials. This leads to multidimensional parameter spaces that can be explored with many potential compounds to be discovered. The so-called high-throughput method is very useful when it comes to screening parameter spaces (Stock, 2010 ). With this method, many different syntheses can be carried out simultaneously while varying the reaction conditions. Some areas of a parameter space lead exclusively to one compound, i.e. phase pure compounds, while in other cases phase mixtures are observed. This work reports the synthesis and structure of the title Ce^III -CP discovered in a screening experiment by reacting equimolar amounts of a cerium nitrate and 2,5-thiophenedicarboxylic acid (H₂TDC) and varying the ratio of acetic acid and ethanol/water mixture. Surprisingly, single crystals of a product were obtained that did not contain TDC^2– dianions, but rather sulfate dianions.

2. Structural commentary

The asymmetric unit of the title compound, [Ce(CH₃COO)(SO₄)(H₂O)₂]_n, consists of a crystallographically independent Ce^III cation, one acetate anion, one sulfate dianion and two crystallographically independent water molecules, all in general positions (Fig. 1). Each Ce^III cation is ninefold coordinated by four O atoms of three symmetry-equivalent acetate anions, three O atoms of three symmetry-equivalent sulfate dianions and two crystallographically independent water molecules. The Ce—O bond lengths range from 2.4385 (10) to 2.6518 (10) Å (Table 1) and the O—Ce—O angles reveal that the coordination geometry around the Ce^III ion is distorted. Two of the three acetate anions are coordinated with only one carboxyl O atom to the metal centres, whereas the third anion is coordinated with both O atoms to the Ce^III cations. Chains are formed by the acetate anions coordinated by three symmetry-equivalent Ce^III cations via the μ₃-(O,O′,O,O′) bridging mode, which extend in the crystallographic b-axis direction (Fig. 2). The acetate C—O bond distances are almost the same (Table 1), indicating complete delocalization of the negative charge. The chains of cerium cations and acetate anions are linked by sulfate dianions to form layers lying parallel to the ab plane (Fig. 3). These layers are stacked along the crystallographic c-axis (Figs. 4 and 5).

Table 1
Selected bond lengths (Å)

Ce1—O1	2.4608 (10)	Ce1—O5^iv	2.4836 (10)
Ce1—O1ⁱ	2.6518 (10)	Ce1—O7	2.5678 (11)
Ce1—O2ⁱⁱ	2.5996 (10)	Ce1—O8	2.5127 (11)
Ce1—O2ⁱ	2.5992 (10)	C1—O1	1.2706 (16)
Ce1—O3	2.4385 (10)	C1—O2	1.2783 (17)
Ce1—O4ⁱⁱⁱ	2.5119 (10)
Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .

Figure 1
Crystal structure of the title compound with labelling and displacement ellipsoids drawn at the 50% probability level. Symmetry codes: (i) −x, −y + 1, −z + 1; (ii) x, y − 1, z; (iii) −x + 1, −y + 1, −z + 1; (iv) x − 1, y, z.

Figure 2
Crystal structure of the title compound showing a section of a cerium–acetate chain.

Figure 3
Connection of the cerium–acetate chains by sulfate dianions into layers. The methyl groups of the acetate anions and the water molecules were omitted for clarity.

Figure 4
Crystal structure of the title compound viewed along the crystallographic a axis. The CeO₉ units are displayed as polyhedra.

Figure 5
Crystal structure of the title compound viewed along the crystallographic b axis. The CeO₉ units are displayed as polyhedra.

