Crystal structure and photoluminescent properties of a new EuIII–phthalate–acetate coordination polymer

Jittipiboonwat, P.; Chuasaard, T.; Rujiwatra, A.

doi:10.1107/S2056989022004339

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ISSN: 2056-9890

Volume 78| Part 5| May 2022| Pages 536-539

https://doi.org/10.1107/S2056989022004339

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Crystal structure and photoluminescent properties of a new Eu^III–phthalate–acetate coordination polymer

Prakottakarn Jittipiboonwat,^a Thammanoon Chuasaard ^a and Apinpus Rujiwatra ^a,^b ^*

^aDepartment of Chemistry, Faculty of Science, Chiang Mai University, Chiang Mai, 50200, Thailand, and ^bMaterials Science Research Center, Faculty of Science, Chiang Mai University, Chiang Mai 50200, Thailand
^*Correspondence e-mail: apinpus.rujiwatra@cmu.ac.th

Edited by A. Briceno, Venezuelan Institute of Scientific Research, Venezuela (Received 8 April 2022; accepted 22 April 2022; online 28 April 2022)

A new coordination polymer, poly[(acetato)aqua(μ₃-phthalato)europium(III)], [Eu(C₈H₄O₄)(CH₃O₂)(H₂O)]_n or [Eu^III(phth)(OAc)(H₂O)] (phth²⁻ = phthalate and OAc⁻ = acetate) was synthesized and characterized, revealing it to be a supramolecular assembly of one-dimensional [Eu^III(phth)(OAc)(H₂O)] chains. Each chain is built up of edge-sharing distorted tricapped trigonal–prismatic TPRS-{Eu^IIIO₉} building motifs and assembled in a regular fashion through hydrogen-bonding and aromatic π–π interactions. The fully deprotonated phth²⁻ ligand was shown to be an effective sensitizer, promoting the characteristic ⁵D₀→⁷F_J (J = 1–4) emissions of Eu^III even in the presence of the non-sensitizing OAc⁻ group.

Keywords: coordination polymer; lanthanide; phthalate; acetate; crystal structure; photoluminescence.

CCDC reference: 2168116

1. Chemical context

Interest in crystal engineering of lanthanide coordination polymers has been driven by the unique coordination chemistry and electronic properties of trivalent lanthanides (Ln^III), which bring about a wide variety of potential applications ranging from, for instance, luminescence sensing (Hasegawa & Kitagawa, 2022 ), magnetism (Hu et al., 2021 ), catalysis (Sinchow et al., 2021 ), gas storage and separation (Li & Chen, 2014 ), to drug delivery (Wei et al., 2020 ) and biomolecular imaging (Miller et al., 2016 ). However, the high coordination numbers, flexible coordination geometries and lack of directionality of Ln—O bonds complicate prediction of the designed polymeric frameworks, which are also greatly influenced by differences in synthetic parameters, i.e. reaction temperature and time, solvent, pH of reaction, etc (Bünzli, 2014 ; Qiu & Zhu, 2009 ). The study of structure–property relationships, which is an essence of property design, is consequently limited.

Unlike transition-metal-based coordination polymers in which the preferred coordination geometries of the transition-metal ions play an important role in directing the framework architecture (Kitagawa et al., 2004 ), those based on Ln^III are principally governed by the organic ligands. Polycarboxylic acids are notably the most commonly utilized, facilitating diversity through their modes of coordination such as those found for phthalic acid (H₂phth) (Fig. 1). These coordination modes can also be diversified through the presence of the other ligands such as those found in, for instance, [Ln^I^II(bdc)_0.5(phth)(H₂O)₂] (Ln^III = Eu^III, Tb^III, Ho^III, Er^III and Tm^III, H₂bdc = terephthalic acid; Chuasaard et al., 2020 ), [Ln^III(abdc)_0.5(phth)(H₂O)₂]·2H₂O (Ln^III = Eu^III, Gd^III and Tb^III, H₂abdc = azobenzene-4,4′-dicarboxylic acid; Chuasaard et al., 2022 ) and [Ln^III(ox)(phth)(H₂O)₂]·0.5H₂O (Ln^III = Sm^III and Tb^III, H₂ox = oxalic acid; Wang et al., 2010 ).

