Crystal structure of a new europium(III) compound based on thio­phene­acrylic acid

Jiajaroen, S.; Diaz-Torres, R.; Laksee, S.; Chainok, K.

doi:10.1107/S2056989022011884

research communications

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ISSN: 2056-9890

Volume 79| Part 1| January 2023| Pages 38-43

https://doi.org/10.1107/S2056989022011884

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Crystal structure of a new europium(III) compound based on thiopheneacrylic acid

Suwadee Jiajaroen,^a Raul Diaz-Torres,^a Sakchai Laksee ^b and Kittipong Chainok ^a ^*

^aThammasat University Research Unit in Multifunctional Crystalline Materials and Applications (TU-MCMA), Faculty of Science and Technology, Thammasat University, Pathum Thani 12121, Thailand, and ^bNuclear Technology Research and Development Center, Thailand Institute of Nuclear Technology (Public Organization), Nakhon Nayok 26120, Thailand
^*Correspondence e-mail: kc@tu.ac.th

Edited by V. Jancik, Universidad Nacional Autónoma de México, México (Received 11 July 2022; accepted 13 December 2022; online 1 January 2023)

A europium(III) coordination compound based on thiopheneacrylic acid (Htpa), triaquatris[3-(thiophen-2-yl)prop-2-enoato-κ²O,O′]europium(III)–3-(thiophen-2-yl)prop-2-enoic acid (1/3), [Eu(C₇H₅O₂S)₃(H₂O)₃]·3C₇H₆O₂S or [Eu(tpa)₃(H₂O)₃]·3(Htpa) (1), where tpa is the conjugate base of Htpa, has been synthesized and structurally characterized. Compound 1 crystallizes in the trigonal space group R3. The structure of 1 consists of a discrete molecular complex [Eu(tpa)₃(H₂O)₃] species and the Htpa molecule. In the crystal, the two components are involved in O—H⋯O [ring motif R₂²(8)] and C—H⋯π hydrogen-bonding interactions. These interactions were further investigated by Hirshfeld surface analysis, which showed high contributions of H⋯H, H⋯C/C⋯H and H⋯O/O⋯H contacts to the total Hirshfeld surfaces.

Keywords: crystal structure; europium(III); coordination compound; hydrogen bonds; lanthanide.

CCDC reference: 2226237

1. Chemical context

In crystal engineering, non-covalent interactions are used as a tool in the design and synthesis of functional crystalline materials with predictable structures and desirable physical properties (Desiraju, 2013 ; Mirzaei et al., 2014 ). Despite the significant number of structures known, this still remains a challenging task, and more especially for the lanthanide-based systems. This is due to the high and variable coordination number exhibited by the 4f metals and their small energy difference among various coordination geometries, which can give rise to the appearance of multiple-connected framework structures with a variety of topologies (Sairenji et al., 2016 ). In recent years, the design and synthesis of porous materials combining crystal engineering and coordination chemistry have attracted great attention because of their appealing structures and their potential applications in catalysis, ion-exchange, molecular adsorption and chemical sensing (Cawthray et al., 2015 ; Pan et al., 2021 ; Theppitak et al., 2021 ; Jiajaroen et al., 2022 ). However, the successful construction of such materials comes only from understanding and controlling the relationship between the geometry frameworks and the involved intermolecular interactions. In this work, we report the synthesis and supramolecular structure of a new europium(III) compound based on thiopheneacrylate (tpa), [Eu(tpa)₃(H₂O)₃]·3(Htpa)] (1). The intermolecular interactions involved in the formation of the supramolecular structure of the title compound 1 are discussed in detail. In addition, a Hirshfeld surface analysis was performed to investigate the intermolecular interactions.

2. Structural commentary

Single crystal X-ray structural analysis reveals that the title compound 1 crystallizes in the trigonal system with space group R3. The Flack parameter (Parsons et al., 2013 ) of −0.025 (2) demonstrates the enantiomeric purity of the tested single crystal. The asymmetric unit consists of one crystallographically independent Eu^III ion, one tpa ligand, one Htpa molecule and one coordinated water molecule. As shown in Fig. 1, the structure of 1 consists of a discrete molecular complex [Eu(tpa)₃(H₂O)₃] and the Htpa molecule. In the discrete complex species, the deprotonated carboxylic group of tpa ligand adopts a μ₁-κ²O,O′-chelating coordination mode to the Eu^III ion. The central Eu^III ion is nine-coordinated with six oxygen atoms from three different tpa ligands and three oxygen atoms from coordinated water molecules. With the assistance of the SHAPE program (Llunell et al., 2013 ), the coordination geometry around the Eu^III center in 1 could be described as a distorted spherical tricapped trigonal prism [TCTPR-9; shape, D_3h symmetry; distortion (τ), 2.761], wherein a trigonal–prismatic geometry is formed by the vertical pairs: O1⋯O3′, O1′⋯O3′′, and O1′′··O3, while the O2, O2′, and O3′′ atoms act as caps as shown in Fig. 2. The Eu—O bond lengths range from 2.400 (2) to 2.511 (2) Å, and the bond angles range from 51.62 (5) to 157.80 (6)°, which are in the normal ranges of those observed in the reported europium(III) compounds (Behrsing et al., 2016 ; Sun et al., 2016 ; Alexander et al., 2019 ). In addition, the [Eu(tpa)₃(H₂O)₃] complex interacts with the Htpa molecule through the formation of an R₂²(8) ring motif in terms of graph-set notation (Etter et al., 1990 ).