3. Supramolecular features

Within the cerium–sulfate–acetate layers, intralayer O—H⋯O hydrogen bonds (O7—H7A⋯O4, O8—H8B⋯O6) are observed between water H atoms (O7, O8) and sulfate O atoms (O4, O6) that are not involved in metal coordination (Fig. 6 left and Table 2). The same types of hydrogen bonds are also observed in the interconnection of the layers by interlayer O—H⋯O hydrogen bonds (O7—H7B⋯O6, O8—H8A⋯O5) between the H atoms of the water molecules (O7, O8) and the O atoms (O6, O5) of the sulfate dianion. Also, interlayer hydrogen bonding (O8—H8A⋯O7) between the two water molecules is observed (Fig. 6 right). Most of the H⋯O distances are relatively short and the O—H⋯O angles are close to linear (Table 2), indicating that these are strong interactions (1.5–2.2 Å, 130–180°; Desiraju & Steiner, 1999 ). According to Table 2, the interlayer hydrogen bonds O8—H8A⋯O5 and O8—H8A⋯O7 are rather weak. Two weak C—H⋯O interactions also occur. As a result of the interlayer hydrogen bonding, a three-dimensional supramolecular network is formed.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O7—H7A⋯O4^v	0.78 (3)	2.08 (3)	2.8400 (15)	165 (3)
O7—H7B⋯O6^vi	0.79 (3)	1.95 (3)	2.7412 (15)	175 (3)
O8—H8A⋯O5^vi	0.78 (3)	2.59 (3)	3.1389 (15)	129 (2)
O8—H8A⋯O7^vii	0.78 (3)	2.30 (3)	3.0386 (16)	158 (2)
O8—H8B⋯O6	0.87 (2)	1.99 (2)	2.7976 (15)	154 (2)
C2—H2A⋯O4	0.98	2.43	3.3245 (18)	152
C2—H2C⋯O3^viii	0.98	2.40	3.2909 (18)	151
Symmetry codes: (v) ; (vi) ; (vii) ; (viii) .

Figure 6
View along the layers with the intralayer (left) and interlayer (right) hydrogen bonds shown as dashed lines. The acetate anions were omitted for clarity.

4. Database survey

A search for crystal structures containing any lanthanide, sulfate and acetate ions in the Cambridge Structural Database (CSD version 5.45, last update September 2024; Groom et al., 2016 ) using CONQUEST (Bruno et al., 2002 ) revealed six compounds with the composition [Ln(CH₃COO)(SO₄)(H₂O)₂]_n [Ln = La, Pr, Nd, Sm, Eu, CSD refcodes: EXURAR, EXURIZ, EXUREV, EXUROF, EXUQUK (Chen et al., 2011 ) and Ln = Gd (FUSSIW; Liu et al., 2009 )], which are isostructural to the title compound. A search for cerium, sulfate and formate ions yielded two hits for a compound with the composition [Ce(HCOO)(SO₄)(H₂O)]_n (VESBOM, VESBOM01; Ju et al., 2012 ), which is not isostructural to the title compound. This compound exhibits a chiral three-dimensional framework.

Searching for cerium(III) acetates (allowing the elements Ce, C, H, O), two compounds with three reported structures are encountered: [Ce(CH₃COO)₃(H₂O)]_n (CEACET, CEACET01; Sadikov et al., 1967 ; Junk et al., 1999 ) and [Ce₂(CH₃COO)₆(H₂O)₂]_n·H₂O (XECKEV; Junk et al., 1999). In [Ce(CH₃COO)₃(H₂O)]_n, mono-periodic cerium acetate chains are present, which are interconnected by hydrogen bonding between coordinating water molecules and the acetate anions. [Ce₂(CH₃COO)₆(H₂O)₂]_n·H₂O is build up by cerium acetate layers, which are bridged into a three-dimensional framework by hydrogen bonding between the water solvate molecules and the acetate anions.

In the Inorganic Crystal Structure Database (ICSD release 2024.1; Zagorac et al., 2019 ) twelve structures have been deposited for cerium(III) sulfates (composition: Ce^III, S, O, H; number of elements: 4), namely Ce₂(SO₄)₃(H₂O)₉ (ICSD-24184; Dereigne & Pannetier, 1968 ), Ce₂(SO₄)₃(H₂O)₈ (ICSD-87633; Kepert et al., 1999; ICSD-417418; Casari & Langer, 2007 ), Ce₂(SO₄)₃(H₂O)₅ (ICSD-87635; Kepert et al., 1999), Ce₂(SO₄)₃(H₂O)₄ (ICSD-240937; Xu, 2008 ; ICSD-417417; Casari & Langer, 2007, ICSD-21073; Dereigne et al., 1972 ), Ce(OH)(SO₄) (ICSD-59922; Yang et al., 2005 ), Ce(H₃O)_0.5(SO₄)_1.5(HSO₄)_0.5 (ICSD-414161; Yu et al., 2004 ), Ce(HSO₄)₃ (ICSD-408961; Wickleder, 1998 ), (H₃O)_0.444Ce_0.888(Ce_0.08 (H₃O)_0.14)(SO₄)₂(H₂O)_4.34 (ICSD-92999; Filipenko et al., 2001 ), (H₃O)(Ce(SO₄)₂)(H₂O) (ICSD-26559; Gatehouse & Pring, 1981 ). No crystal structure of anhydrous cerium(III) sulfate has been reported. Therefore, to the best of our knowledge, [Ce(CH₃COO)(SO₄)(H₂O)₂]_n is the first reported cerium acetate sulfate.