Figure 1
Coordination modes of phth²⁻ and Hphth⁻ found in lanthanide coordination compounds deposited to the CSD (Groom et al., 2016

) with frequency of appearance in parentheses.

With respect to photoluminescence, phth²⁻ is acknowledged as a good sensitizer and can effectively promote f–f emissions in, for example, [Eu^III₂(phth)₃(H₂O)] (Wan et al., 2002 ). The apparent photoluminescence can, nonetheless, be modulated by the other ligands such as ad²⁻ in [Ln^III(ad)_0.5(phth)(H₂O)₂] (Chuasaard et al., 2018 ) and bdc²⁻ in [Ln^III(bdc)_0.5(phth)(H₂O)₂] (Chuasaard et al., 2020).

2. Structural commentary

The asymmetric unit of the title compound, [Eu^III(phth)(OAc)(H₂O)], is composed of one crystallographically unique Eu^III ion, a whole molecule of phth²⁻, and the coordinating OAc⁻ and water molecules (Fig. 2). The Eu^III ion is ninefold coordinated to O atoms from three phth²⁻, two OAc⁻ and one water molecule, which define a distorted tricapped trigonal–prismatic TPRS-{Eu^IIIO₉} building motif. The Eu—O bond distances are in the range 2.352 (2)-2.605 (2) Å (Table 1), which are consistent with those reported for other Eu^III frameworks of phth²⁻ and OAc⁻, viz. [Eu^III(abdc)_0.5(phth)(H₂O)₂]·2H₂O (Chuasaard et al., 2022), [Eu^III(phth)(STP)] (NaSTP = sodium 2-(2,2′:6′,2′′-terpyridin-4′-yl)benzenesulfonate; Hu et al., 2019 ) and [C₂mim]₂[Eu₂(OAc)₈] (C₂mim = 1-ethyl-3-methylimidazolium; Bousrez et al., 2021 ). The TPRS-{Eu^IIIO₉} motifs are fused through the μ₂-O atoms of phth²⁻, forming an infinite one-dimensional zigzag chain of edge-sharing TPRS-{Eu^IIIO₉} motifs extending along the b-axis direction. Not only phth²⁻, which helps facilitating the formation of the one-dimensional chain through the overall μ₃-η¹:η²:η²:η¹ mode of coordination (mode i in Fig. 1), but also the smaller OAc⁻ link adjacent Eu^III centers in a bridging μ₂-η¹:η¹ coordination mode.

Table 1
Selected bond lengths (Å)

Eu1—O1ⁱ	2.570 (2)	Eu1—O4ⁱⁱ	2.605 (2)
Eu1—O1	2.397 (2)	Eu1—O5	2.352 (2)
Eu1—O2ⁱ	2.474 (2)	Eu1—O6ⁱ	2.434 (3)
Eu1—O3	2.381 (2)	Eu1—O7	2.446 (2)
Eu1—O3ⁱⁱ	2.484 (2)
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Figure 2
Extended asymmetric unit of the title compound drawn using 50% probability for ellipsoids (hydrogen atoms are omitted for clarity). Symmetry codes: (i) $[{3\over 2}]$ − x, $[{1\over 2}]$ + y, $[{3\over 2}]$ − z; (ii) $[{3\over 2}]$ − x, − $[{1\over 2}]$ + y, $[{3\over 2}]$ − z.

3. Supramolecular features

The three-dimensional supramolecular assembly of [Eu^III(phth)(OAc)(H₂O)] chains are facilitated by hydrogen bonding and aromatic π–π interactions (Fig. 3). The hydrogen-bonding interactions can be divided into the interchain O7—H7A⋯O4 and the intrachain O7—H7B⋯O6 and C3—H3⋯O2 interactions (Table 2). The π–π interaction between neighboring chains is considered to be of the displaced-stacking type (Banerjee et al., 2019 ; Yao et al., 2018 ), with an interplanar angle of 0°, an offset distance of ca 1.0 Å and a centroid-to-centroid distance of ca 3.6 Å.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O7—H7A⋯O4ⁱⁱⁱ	0.85	2.17	2.9384	149
O7—H7B⋯O6^iv	0.85	2.28	3.0438	150
C3—H3⋯O2	0.93	2.46	2.7741	100
Symmetry codes: (iii) $[x, -y, z-{\script{1\over 2}}]$ ; (iv) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 3
Depiction of (a) intrachain and (b) interchain hydrogen-bonding interactions, and (c) π–π interactions.