Figure 1
Molecular structure of the title compound 1. Displacement ellipsoids are drawn at the 30% probability level. All hydrogen atoms were omitted for clarity. Symmetry codes: (i) −x + y, −x + 1, z; (ii) −y + 1, x − y + 1, z.

Figure 2
View of the distorted spherical tricapped trigonal prism (TCTPR-9) of the central Eu^III ion in the title compound 1. Symmetry codes: (i) −x + y, −x + 1, z; (ii) −y + 1, x − y + 1, z.

3. Supramolecular features

As depicted in Fig. 3, the discrete complex [Eu(tpa)₃(H₂O)₃] forms a supramolecular chain extending parallel to the c axis with its symmetry-related molecules through classical O—H⋯O hydrogen-bonding interactions (Table 1) between the coordinated water molecules and the carboxylate groups of tpa ligands, which can be described by the R₂²(8) graph-set motif. The chains are further linked via C—H⋯π interactions involving the thiophene moieties of adjacent tpa ligands [C7—H7⋯Cg distance = 3.869 (3); symmetry code = − $[{2\over 3}]$ + y − x, −4/3 − x, − $[{1\over 3}]$ + z] . As a result (illustrated in Fig. 4), a three-dimensional hydrogen-bonded network is created with large channels running along the crystallographic c-axis direction. The Htpa molecules are located in the cavities of the network, and are hydrogen bonded to both the tpa and water molecules through intermolecular O—H⋯O interactions with the R₂²(8) ring motif. It should be noted that no evidence for π–π stacking interactions of neighboring aromatic thiophene rings is observed.

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the S1/C4–C7 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3A⋯O5	0.82 (1)	1.94 (2)	2.729 (3)	162 (3)
O3—H3B⋯O1ⁱ	0.82 (1)	1.89 (2)	2.693 (2)	165 (3)
O4—H4⋯O2	0.84 (1)	1.78 (2)	2.614 (3)	177 (4)
C7—H7⋯Cg1ⁱⁱ	0.93	3.10	3.869 (3)	141
Symmetry codes: (i) ; (ii) $[-x+y-{\script{2\over 3}}, -x-{\script{4\over 3}}, z-{\script{1\over 3}}]$ .

Figure 3
The one-dimensional hydrogen-bonded chain in the title compound 1 running parallel to the c axis.

Figure 4
Crystal packing diagram of the title compound 1, showing the three-dimensional hydrogen-bonded networks of the complex [Eu(tpa)₃(H₂O)₃] species with the Htpa molecules in space-filling representation.

4. Hirshfeld surface analysis

The Hirshfeld surfaces and two-dimensional fingerprint plots was generated using CrystalExplorer 21.5 (Spackman et al., 2021 ) in order to quantify and visualize the intermolecular interactions in the crystal structure of the title compound 1. As can be seen in Fig. 5, the Hirshfeld surfaces mapped over d_norm shows the most intense red spots around the carboxylate groups and water molecules resulting from the O—H⋯O hydrogen-bonding interactions between the complex [Eu(tpa)₃(H₂O)₃] species and the Htpa molecules. Furthermore, analysis of the two-dimensional fingerprint plots, Fig. 6, reveals that H⋯H (32.1%) contacts, which represent van der Waals interactions, are the major contributors toward the Hirshfeld surface. Meanwhile, H⋯C/C⋯H (24.9%, i.e. C—H⋯π) and H⋯O/O⋯H (22.0%, i.e. O—H⋯O) contacts also make a significant contribution. The H⋯S/S⋯H (14.8%), C⋯O/O⋯C (3.1%) and C⋯S/S⋯C (1.6%) contacts make a small contribution to the entire Hirshfeld surface. Therefore, it can be concluded that O—H⋯O and C—H⋯π hydrogen bonds as well as H⋯H and H⋯S van der Waals contacts contribute significantly to the overall stability of the packing arrangement of the crystal structure of the title compound 1.