5. Synthesis and crystallization

The synthesis was conducted applying the high-throughput method as described in the literature with our custom-made high-throughput setup (Radke et al. (2023 ). Single crystals of the title compound were serendipitously obtained by the reaction of 9.2 mg (0.053 mmol) of H₂TDC, 400 µl (0.053 mmol) of a Ce(NO₃)₃·6H₂O solution (c = 0.133 mol l⁻¹) in H₂O/EtOH (68:32), 365 µl of H₂O/EtOH (68:32) and 235 µl of acetic acid in a 2 ml Teflon vial. The reactor was sealed and placed in a Memmert UFP400 oven heating the reaction mixture to 423 K over 24 h, holding that temperature for 192 h and afterwards slowly cooling down to room temperature over 48 h. The reaction mixture was filtered off and washed with H₂O/EtOH (68:32) and dried under air. The product was obtained as a minor phase as indicated by powder X-ray diffraction (Fig. 7) but in the form of single crystals, which were suitable for single-crystal X-ray diffraction.

Figure 7
Experimental X-ray powder diffraction pattern of the batch from which the crystals were selected (red) and the calculated X-ray powder diffraction pattern of the title compound (black). The experimental pattern is very noisy because the yield was very low.

No sulfate-containing compounds were used consciously. Attempts to locate the source of the sulfate anions by testing the reactants and solvents for sulfate anions with aqueous BaCl₂ for observing the formation of insoluble BaSO₄ were unsuccessful. In an energy dispersive X-ray spectroscopy measurement of the used Ce(NO₃)₃·6H₂O, no sulfur was found. Since the quantity of sulfate anions involved in the formation of the title compound seems to be untraceable, we find it most likely that the sulfate anions originate from leaching from the Teflon reactors, which were treated with peroxymonosulfuric acid prior to its use.

Attempts to prepare the title compound phase pure were unsuccessful. Conducting the described synthesis in a 7 ml pyrex tube for 6 h in absence of H₂TDC, only an X-ray amorphous product was obtained. In addition, using equimolar amounts of Na₂SO₄ and Ce(NO₃)₃ only lead to the formation of an unknown crystalline compound. It should be noted that in the syntheses of [Ln(CH₃COO)(SO₄)(H₂O)₂]_n (Ln = La, Pr, Nd, Sm, Eu; Chen et al., 2011), no sulfate source was used and the authors concluded that the sulfate dianions probably originate from the metal salts employed in the syntheses.

The powder X-ray diffraction pattern was 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 3. The C-bound H atoms were positioned with idealized geometry allowed to rotate but not to tip and were refined isotropically with U_iso(H) = 1.5U_eq(C) using a riding model. The O-bound H atoms were located in difference maps and were refined isotropically with varying coordinates.

Table 3
Experimental details

Crystal data
Chemical formula	[Ce(C₂H₃O₂)(SO₄)(H₂O)₂]
M_r	331.26
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	100
a, b, c (Å)	6.8424 (1), 6.9984 (1), 8.7888 (2)
α, β, γ (°)	110.448 (2), 90.099 (2), 107.307 (2)
V (Å³)	373.85 (1)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	6.38
Crystal size (mm)	0.08 × 0.08 × 0.03

Data collection
Diffractometer	XtaLAB Synergy, Dualflex, HyPix
Absorption correction	Multi-scan (CrysAlisPr; Rigaku OD, 2023 $[Rigaku OD (2023). CrysAlis PRO. Rigaku Oxford Diffraction. Yarnton, England.]$ )
T_min, T_max	0.243, 0.264
No. of measured, independent and observed [I > 2σ(I)] reflections	8752, 2085, 2066
R_int	0.014
(sin θ/λ)_max (Å⁻¹)	0.708

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.010, 0.025, 1.08
No. of reflections	2085
No. of parameters	126
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.75, −0.40
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 ).