4. Photoluminescent properties

The emission spectrum of ground crystals of the title compound was recorded at room temperature. Upon the excitation at 370 nm, the characteristic red emission originating from the ⁵D₀→⁷F_J (J = 1–4) transitions of Eu^III were displayed (Fig. 4). This indicates the efficiency of phth²⁻ as a good sensitizer, even in the presence of the non-sensitizing OAc⁻. A split of the very intense ⁵D₀→⁷F₂ emission suggests that the Eu^III ion is not located at a site with a center of symmetry (Binnemans, 2015 ), which is consistent with its distorted tricapped trigonal–prismatic coordination geometry. The split of the ⁵D₀→⁷F₄ emission, on the other hand, should be due to the ligand-field effect (Gupta et al., 2015 ; Okayasu & Yuasa, 2021 ; Puntus et al., 2010 ).

Figure 4
Room-temperature photoluminescent emission spectrum of the title compound.

5. Database survey

A search of the CSD database (CSD version 5.43, update of November 2021; Groom et al., 2016 ) using the ConQuest software (version 2021.3.0; Bruno et al., 2002 ), found 115 structures of lanthanide compounds including phth²⁻. In six of these structures, phth²⁻ adopts the same μ₃-η¹:η²:η²:η¹ mode of coordination as in the title compound. This mode of coordination apparently promotes the formation of a one-dimensional coordination framework, as, for example, in [Pr₃(phen)₂(phth)₄(NO₃)]·H₂O (phen = 1,10-phenanthroline) (refcode: LAXWOX; Thirumurugan & Natarajan, 2005 ), [Nd(Nphgly)(phth)(H₂O)]·2H₂O (Nphgly = N-phthaloylglycine) (refcode: TOHJEH; Yang et al., 2014 ), and [Gd₂Ni(2,5-pdc)₂(phth)₂(H₂O)₄]·8H₂O (2,5-H₂pdc = 2,5-pyridinedicarboxylic acid) (refcode: XOZYER; Mahata et al., 2009 ).

Regarding OAc⁻, there are 566 structures containing this deposited in the CSD, none of which also contains phth²⁻. There are, however, structures containing both OAc⁻ and isophthalate (iso-phth²⁻), e.g. [Sm₂(iso-phth)₂(OAc)₂(H₂O)₄]·H₂O (refcode: VOJNAK; Jin et al., 2008 ), and [Dy₄(iso-phth)₄(OAc)₄(H₂O)₈]·2H₂O (refcode: DIBZEU; Hu et al., 2007 ).

6. Synthesis and crystallization

All chemicals used in this work were obtained commercially and used without purification: Eu₂O₃ (Strategic Elements, 99.99%), phthalic acid (H₂phth; C₈H₆O₄, BDH laboratory, 99%), NaOH (RCI Labscan, 99.0%), glacial acetic acid (AcOH; CH₃COOH, QRëC, 99.8%), tetrahydrofuran (THF; C₄H₈O, RCI Labscan, 99.8%), ethanol (EtOH; C₂H₅OH, RCI Labscan, 99.7%). Eu(OAc)₃·4H₂O, was prepared by dissolving Eu₂O₃ (2.5000 g, 7.1038 mmol) in 50.0 mL of deionized water with a few drops of glacial acetic acid (HOAc). After the pH of the suspension was adjusted to 3 using HOAc, the mixture was gently heated and a colorless homogeneous solution was attained. The white powder of Eu(OAc)₃·4H₂O was then recovered through slow evaporation of the solvent.

To synthesize the title compound, Eu(OAc)₃·4H₂O (0.16 g, 0.40 mmol) was dissolved in 2.0 mL of deionized water to prepare solution A. Solution B was separately prepared by dissolving Na₂phth (84 mg, 0.40 mmol) and NaOAc (33 mg, 0.4 mmol) in a mixed solvent prepared from 1.0 mL of deionized water and 5.0 mL of tetrahydrofuran (THF). Solutions A and B were then mixed in a 15 mL glass vial. The volume of the reaction was adjusted to 10.0 mL using deionized water and the pH of the solution was adjusted to 4 using HOAc. The reaction was left under stirring at room temperature for 2 h, after which the solvent was slowly evaporated, leading to the crystallization of colorless block-shaped crystals of [Eu(phth)(OAc)(H₂O)] (78% yield based on Eu^III). The crystals were characterized using FT–IR spectroscopy (PerkinElmer/Frontier FT–IR instrument; ATR mode; cm⁻¹): 3541(br), 3419(br), 2978(w), 1548(w), 1402(m), 1373(m), 804(s), 754(s), 707(s), 650(s), 543(m), 503(m). The room-temperature photoluminescent spectrum was collected using a ASEQ LR-1T broad-range spectrophotometer equipped with an Ultrafire G60 UV LED Flashlight Torch excitation source (5 W, 370 nm)