Figure 5
Hirshfeld surface mapped over d_norm of the title compound 1, highlighting the O—H⋯O interactions.

Figure 6
Two-dimensional fingerprint plots of the title compound 1, showing (a) all interactions, and those delineated into (b) H⋯H, (c) H⋯C/C⋯H, (d) H⋯O/O⋯H, (e) H⋯S/S⋯H, (f) O⋯C/C⋯O, (g) S⋯C/C⋯S, (h) C⋯C, (i) S⋯S, and (j) O⋯O contacts [d_e and d_i represent the distances from a point on the Hirshfeld surface to the nearest atoms outside (external) and inside (internal) the surface, respectively].

5. Infrared spectroscopy

The infrared (IR) spectrum of the title compound 1 was recorded on a Perkin Elmer model Spectrum 100 spectrometer using the attenuated total reflectance (ATR) mode in the range of 650–4000 cm⁻¹. As can be seen in Fig. 7, the broad absorption bands in the region 3020–3400 cm⁻¹ are assigned to the stretching vibrations of the hydroxyl (O—H) groups. The band at 2978 cm⁻¹ corresponds to the C—H stretching vibrations. The strong band at 1670 cm⁻¹ indicates the existence of the carboxylic groups while the strong bands appearing in the region 1305–1610 cm⁻¹ can be ascribed to the asymmetric and symmetric stretching vibrations of the carboxylate groups. The bands at 705 and 750 cm⁻¹ can be assigned to C—S stretching vibrations.

Figure 7
IR spectrum of the title compound 1.

6. Thermal stability

The thermal stability of the title compound 1 was studied by thermogravimetric analysis (TGA). The sample was studied on TGA55 TA Instrument from room temperature to 1073 K under a N₂ atmosphere (heating rate of 10^oC min⁻¹). As shown in Fig. 8, the TGA curve of 1 displays two steps of weight loss. The first weight loss of 52.1% from 325–500 K can be ascribed to the removal of water and Htpa molecules (calculated 50.7%). Then the structure begins to collapse at around 630 K.

Figure 8
TGA curve of the title compound 1.

7. Database survey

A ConQuest search for the metal complexes bearing the thiopheneacrylate ligand in the Cambridge Structural Database (CSD version 5.42, September 2021 update; Bruno et al., 2002 ; Groom et al., 2016 ) resulted in ten hits, namely, the complexes with the Mo^V ion (GAKPUF, Vrdoljak et al., 2010 ; DAMRUG, Alberding et al., 2011 ), Sb^V ion (GIFPET, GIFPIX, Sarwar et al., 2018 ), Sn^IV ion (NUJGII, Danish et al., 1996 ; RIWBII, Parvez et al., 1997 ; TEDTIF, TEDTOL, Danish et al., 1995 ), Ga^III ion (YUWCAV, Uhl et al., 2010 ), and Pd^II ion (ZIJNAK, Vasseur et al., 2018 ). In these complexes, the tpa ligand displays four distinct coordination modes with the carboxylate anions being monodentate μ₁-κ¹O (GIFPET, GIFPIX), bidentate chelating μ₁-κ²O,O′ (RIWBII, ZIJNAK, similar to that found in the title compound 1) and μ₂-κO:κO (DAMRUG, GAKPUF, NUJGII, YUWCAV), or bidentate bridging μ₂-κO:κO′ (TEDTIF, TEDTOL). In addition, 69 hits for lanthanide complexes with the [Ln(COO)₃(H₂O)₃] coordination sphere similar to that in the title compound 1 were found. Twelve of them viz. CSD refcodes HIVCEW, HIVCIA, HIVCOG, HIVCUM, HIVDAT (Marques et al., 2013 ), LOMNAE (Tsaryuk et al., 2014 ), VUSGIZ, VUSGOF, VUSGUL (Zeng & Pan, 1992 ), XILLUA (Kameshwar et al., 2007a ), XILNUC (Kameshwar et al., 2007b ), and YENHOO (Rzaczynska & Belskii, 1994 ) crystallized in the trigonal system with space group R3, and the central Ln³⁺ cation exhibiting a nine-coordinated tricapped trigonal–prismatic (TTP) geometry.

8. Synthesis and crystallization

All reagents were purchased as analytical grade and used without further purification. The Htpa ligand (30.8 mg, 0.2 mmol) was dissolved in an isopropanol solution (2 ml) and was then added dropwise to an aqueous solution (5 ml) of Eu(NO₃)₃·6H₂O (44.61 mg, 0.1 mmol). The mixture was stirred for 1 h at room temperature and then filtered to remove any undissolved solid. The solution was slowly evaporated at room temperature. Colorless block-shaped crystals of 1 were obtained in 20% yield (8.9 mg) based on Eu³⁺ source.

9. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. All non-hydrogen atoms were refined anisotropically. Hydrogen atoms attached to carbon atoms were refined in the riding-model approximation with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C). Hydrogen atoms bounded to oxygen atoms of coordinated water (O3) and carboxylic acid (O4) were located from difference-Fourier maps but were refined with distance restraints of O—H = 0.84 ± 0.01 Å and with U_iso(H) = 1.5U_eq(O). The thiophene ring of the Htpa molecule was found to be disordered over two positions and the site occupancies of the disordered fragments were refined to 0.778 (4) and 0.222 (4). The restraints of the SADI, RIGU and FLAT commands were applied to accommodate the disordered thiophene ring.

Table 2
Experimental details

Crystal data
Chemical formula	[Eu(C₇H₅O₂S)₃(H₂O)₃]·3C₇H₆O₂S
M_r	1128.05
Crystal system, space group	Trigonal, R3
Temperature (K)	296
a, c (Å)	26.5369 (6), 5.9386 (1)
V (Å³)	3621.72 (17)
Z	3
Radiation type	Mo Kα
μ (mm⁻¹)	1.62
Crystal size (mm)	0.28 × 0.22 × 0.12

Data collection
Diffractometer	Bruker D8 QUEST CMOS
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.690, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	54319, 4921, 4921
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.715

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.015, 0.032, 1.07
No. of reflections	4921
No. of parameters	252
No. of restraints	88
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.25
Absolute structure	Flack x determined using 2459 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013)
Absolute structure parameter	−0.024 (2)
Computer programs: APEX4 and SAINT (Bruker, 2019 ), SHELXT (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ), and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 2226237

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989022011884/jq2020sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989022011884/jq2020Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989022011884/jq2020Isup3.cdx

checkCIF report

Computing details top

Data collection: APEX4 (Bruker, 2019); cell refinement: SAINT (Bruker, 2019); data reduction: SAINT (Bruker, 2019); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: Olex2 (Dolomanov et al., 2009); software used to prepare material for publication: Olex2 (Dolomanov et al., 2009).

Triaquatris[3-(thiophen-2-yl)prop-2-enoato-κ²O,O'}europium(III)–3-(thiophen-2-yl)prop-2-enoic acid (1/3) top

Crystal data top

[Eu(C₇H₅O₂S)₃(H₂O)₃]·3C₇H₆O₂S	D_x = 1.552 Mg m⁻³
M_r = 1128.05	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3	Cell parameters from 9889 reflections
a = 26.5369 (6) Å	θ = 2.7–30.4°
c = 5.9386 (1) Å	µ = 1.62 mm⁻¹
V = 3621.72 (17) Å³	T = 296 K
Z = 3	Block, colourless
F(000) = 1710	0.28 × 0.22 × 0.12 mm

Data collection top

Bruker D8 QUEST CMOS diffractometer	4921 independent reflections
Radiation source: sealed x-ray tube, Mo	4921 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.036
Detector resolution: 7.39 pixels mm^-1	θ_max = 30.6°, θ_min = 2.7°
φ and ω scans	h = −37→37
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	k = −37→37
T_min = 0.690, T_max = 0.746	l = −8→8
54319 measured reflections

Refinement top

Refinement on F²	H atoms treated by a mixture of independent and constrained refinement
Least-squares matrix: full	w = 1/[σ²(F_o²) + (0.0145P)² + 0.9645P] where P = (F_o² + 2F_c²)/3
R[F² > 2σ(F²)] = 0.015	(Δ/σ)_max = 0.001
wR(F²) = 0.032	Δρ_max = 0.21 e Å⁻³
S = 1.07	Δρ_min = −0.25 e Å⁻³
4921 reflections	Extinction correction: SHELXL-2018/3 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
252 parameters	Extinction coefficient: 0.00059 (8)
88 restraints	Absolute structure: Flack x determined using 2459 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
Hydrogen site location: mixed	Absolute structure parameter: −0.024 (2)