Supporting information

CCDC reference: 2411959

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989024012313/hb8117sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989024012313/hb8117Isup2.hkl

checkCIF report

Computing details top

Poly[µ₃-acetato-diaqua-µ₃-sulfato-cerium(III)] top

Crystal data top

[Ce(C₂H₃O₂)(SO₄)(H₂O)₂]	Z = 2
M_r = 331.26	F(000) = 314
Triclinic, P1	D_x = 2.943 Mg m⁻³
a = 6.8424 (1) Å	Mo Kα radiation, λ = 0.71073 Å
b = 6.9984 (1) Å	Cell parameters from 7869 reflections
c = 8.7888 (2) Å	θ = 2.5–30.2°
α = 110.448 (2)°	µ = 6.38 mm⁻¹
β = 90.099 (2)°	T = 100 K
γ = 107.307 (2)°	Plate, colorless
V = 373.85 (1) Å³	0.08 × 0.08 × 0.03 mm

Data collection top

XtaLAB Synergy, Dualflex, HyPix diffractometer	2085 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Mo) X-ray Source	2066 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.014
Detector resolution: 10.0000 pixels mm^-1	θ_max = 30.2°, θ_min = 2.5°
ω scans	h = −9→9
Absorption correction: multi-scan (CrysAlisPr; Rigaku OD, 2023)	k = −9→9
T_min = 0.243, T_max = 0.264	l = −12→12
8752 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.010	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.025	w = 1/[σ²(F_o²) + (0.0141P)² + 0.1685P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max = 0.001
2085 reflections	Δρ_max = 0.75 e Å⁻³
126 parameters	Δρ_min = −0.40 e Å⁻³
0 restraints

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.

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

	x	y	z	U_iso*/U_eq
Ce1	0.12292 (2)	0.35141 (2)	0.63283 (2)	0.00574 (3)
O1	0.17608 (15)	0.68328 (15)	0.57726 (12)	0.00892 (18)
O2	0.18457 (16)	0.98045 (16)	0.54087 (12)	0.00910 (18)
C1	0.2619 (2)	0.8836 (2)	0.61166 (17)	0.0078 (2)
C2	0.4512 (2)	1.0007 (2)	0.73196 (19)	0.0123 (3)
H2A	0.565935	0.952456	0.685357	0.015*
H2B	0.426361	0.970895	0.832451	0.015*
H2C	0.485570	1.155597	0.757098	0.015*
S1	0.70445 (5)	0.60045 (5)	0.75494 (4)	0.00687 (6)
O3	0.49759 (15)	0.45194 (16)	0.67514 (13)	0.00991 (19)
O4	0.79111 (16)	0.73412 (16)	0.65621 (12)	0.00951 (19)
O5	0.84036 (15)	0.47553 (16)	0.76662 (12)	0.00945 (18)
O6	0.68899 (16)	0.74388 (17)	0.92067 (12)	0.01042 (19)
O7	0.00409 (18)	0.17358 (18)	0.84206 (14)	0.0114 (2)
H7A	−0.055 (4)	0.050 (4)	0.807 (3)	0.034 (7)*
H7B	0.088 (5)	0.193 (5)	0.913 (4)	0.044 (8)*
O8	0.26010 (17)	0.62451 (18)	0.91554 (13)	0.0125 (2)
H8A	0.203 (4)	0.659 (4)	0.992 (3)	0.028 (6)*
H8B	0.391 (4)	0.673 (4)	0.950 (3)	0.023 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ce1	0.00598 (4)	0.00511 (4)	0.00627 (4)	0.00165 (3)	0.00012 (3)	0.00234 (3)
O1	0.0103 (5)	0.0069 (4)	0.0098 (5)	0.0026 (4)	0.0007 (4)	0.0036 (4)
O2	0.0097 (4)	0.0078 (4)	0.0107 (5)	0.0032 (4)	−0.0004 (4)	0.0041 (4)
C1	0.0073 (6)	0.0083 (6)	0.0078 (6)	0.0031 (5)	0.0025 (5)	0.0026 (5)
C2	0.0118 (6)	0.0102 (6)	0.0137 (7)	0.0021 (5)	−0.0033 (5)	0.0043 (5)
S1	0.00646 (14)	0.00716 (14)	0.00742 (14)	0.00237 (11)	0.00052 (11)	0.00302 (11)
O3	0.0067 (4)	0.0099 (4)	0.0115 (5)	0.0014 (4)	−0.0003 (4)	0.0030 (4)
O4	0.0114 (5)	0.0088 (4)	0.0098 (5)	0.0032 (4)	0.0025 (4)	0.0050 (4)
O5	0.0088 (4)	0.0111 (5)	0.0113 (5)	0.0055 (4)	0.0012 (4)	0.0054 (4)
O6	0.0107 (5)	0.0121 (5)	0.0078 (5)	0.0044 (4)	0.0012 (4)	0.0024 (4)
O7	0.0135 (5)	0.0087 (5)	0.0111 (5)	0.0014 (4)	−0.0022 (4)	0.0044 (4)
O8	0.0094 (5)	0.0153 (5)	0.0085 (5)	0.0018 (4)	0.0009 (4)	0.0012 (4)