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. All H atoms were positioned geometrically and refined isotropically using a riding model. The C—H bond lengths in the aromatic phth²⁻ linker and in OAc⁻ were restrained to 0.93 Å [U_iso(H) = 1.2U_eq(C)] and 0.96 Å [U_iso(H) = 1.5U_eq(C)], respectively. The O—H bond lengths in the coordinated water molecule were restrained to 0.85 Å with U_iso(H) = 1.5U_eq(O).

Table 3
Experimental details

Crystal data
Chemical formula	[Eu(C₈H₄O₄)(CH₃O₂)(H₂O)]
M_r	393.13
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	26.5184 (15), 7.2632 (2), 15.3622 (8)
β (°)	130.906 (9)
V (Å³)	2236.3 (3)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	5.63
Crystal size (mm)	0.2 × 0.1 × 0.1

Data collection
Diffractometer	Rigaku SuperNova, single source at offset/far, HyPix3000
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2019 $[Rigaku OD (2019). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )
T_min, T_max	0.218, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	9923, 2393, 2138
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.648

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.024, 0.052, 1.05
No. of reflections	2393
No. of parameters	167
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.64, −0.79
Computer programs: CrysAlis PRO (Rigaku OD, 2019 $[Rigaku OD (2019). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ), SHELXT2018/2 (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 2168116

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989022004339/zn2019sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989022004339/zn2019Isup2.hkl

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Rigaku OD, 2019); cell refinement: CrysAlis PRO (Rigaku OD, 2019); data reduction: CrysAlis PRO (Rigaku OD, 2019); program(s) used to solve structure: SHELXT2018/2 (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).

Poly[(acetato)aqua(µ₃-phthalato)europium(III)] top

Crystal data top

[Eu(C₈H₄O₄)(CH₃O₂)(H₂O)]	F(000) = 1504
M_r = 393.13	D_x = 2.335 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 26.5184 (15) Å	Cell parameters from 7078 reflections
b = 7.2632 (2) Å	θ = 2.0–27.4°
c = 15.3622 (8) Å	µ = 5.63 mm⁻¹
β = 130.906 (9)°	T = 293 K
V = 2236.3 (3) Å³	Block, clear light colourless
Z = 8	0.2 × 0.1 × 0.1 mm

Data collection top

Rigaku SuperNova, Single source at offset/far, HyPix3000 diffractometer	2393 independent reflections
Radiation source: micro-focus sealed X-ray tube, SuperNova (Mo) X-ray Source	2138 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.032
Detector resolution: 10.0000 pixels mm^-1	θ_max = 27.4°, θ_min = 2.0°
ω scans	h = −33→33
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2019)	k = −9→9
T_min = 0.218, T_max = 1.000	l = −19→18
9923 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.024	H-atom parameters constrained
wR(F²) = 0.052	w = 1/[σ²(F_o²) + (0.0235P)² + 1.2859P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
2393 reflections	Δρ_max = 0.64 e Å⁻³
167 parameters	Δρ_min = −0.79 e Å⁻³
1 restraint