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	Occ. (<1)
Eu1	0.333333	0.666667	0.48411 (2)	0.02639 (5)
S1	0.36988 (4)	0.42204 (3)	0.93748 (13)	0.05608 (18)
S2	0.07634 (8)	0.25613 (8)	0.0719 (3)	0.0619 (4)	0.778 (4)
S2A	0.0659 (6)	0.3006 (7)	−0.330 (2)	0.075 (2)	0.222 (4)
O1	0.36847 (8)	0.62424 (7)	0.7756 (3)	0.0377 (3)
O2	0.30981 (8)	0.56296 (7)	0.5258 (3)	0.0445 (4)
O3	0.26557 (8)	0.60435 (7)	0.2042 (3)	0.0391 (3)
H3A	0.2574 (13)	0.5703 (7)	0.197 (5)	0.031 (7)*
H3B	0.2612 (13)	0.6169 (12)	0.083 (3)	0.051 (8)*
O4	0.24635 (12)	0.45449 (9)	0.3997 (5)	0.0819 (8)
H4	0.2673 (14)	0.4894 (8)	0.436 (6)	0.077 (11)*
O5	0.22298 (10)	0.48956 (8)	0.1065 (4)	0.0591 (5)
C1	0.34166 (10)	0.57296 (10)	0.6978 (4)	0.0327 (4)
C2	0.34785 (11)	0.52549 (10)	0.7943 (4)	0.0405 (5)
H2	0.330251	0.489999	0.719057	0.049*
C3	0.37665 (11)	0.52981 (11)	0.9802 (4)	0.0403 (5)
H3	0.391555	0.564646	1.059115	0.048*
C4	0.38750 (10)	0.48571 (10)	1.0746 (4)	0.0395 (5)
C5	0.41575 (12)	0.48962 (11)	1.2707 (4)	0.0477 (6)
H5	0.428911	0.520927	1.369331	0.057*
C6	0.42297 (13)	0.44089 (13)	1.3086 (5)	0.0548 (7)
H6	0.441164	0.436683	1.435195	0.066*
C7	0.40079 (14)	0.40149 (13)	1.1425 (5)	0.0541 (7)
H7	0.402122	0.367138	1.139609	0.065*
C8	0.21768 (11)	0.44876 (11)	0.2140 (5)	0.0476 (6)
C9	0.17650 (12)	0.38762 (11)	0.1581 (5)	0.0513 (6)
H9	0.174401	0.358161	0.249464	0.062*
C10	0.14254 (11)	0.37414 (12)	−0.0201 (5)	0.0496 (6)
H10	0.148027	0.405028	−0.110983	0.060*	0.778 (4)
H10A	0.146668	0.403635	−0.116266	0.060*	0.222 (4)
C11	0.0978 (3)	0.3170 (2)	−0.0906 (16)	0.050 (2)	0.778 (4)
C11A	0.0989 (6)	0.3144 (9)	−0.070 (5)	0.051 (7)	0.222 (4)
C12	0.0688 (7)	0.3046 (7)	−0.282 (2)	0.080 (3)	0.778 (4)
H12	0.072978	0.332514	−0.386972	0.097*	0.778 (4)
C12A	0.0791 (12)	0.2676 (11)	0.049 (5)	0.085 (11)	0.222 (4)
H12A	0.092117	0.267347	0.194105	0.102*	0.222 (4)
C13	0.0297 (3)	0.2428 (3)	−0.3118 (14)	0.080 (2)	0.778 (4)
H13	0.007440	0.226422	−0.440497	0.095*	0.778 (4)
C13A	0.0345 (12)	0.2148 (11)	−0.063 (4)	0.063 (6)	0.222 (4)
H13A	0.016090	0.177634	−0.001909	0.076*	0.222 (4)
C14	0.0292 (4)	0.2116 (4)	−0.1301 (15)	0.073 (2)	0.778 (4)
H14	0.006362	0.171352	−0.117203	0.087*	0.778 (4)
C14A	0.0245 (10)	0.2287 (9)	−0.269 (5)	0.075 (8)	0.222 (4)
H14A	−0.002560	0.201670	−0.368413	0.090*	0.222 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Eu1	0.02863 (5)	0.02863 (5)	0.02191 (6)	0.01432 (3)	0.000	0.000
S1	0.0759 (5)	0.0441 (3)	0.0540 (4)	0.0343 (3)	−0.0218 (3)	−0.0081 (3)
S2	0.0656 (9)	0.0470 (7)	0.0633 (8)	0.0208 (6)	−0.0086 (6)	−0.0082 (5)
S2A	0.067 (4)	0.078 (4)	0.069 (5)	0.029 (3)	−0.032 (3)	−0.025 (3)
O1	0.0486 (10)	0.0343 (8)	0.0331 (8)	0.0229 (7)	−0.0127 (7)	−0.0072 (6)
O2	0.0589 (10)	0.0349 (8)	0.0390 (8)	0.0228 (8)	−0.0222 (7)	−0.0056 (6)
O3	0.0454 (9)	0.0355 (9)	0.0316 (8)	0.0168 (8)	−0.0122 (7)	0.0017 (7)
O4	0.0987 (18)	0.0395 (11)	0.0989 (19)	0.0282 (12)	−0.0581 (15)	−0.0183 (11)
O5	0.0659 (13)	0.0417 (10)	0.0584 (12)	0.0184 (9)	−0.0173 (10)	−0.0091 (9)
C1	0.0378 (11)	0.0333 (10)	0.0296 (10)	0.0197 (9)	−0.0047 (8)	−0.0011 (8)
C2	0.0485 (13)	0.0355 (11)	0.0410 (11)	0.0236 (10)	−0.0105 (10)	−0.0018 (9)
C3	0.0484 (13)	0.0383 (11)	0.0400 (12)	0.0260 (10)	−0.0104 (10)	−0.0042 (9)
C4	0.0435 (12)	0.0381 (11)	0.0391 (11)	0.0220 (10)	−0.0072 (9)	0.0003 (9)
C5	0.0566 (15)	0.0428 (13)	0.0455 (13)	0.0264 (12)	−0.0154 (11)	−0.0030 (10)
C6	0.0565 (16)	0.0552 (15)	0.0552 (15)	0.0298 (13)	−0.0139 (12)	0.0118 (12)
C7	0.0628 (17)	0.0456 (14)	0.0621 (17)	0.0333 (13)	−0.0067 (14)	0.0098 (12)
C8	0.0432 (13)	0.0411 (12)	0.0607 (15)	0.0229 (11)	−0.0098 (11)	−0.0137 (11)
C9	0.0528 (15)	0.0400 (13)	0.0625 (17)	0.0243 (12)	−0.0142 (12)	−0.0133 (11)
C10	0.0483 (14)	0.0447 (13)	0.0571 (15)	0.0242 (11)	−0.0070 (11)	−0.0108 (11)
C11	0.049 (4)	0.046 (2)	0.054 (3)	0.022 (2)	−0.009 (3)	−0.009 (2)
C11A	0.025 (9)	0.058 (6)	0.069 (15)	0.019 (6)	−0.010 (8)	−0.028 (8)
C12	0.073 (5)	0.065 (4)	0.069 (5)	0.008 (4)	−0.025 (4)	−0.012 (4)
C12A	0.090 (17)	0.054 (8)	0.083 (15)	0.014 (8)	−0.008 (10)	−0.023 (8)
C13	0.055 (3)	0.074 (5)	0.070 (3)	0.003 (3)	−0.021 (2)	−0.018 (3)
C13A	0.063 (11)	0.051 (7)	0.074 (15)	0.027 (7)	−0.002 (9)	−0.016 (7)
C14	0.058 (3)	0.055 (3)	0.073 (5)	0.003 (2)	−0.002 (3)	−0.018 (3)
C14A	0.061 (12)	0.026 (7)	0.096 (15)	−0.011 (6)	−0.021 (10)	−0.002 (7)