Geometric parameters (Å, º) top

Ce1—O1	2.4608 (10)	C1—C2	1.4916 (19)
Ce1—O1ⁱ	2.6518 (10)	C2—H2A	0.9800
Ce1—O2ⁱⁱ	2.5996 (10)	C2—H2B	0.9800
Ce1—O2ⁱ	2.5992 (10)	C2—H2C	0.9800
Ce1—O3	2.4385 (10)	S1—O3	1.4790 (10)
Ce1—O4ⁱⁱⁱ	2.5119 (10)	S1—O4	1.4895 (10)
Ce1—O5^iv	2.4836 (10)	S1—O5	1.4784 (10)
Ce1—O7	2.5678 (11)	S1—O6	1.4773 (11)
Ce1—O8	2.5127 (11)	O7—H7A	0.78 (3)
Ce1—C1ⁱ	3.0316 (14)	O7—H7B	0.79 (3)
C1—O1	1.2706 (16)	O8—H8A	0.78 (3)
C1—O2	1.2783 (17)	O8—H8B	0.87 (2)

O1—Ce1—O1ⁱ	67.57 (4)	O7—Ce1—C1ⁱ	97.45 (4)
O1—Ce1—O2ⁱⁱ	145.60 (3)	O8—Ce1—O1ⁱ	130.03 (3)
O1—Ce1—O2ⁱ	116.63 (3)	O8—Ce1—O2ⁱⁱ	120.31 (3)
O1ⁱ—Ce1—C1ⁱ	24.69 (3)	O8—Ce1—O2ⁱ	144.47 (3)
O1—Ce1—C1ⁱ	92.06 (3)	O8—Ce1—C1ⁱ	143.46 (4)
O1—Ce1—O4ⁱⁱⁱ	74.19 (3)	O8—Ce1—O7	71.10 (4)
O1—Ce1—O5^iv	78.93 (3)	Ce1—O1—Ce1ⁱ	112.43 (4)
O1—Ce1—O7	143.73 (3)	C1—O1—Ce1	151.89 (9)
O1—Ce1—O8	80.50 (3)	C1—O1—Ce1ⁱ	94.63 (8)
O2ⁱⁱ—Ce1—O1ⁱ	107.17 (3)	Ce1ⁱ—O2—Ce1^v	116.36 (4)
O2ⁱ—Ce1—O1ⁱ	49.44 (3)	C1—O2—Ce1^v	134.95 (9)
O2ⁱ—Ce1—O2ⁱⁱ	63.64 (4)	C1—O2—Ce1ⁱ	96.92 (8)
O2ⁱ—Ce1—C1ⁱ	24.75 (3)	O1—C1—Ce1ⁱ	60.68 (7)
O2ⁱⁱ—Ce1—C1ⁱ	85.25 (3)	O1—C1—O2	119.01 (12)
O3—Ce1—O1	86.58 (3)	O1—C1—C2	119.73 (12)
O3—Ce1—O1ⁱ	140.56 (3)	O2—C1—Ce1ⁱ	58.33 (7)
O3—Ce1—O2ⁱⁱ	77.38 (3)	O2—C1—C2	121.26 (12)
O3—Ce1—O2ⁱ	137.85 (3)	C2—C1—Ce1ⁱ	179.59 (10)
O3—Ce1—C1ⁱ	146.27 (3)	C1—C2—H2A	109.5
O3—Ce1—O4ⁱⁱⁱ	78.81 (3)	C1—C2—H2B	109.5
O3—Ce1—O5^iv	139.02 (3)	C1—C2—H2C	109.5
O3—Ce1—O7	103.44 (4)	H2A—C2—H2B	109.5
O3—Ce1—O8	69.46 (4)	H2A—C2—H2C	109.5
O4ⁱⁱⁱ—Ce1—O1ⁱ	66.07 (3)	H2B—C2—H2C	109.5
O4ⁱⁱⁱ—Ce1—O2ⁱ	75.14 (3)	O3—S1—O4	108.88 (6)
O4ⁱⁱⁱ—Ce1—O2ⁱⁱ	72.95 (3)	O5—S1—O3	109.66 (6)
O4ⁱⁱⁱ—Ce1—C1ⁱ	68.47 (3)	O5—S1—O4	110.12 (6)
O4ⁱⁱⁱ—Ce1—O7	141.63 (3)	O6—S1—O3	109.99 (6)
O4ⁱⁱⁱ—Ce1—O8	140.26 (4)	O6—S1—O4	108.79 (6)
O5^iv—Ce1—O1ⁱ	66.55 (3)	O6—S1—O5	109.39 (6)
O5^iv—Ce1—O2ⁱⁱ	131.94 (3)	S1—O3—Ce1	153.24 (6)
O5^iv—Ce1—O2ⁱ	82.17 (3)	S1—O4—Ce1ⁱⁱⁱ	133.75 (6)
O5^iv—Ce1—C1ⁱ	73.04 (3)	S1—O5—Ce1^vi	140.99 (6)
O5^iv—Ce1—O4ⁱⁱⁱ	131.50 (3)	Ce1—O7—H7A	116.9 (19)
O5^iv—Ce1—O7	70.70 (3)	Ce1—O7—H7B	118 (2)
O5^iv—Ce1—O8	70.42 (4)	H7A—O7—H7B	106 (3)
O7—Ce1—O1ⁱ	115.10 (3)	Ce1—O8—H8A	129.9 (18)
O7—Ce1—O2ⁱⁱ	70.36 (3)	Ce1—O8—H8B	121.1 (15)
O7—Ce1—O2ⁱ	78.89 (3)	H8A—O8—H8B	107 (2)