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
Eu1	0.75770 (2)	0.36927 (2)	0.71208 (2)	0.01709 (7)
O1	0.69745 (10)	0.1993 (3)	0.7522 (2)	0.0219 (5)
O4	0.68510 (12)	0.6542 (3)	0.8366 (2)	0.0264 (6)
O3	0.68174 (10)	0.5756 (3)	0.69468 (19)	0.0185 (5)
O6	0.69030 (12)	−0.0954 (3)	0.5869 (2)	0.0290 (6)
O2	0.62648 (11)	−0.0281 (3)	0.6844 (2)	0.0273 (6)
O7	0.72235 (14)	0.5336 (4)	0.5410 (2)	0.0422 (7)
H7A	0.697069	0.483288	0.474914	0.063*
H7B	0.708422	0.643920	0.528604	0.063*
O5	0.67155 (11)	0.2044 (3)	0.5460 (2)	0.0308 (6)
C7	0.59568 (15)	0.4602 (4)	0.6922 (3)	0.0185 (7)
C2	0.58415 (15)	0.2718 (4)	0.6633 (3)	0.0185 (7)
C8	0.65937 (15)	0.5624 (4)	0.7479 (3)	0.0181 (7)
C9	0.66224 (16)	0.0380 (5)	0.5165 (3)	0.0257 (8)
C1	0.63844 (17)	0.1403 (4)	0.7002 (3)	0.0196 (8)
C10	0.61510 (19)	−0.0007 (5)	0.3902 (3)	0.0412 (10)
H10A	0.616586	−0.129448	0.377789	0.062*
H10B	0.627783	0.070141	0.354452	0.062*
H10C	0.570626	0.032152	0.357152	0.062*
C6	0.54332 (17)	0.5698 (5)	0.6621 (3)	0.0282 (8)
H6	0.551117	0.692945	0.683999	0.034*
C3	0.52024 (16)	0.2027 (5)	0.6028 (3)	0.0257 (8)
H3	0.512351	0.077936	0.585067	0.031*
C4	0.46810 (17)	0.3156 (5)	0.5685 (3)	0.0301 (9)
H4	0.425093	0.268326	0.524046	0.036*
C5	0.47994 (17)	0.4983 (5)	0.6002 (3)	0.0318 (9)
H5	0.445276	0.573408	0.579933	0.038*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Eu1	0.01881 (11)	0.01068 (11)	0.02213 (12)	0.00003 (6)	0.01356 (9)	−0.00015 (6)
O1	0.0190 (12)	0.0157 (11)	0.0322 (14)	0.0006 (10)	0.0173 (11)	0.0032 (11)
O4	0.0294 (14)	0.0245 (14)	0.0270 (14)	−0.0045 (10)	0.0191 (12)	−0.0049 (11)
O3	0.0205 (12)	0.0112 (11)	0.0261 (13)	−0.0006 (9)	0.0162 (11)	0.0012 (10)
O6	0.0311 (14)	0.0253 (14)	0.0243 (14)	0.0014 (11)	0.0154 (12)	0.0038 (11)
O2	0.0255 (13)	0.0127 (12)	0.0439 (15)	−0.0017 (10)	0.0228 (12)	−0.0027 (11)
O7	0.0635 (19)	0.0265 (15)	0.0297 (15)	−0.0021 (14)	0.0275 (15)	0.0026 (12)
O5	0.0299 (14)	0.0218 (13)	0.0312 (14)	−0.0048 (11)	0.0158 (12)	−0.0053 (11)
C7	0.0202 (17)	0.0164 (17)	0.0204 (17)	0.0005 (13)	0.0139 (15)	0.0027 (14)
C2	0.0191 (17)	0.0157 (17)	0.0214 (17)	0.0006 (13)	0.0136 (15)	0.0012 (14)
C8	0.0174 (16)	0.0097 (16)	0.0256 (18)	0.0063 (13)	0.0135 (15)	0.0054 (14)
C9	0.0231 (18)	0.028 (2)	0.0270 (19)	−0.0079 (16)	0.0168 (17)	−0.0048 (17)
C1	0.0243 (19)	0.0166 (18)	0.0210 (19)	0.0015 (13)	0.0161 (16)	0.0041 (13)
C10	0.049 (3)	0.037 (2)	0.023 (2)	−0.0107 (19)	0.017 (2)	−0.0014 (18)
C6	0.029 (2)	0.0200 (18)	0.041 (2)	0.0016 (16)	0.0257 (18)	0.0003 (17)
C3	0.0239 (18)	0.0208 (18)	0.0279 (19)	−0.0018 (15)	0.0149 (16)	0.0013 (16)
C4	0.0168 (18)	0.033 (2)	0.035 (2)	−0.0030 (16)	0.0143 (17)	0.0025 (18)
C5	0.0228 (19)	0.027 (2)	0.044 (2)	0.0075 (15)	0.0213 (18)	0.0055 (18)