Geometric parameters (Å, º) top

Eu1—O1ⁱ	2.4868 (16)	C3—C4	1.451 (3)
Eu1—O1ⁱⁱ	2.4868 (16)	C4—C5	1.361 (3)
Eu1—O1	2.4868 (16)	C5—H5	0.9300
Eu1—O2ⁱⁱ	2.5113 (16)	C5—C6	1.417 (4)
Eu1—O2	2.5112 (16)	C6—H6	0.9300
Eu1—O2ⁱ	2.5113 (16)	C6—C7	1.340 (4)
Eu1—O3ⁱ	2.3996 (15)	C7—H7	0.9300
Eu1—O3ⁱⁱ	2.3997 (15)	C8—C9	1.471 (3)
Eu1—O3	2.3997 (15)	C9—H9	0.9300
S1—C4	1.716 (2)	C9—C10	1.318 (4)
S1—C7	1.703 (3)	C10—H10	0.9300
S2—C11	1.715 (9)	C10—H10A	0.9300
S2—C14	1.710 (7)	C10—C11	1.443 (6)
S2A—C11A	1.72 (3)	C10—C11A	1.452 (17)
S2A—C14A	1.70 (2)	C11—C12	1.322 (14)
O1—C1	1.266 (3)	C11A—C12A	1.29 (3)
O2—O4ⁱⁱⁱ	11.564 (3)	C12—H12	0.9300
O2—C1	1.266 (3)	C12—C13	1.446 (15)
O3—H3A	0.818 (13)	C12A—H12A	0.9300
O3—H3B	0.826 (13)	C12A—C13A	1.47 (3)
O4—H4	0.836 (14)	C13—H13	0.9300
O4—C8	1.305 (3)	C13—C14	1.358 (9)
O5—C8	1.203 (3)	C13A—H13A	0.9300
C1—C2	1.466 (3)	C13A—C14A	1.34 (2)
C2—H2	0.9300	C14—H14	0.9300
C2—C3	1.315 (3)	C14A—H14A	0.9300
C3—H3	0.9300