Ce1—O1—C1—Ce1ⁱ	−164.6 (2)	O3—S1—O4—Ce1ⁱⁱⁱ	−60.31 (9)
Ce1—O1—C1—O2	−165.26 (13)	O3—S1—O5—Ce1^vi	102.11 (10)
Ce1ⁱ—O1—C1—O2	−0.66 (13)	O4—S1—O3—Ce1	−92.36 (15)
Ce1ⁱ—O1—C1—C2	179.93 (11)	O4—S1—O5—Ce1^vi	−17.68 (11)
Ce1—O1—C1—C2	15.3 (3)	O5—S1—O3—Ce1	147.09 (13)
Ce1^v—O2—C1—Ce1ⁱ	138.87 (12)	O5—S1—O4—Ce1ⁱⁱⁱ	59.96 (9)
Ce1ⁱ—O2—C1—O1	0.68 (13)	O6—S1—O3—Ce1	26.76 (16)
Ce1^v—O2—C1—O1	139.54 (11)	O6—S1—O4—Ce1ⁱⁱⁱ	179.83 (7)
Ce1ⁱ—O2—C1—C2	−179.92 (11)	O6—S1—O5—Ce1^vi	−137.19 (9)
Ce1^v—O2—C1—C2	−41.1 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7A···O4^vii	0.78 (3)	2.08 (3)	2.8400 (15)	165 (3)
O7—H7B···O6^viii	0.79 (3)	1.95 (3)	2.7412 (15)	175 (3)
O8—H8A···O5^viii	0.78 (3)	2.59 (3)	3.1389 (15)	129 (2)
O8—H8A···O7^ix	0.78 (3)	2.30 (3)	3.0386 (16)	158 (2)
O8—H8B···O6	0.87 (2)	1.99 (2)	2.7976 (15)	154 (2)
C2—H2A···O4	0.98	2.43	3.3245 (18)	152
C2—H2C···O3^v	0.98	2.40	3.2909 (18)	151

Symmetry codes: (v) x, y+1, z; (vii) x−1, y−1, z; (viii) −x+1, −y+1, −z+2; (ix) −x, −y+1, −z+2.

Funding information

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

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