Geometric parameters (Å, º) top

Eu1—O1ⁱ	2.570 (2)	Eu1—O4ⁱⁱ	2.605 (2)
Eu1—O1	2.397 (2)	Eu1—O5	2.352 (2)
Eu1—O2ⁱ	2.474 (2)	Eu1—O6ⁱ	2.434 (3)
Eu1—O3	2.381 (2)	Eu1—O7	2.446 (2)
Eu1—O3ⁱⁱ	2.484 (2)

O1—Eu1—Eu1ⁱ	100.62 (6)	Eu1—O3—Eu1ⁱ	107.20 (8)
O1ⁱ—Eu1—Eu1ⁱ	36.44 (5)	C8—O3—Eu1ⁱ	95.16 (19)
O1—Eu1—O1ⁱ	135.94 (6)	C8—O3—Eu1	126.05 (19)
O1—Eu1—O4ⁱⁱ	112.11 (8)	C9—O6—Eu1ⁱⁱ	133.7 (2)
O1ⁱ—Eu1—O4ⁱⁱ	110.21 (7)	C1—O2—Eu1ⁱⁱ	96.9 (2)
O1—Eu1—O3ⁱⁱ	72.40 (7)	Eu1—O7—H7A	121.4
O1—Eu1—O6ⁱ	69.36 (8)	Eu1—O7—H7B	120.3
O1—Eu1—O2ⁱ	138.23 (8)	H7A—O7—H7B	104.5
O1—Eu1—O7	132.57 (9)	C9—O5—Eu1	134.6 (2)
O4ⁱⁱ—Eu1—Eu1ⁱ	146.65 (5)	C2—C7—C8	126.3 (3)
O3—Eu1—Eu1ⁱ	37.29 (5)	C6—C7—C2	119.2 (3)
O3ⁱⁱ—Eu1—Eu1ⁱ	141.16 (5)	C6—C7—C8	114.4 (3)
O3—Eu1—O1ⁱ	71.11 (7)	C7—C2—C1	123.0 (3)
O3—Eu1—O1	72.28 (8)	C3—C2—C7	118.7 (3)
O3ⁱⁱ—Eu1—O1ⁱ	130.07 (7)	C3—C2—C1	118.3 (3)
O3ⁱⁱ—Eu1—O4ⁱⁱ	51.12 (7)	O4—C8—Eu1ⁱ	63.93 (18)
O3—Eu1—O4ⁱⁱ	162.55 (8)	O4—C8—O3	120.3 (3)
O3—Eu1—O3ⁱⁱ	141.75 (4)	O4—C8—C7	119.7 (3)
O3—Eu1—O6ⁱ	79.11 (8)	O3—C8—Eu1ⁱ	58.54 (16)
O3—Eu1—O2ⁱ	119.05 (7)	O3—C8—C7	119.3 (3)
O3—Eu1—O7	82.61 (9)	C7—C8—Eu1ⁱ	156.5 (2)
O6ⁱ—Eu1—Eu1ⁱ	66.91 (5)	O6—C9—C10	119.2 (3)
O6ⁱ—Eu1—O1ⁱ	80.35 (8)	O5—C9—O6	124.1 (3)
O6ⁱ—Eu1—O4ⁱⁱ	118.34 (8)	O5—C9—C10	116.7 (3)
O6ⁱ—Eu1—O3ⁱⁱ	75.15 (8)	O1—C1—Eu1ⁱⁱ	62.34 (16)
O6ⁱ—Eu1—O2ⁱ	73.70 (8)	O1—C1—C2	120.2 (3)
O6ⁱ—Eu1—O7	144.26 (8)	O2—C1—Eu1ⁱⁱ	57.86 (16)
O2ⁱ—Eu1—Eu1ⁱ	81.77 (5)	O2—C1—O1	120.1 (3)
O2ⁱ—Eu1—O1ⁱ	51.37 (7)	O2—C1—C2	119.6 (3)
O2ⁱ—Eu1—O4ⁱⁱ	69.76 (7)	C2—C1—Eu1ⁱⁱ	174.1 (2)
O2ⁱ—Eu1—O3ⁱⁱ	79.99 (7)	C9—C10—H10A	109.5
O7—Eu1—Eu1ⁱ	79.97 (7)	C9—C10—H10B	109.5
O7—Eu1—O1ⁱ	64.69 (8)	C9—C10—H10C	109.5
O7—Eu1—O4ⁱⁱ	82.51 (9)	H10A—C10—H10B	109.5
O7—Eu1—O3ⁱⁱ	133.38 (9)	H10A—C10—H10C	109.5
O7—Eu1—O2ⁱ	89.12 (9)	H10B—C10—H10C	109.5
O5—Eu1—Eu1ⁱ	125.35 (6)	C7—C6—H6	119.5
O5—Eu1—O1	71.29 (8)	C5—C6—C7	120.9 (3)
O5—Eu1—O1ⁱ	133.75 (8)	C5—C6—H6	119.5
O5—Eu1—O4ⁱⁱ	73.60 (8)	C2—C3—H3	119.3
O5—Eu1—O3	92.82 (8)	C4—C3—C2	121.3 (3)
O5—Eu1—O3ⁱⁱ	89.44 (7)	C4—C3—H3	119.3
O5—Eu1—O6ⁱ	140.44 (9)	C3—C4—H4	120.1
O5—Eu1—O2ⁱ	139.98 (8)	C5—C4—C3	119.8 (3)
O5—Eu1—O7	70.49 (9)	C5—C4—H4	120.1
Eu1—O1—Eu1ⁱⁱ	104.00 (8)	C6—C5—H5	120.0
C1—O1—Eu1ⁱⁱ	91.53 (18)	C4—C5—C6	119.9 (3)
C1—O1—Eu1	139.6 (2)	C4—C5—H5	120.0
C8—O4—Eu1ⁱ	90.7 (2)