O1ⁱ—Eu1—O1ⁱⁱ	76.88 (6)	C2—C3—H3	116.7
O1ⁱ—Eu1—O1	76.88 (6)	C2—C3—C4	126.5 (2)
O1ⁱⁱ—Eu1—O1	76.88 (6)	C4—C3—H3	116.7
O1—Eu1—O2ⁱⁱ	79.32 (6)	C3—C4—S1	123.01 (17)
O1—Eu1—O2ⁱ	126.87 (6)	C5—C4—S1	110.47 (18)
O1ⁱⁱ—Eu1—O2	126.87 (6)	C5—C4—C3	126.4 (2)
O1ⁱ—Eu1—O2ⁱ	51.62 (5)	C4—C5—H5	123.6
O1ⁱⁱ—Eu1—O2ⁱⁱ	51.62 (5)	C4—C5—C6	112.8 (2)
O1ⁱⁱ—Eu1—O2ⁱ	79.33 (6)	C6—C5—H5	123.6
O1—Eu1—O2	51.62 (5)	C5—C6—H6	123.6
O1ⁱ—Eu1—O2	79.33 (6)	C7—C6—C5	112.8 (2)
O1ⁱ—Eu1—O2ⁱⁱ	126.87 (6)	C7—C6—H6	123.6
O2ⁱⁱ—Eu1—O2	119.037 (14)	S1—C7—H7	124.1
O2ⁱ—Eu1—O2	119.040 (14)	C6—C7—S1	111.7 (2)
O2ⁱ—Eu1—O2ⁱⁱ	119.038 (14)	C6—C7—H7	124.1
O3ⁱ—Eu1—O1	157.80 (6)	O4—C8—C9	112.8 (2)
O3ⁱ—Eu1—O1ⁱⁱ	91.68 (6)	O5—C8—O4	123.0 (2)
O3ⁱⁱ—Eu1—O1ⁱⁱ	119.45 (5)	O5—C8—C9	124.1 (3)
O3ⁱⁱ—Eu1—O1ⁱ	157.80 (6)	C8—C9—H9	119.6
O3—Eu1—O1ⁱⁱ	157.80 (6)	C10—C9—C8	120.7 (3)
O3ⁱⁱ—Eu1—O1	91.68 (6)	C10—C9—H9	119.7
O3—Eu1—O1	119.45 (5)	C9—C10—H10	116.2
O3—Eu1—O1ⁱ	91.68 (6)	C9—C10—H10A	119.2
O3ⁱ—Eu1—O1ⁱ	119.45 (5)	C9—C10—C11	127.5 (5)
O3—Eu1—O2ⁱⁱ	141.12 (6)	C9—C10—C11A	121.6 (13)
O3—Eu1—O2	67.86 (5)	C11—C10—H10	116.2
O3ⁱⁱ—Eu1—O2ⁱⁱ	67.86 (5)	C11A—C10—H10A	119.2
O3ⁱⁱ—Eu1—O2ⁱ	141.12 (6)	C10—C11—S2	122.5 (7)
O3ⁱ—Eu1—O2	141.12 (6)	C12—C11—S2	111.9 (8)
O3ⁱ—Eu1—O2ⁱ	67.86 (5)	C12—C11—C10	125.6 (10)
O3ⁱⁱ—Eu1—O2	78.67 (7)	C10—C11A—S2A	117 (2)
O3ⁱ—Eu1—O2ⁱⁱ	78.67 (7)	C12A—C11A—S2A	111.6 (16)
O3—Eu1—O2ⁱ	78.67 (7)	C12A—C11A—C10	131 (3)
O3ⁱ—Eu1—O3ⁱⁱ	77.30 (7)	C11—C12—H12	123.7
O3—Eu1—O3ⁱⁱ	77.30 (7)	C11—C12—C13	112.6 (12)
O3ⁱ—Eu1—O3	77.30 (7)	C13—C12—H12	123.7
C7—S1—C4	92.19 (13)	C11A—C12A—H12A	122.7
C14—S2—C11	92.3 (5)	C11A—C12A—C13A	115 (3)
C14A—S2A—C11A	91.3 (14)	C13A—C12A—H12A	122.7
C1—O1—Eu1	95.50 (12)	C12—C13—H13	123.9
Eu1—O2—O4ⁱⁱⁱ	150.31 (5)	C14—C13—C12	112.2 (8)
C1—O2—Eu1	94.35 (13)	C14—C13—H13	123.9
C1—O2—O4ⁱⁱⁱ	109.24 (13)	O3ⁱⁱ—C13A—H13A	143.0
Eu1—O3—H3A	119 (2)	C12A—C13A—H13A	125.4
Eu1—O3—H3B	122 (2)	C14A—C13A—C12A	109 (2)
H3A—O3—H3B	113 (3)	C14A—C13A—H13A	125.4
C8—O4—H4	112 (3)	S2—C14—H14	124.6
O1—C1—C2	122.4 (2)	C13—C14—S2	110.8 (6)
O2—C1—O1	118.50 (19)	C13—C14—H14	124.6
O2—C1—C2	119.0 (2)	S2A—C14A—H14A	123.3
C1—C2—H2	117.9	C13A—C14A—S2A	113 (2)
C3—C2—C1	124.3 (2)	C13A—C14A—H14A	123.3
C3—C2—H2	117.9

Eu1—O1—C1—O2	−1.5 (2)	C7—S1—C4—C3	175.6 (2)
Eu1—O1—C1—C2	176.2 (2)	C7—S1—C4—C5	−0.3 (2)
Eu1—O2—C1—O1	1.5 (2)	C8—C9—C10—C11	−176.2 (4)
Eu1—O2—C1—C2	−176.33 (19)	C8—C9—C10—C11A	−175.8 (6)
S1—C4—C5—C6	0.0 (3)	C9—C10—C11—S2	7.3 (6)
S2—C11—C12—C13	−4.1 (14)	C9—C10—C11—C12	−172.7 (10)
S2A—C11A—C12A—C13A	0.4 (6)	C9—C10—C11A—S2A	−169.2 (7)
O1—C1—C2—C3	6.8 (4)	C9—C10—C11A—C12A	11.0 (8)
O2—C1—C2—C3	−175.5 (3)	C10—C11—C12—C13	175.8 (6)
O3ⁱⁱ—C13A—C14A—S2A	−5.5 (5)	C10—C11A—C12A—C13A	−179.8 (3)
O4ⁱⁱⁱ—O2—C1—O1	163.18 (17)	C11—S2—C14—C13	−1.1 (6)
O4ⁱⁱⁱ—O2—C1—C2	−14.6 (2)	C11—C12—C13—C14	3.4 (14)
O4—C8—C9—C10	177.6 (3)	C11A—S2A—C14A—C13A	−0.2 (5)
O5—C8—C9—C10	0.6 (5)	C11A—C12A—C13A—O3ⁱⁱ	18.1 (16)
C1—C2—C3—C4	−175.5 (2)	C11A—C12A—C13A—C14A	−0.5 (8)
C2—C3—C4—S1	6.9 (4)	C12—C13—C14—S2	−1.0 (9)
C2—C3—C4—C5	−177.8 (3)	C12A—C13A—C14A—S2A	0.5 (7)
C3—C4—C5—C6	−175.7 (3)	C14—S2—C11—C10	−176.9 (4)
C4—S1—C7—C6	0.6 (3)	C14—S2—C11—C12	3.1 (9)
C4—C5—C6—C7	0.4 (4)	C14A—S2A—C11A—C10	−179.9 (2)
C5—C6—C7—S1	−0.7 (4)	C14A—S2A—C11A—C12A	−0.1 (4)

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

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the S1/C4–C7 ring.

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O5	0.82 (1)	1.94 (2)	2.729 (3)	162 (3)
O3—H3B···O1^iv	0.82 (1)	1.89 (2)	2.693 (2)	165 (3)
O4—H4···O2	0.84 (1)	1.78 (2)	2.614 (3)	177 (4)
C7—H7···Cg1^v	0.93	3.10	3.869 (3)	141

Symmetry codes: (iv) −x+y, −x+1, z−1; (v) −x+y−2/3, −x−4/3, z−1/3.

Acknowledgements

This study was partially supported by the Thammasat University Research Unit in Multifunctional Crystalline Materials and Applications (TU-McMa).

Funding information

Funding for this research was provided by: Thailand Institute of Nuclear Technology (Public Organization), Thailand, through its program of TINT to University (grant to Kittipong Chainok); The Research Professional Development Project under the Science Achievement Scholarship of Thailand (SAST) (scholarship to Suwadee Jiajaroen).

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Volume 79| Part 1| January 2023| Pages 38-43

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research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Crystal structure of a new europium(III) compound based on thio­phene­acrylic acid

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Hirshfeld surface analysis

5. Infrared spectroscopy

6. Thermal stability

7. Database survey

8. Synthesis and crystallization

9. Refinement

Supporting information

Acknowledgements

Funding information

References

research communications

Crystal structure of a new europium(III) compound based on thiopheneacrylic acid

3. Supramolecular features