Eu1—O1—C1—Eu1ⁱⁱ	113.9 (3)	C7—C2—C3—C4	1.7 (5)
Eu1ⁱⁱ—O1—C1—O2	−3.0 (3)	C7—C6—C5—C4	0.7 (6)
Eu1—O1—C1—O2	110.9 (3)	C2—C7—C8—Eu1ⁱ	140.5 (5)
Eu1ⁱⁱ—O1—C1—C2	174.0 (3)	C2—C7—C8—O4	−127.1 (3)
Eu1—O1—C1—C2	−72.1 (4)	C2—C7—C8—O3	62.7 (4)
Eu1ⁱ—O4—C8—O3	16.5 (3)	C2—C7—C6—C5	−2.9 (5)
Eu1ⁱ—O4—C8—C7	−153.6 (2)	C2—C3—C4—C5	−3.9 (5)
Eu1—O3—C8—Eu1ⁱ	115.7 (2)	C8—C7—C2—C1	8.9 (5)
Eu1—O3—C8—O4	98.2 (3)	C8—C7—C2—C3	−174.4 (3)
Eu1ⁱ—O3—C8—O4	−17.4 (3)	C8—C7—C6—C5	173.7 (3)
Eu1—O3—C8—C7	−91.6 (3)	C1—C2—C3—C4	178.4 (3)
Eu1ⁱ—O3—C8—C7	152.8 (2)	C6—C7—C2—C1	−174.9 (3)
Eu1ⁱⁱ—O6—C9—O5	21.5 (5)	C6—C7—C2—C3	1.7 (5)
Eu1ⁱⁱ—O6—C9—C10	−158.7 (3)	C6—C7—C8—Eu1ⁱ	−35.8 (7)
Eu1ⁱⁱ—O2—C1—O1	3.1 (3)	C6—C7—C8—O4	56.7 (4)
Eu1ⁱⁱ—O2—C1—C2	−173.9 (3)	C6—C7—C8—O3	−113.6 (3)
Eu1—O5—C9—O6	23.5 (5)	C3—C2—C1—O1	177.3 (3)
Eu1—O5—C9—C10	−156.3 (3)	C3—C2—C1—O2	−5.7 (5)
C7—C2—C1—O1	−6.1 (5)	C3—C4—C5—C6	2.7 (5)
C7—C2—C1—O2	170.9 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7A···O4ⁱⁱⁱ	0.85	2.17	2.9384	149
O7—H7B···O6^iv	0.85	2.28	3.0438	150
C3—H3···O2	0.93	2.46	2.7741	100

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

Funding information

This research was funded by Chiang Mai University and the Program Management Unit – Brain Power (PMU B), The Office of National Higher Education Science Research and Innovation Policy Council (NXPO) in a Global Partnership Project.

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