Organically pillared layer framework of [Eu(NH2–BDC)(ox)(H3O)]

Thammakan, S.; Panyarat, K.; Rujiwatra, A.

doi:10.1107/S2056989019014713

research communications

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 75| Part 12| December 2019| Pages 1833-1838

https://doi.org/10.1107/S2056989019014713

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Organically pillared layer framework of [Eu(NH₂–BDC)(ox)(H₃O)]

Supaphorn Thammakan,^a Kitt Panyarat ^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 J. Jasinski, Keene State College, USA (Received 17 October 2019; accepted 30 October 2019; online 8 November 2019)

The non-porous three-dimensional structure of poly[(μ₅-2-aminobenzene-1,4-dicarboxylato)(μ₆-oxalato)(oxomium)europium(III)], [Eu(C₈H₅NO₄)(C₂O₄)(H₃O)]_n or [Eu^III(NH₂–BDC)(ox)(H₃O)]_n (NH₂–BDC²⁻ = 2-aminoterephthalate and ox²⁻ = oxalate) is constructed from two-dimensional layers of Eu^III–carboxylate–oxalate, which are connected by NH₂–BDC²⁻ pillars. The basic structural unit of the layer is an edge-sharing dimer of TPRS-{Eu^IIIO₉}, which is assembled through the ox²⁻ moiety. The intralayer void is partially occupied by TPR-{Eu^IIIO₆} motifs. Weak C—H⋯O and strong, classical intramolecular N—H⋯O and intermolecular O—H⋯O hydrogen-bonding interactions, as well as weak π–π stacking interactions, affix the organic pillars within the framework. The two-dimensional layer can be simplified to a uninodal 4-connected sql/Shubnikov tetragonal plane net with point symbol {4⁴.6²}.

Keywords: coordination polymer; lanthanide; 2-aminoterephthalic acid; oxalic acid; crystal structure.

CCDC references: 1962371; 1962371

1. Chemical context

Lanthanide coordination polymers (LnCPs) have emerged as authentic multifunctional materials finding potential in various applications, e.g. magnetism, optics, luminescence and in heterogeneous catalysis (Roy et al., 2014 ). In the crystal engineering of LnCPs, the judicious choice of organic ligands is critical. Among the widely employed dicarboxylates, 1,4-benzenedicarboxylic acid (H₂BDC) tends to provide three-dimensional frameworks with permanent porosity. To enhance interactions with guest species, additional functional groups can be introduced onto the phenyl ring of BDC²⁻, e.g. 2-amino-1,4-benzenediarboxylic acid (NH₂-H₂BDC) in NH₂-MIL-53(Al) enhanced the carbon dioxide capture capacity (Stavitski et al., 2011 ; Flaig et al., 2017 ; Wang et al., 2012 ). The smallest dicarboxylic acid, i.e. oxalic acid (H₂ox), on the other hand, may not facilitate the porous framework (Zhang et al., 2016 ; Xiahou et al., 2013 ) and its presence as a secondary ligand in the fabrication may lead to diversity in the framework structures.

Herein, NH₂-H₂BDC and H₂ox were employed as mixed linkers in the synthesis of a new three-dimensional framework of europium, i.e. [Eu(NH₂-BDC)(ox)(H₃O)] (I). The crystal structure of I, which exhibits site disorder at both the Eu^III ion and the amino group, is reported. Weak intermolecular interactions and the framework topology are also described.

2. Structural commentary

[Eu(NH₂–BDC)(ox)(H₃O)] crystallizes in the monoclinic space group P2₁/c. Its asymmetric unit comprises one Eu^III ion, which is disordered over two crystallographic sites with an occupying ratio of 0.86 (Eu1A): 0.14 (Eu1B) and whole molecules of NH₂–BDC²⁻, ox²⁻ and H₃O⁺ (Fig. 1). Eu1A is ninefold coordinated to nine O atoms from one chelating NH₂-–BDC²⁻, two monodentate NH₂–BDC²⁻, two chelating ox²⁻ and one monodentate ox²⁻ groups, all of which delineate into a distorted tricapped trigonal–prismatic geometry, i.e. TPRS-{Eu^IIIO₉}. Eu1B, on the other hand, adopts a sixfold coordination of trigonal anti-prismatic geometry, i.e. TPR-{Eu^IIIO₆}, which is completed by six O atoms from two monodentate NH₂–BDC²⁻, three monodentate ox²⁻ and one H₃O⁺ moieties. Noticeably, the three monodentate ox²⁻ moieties form one trigonal face whereas the two monodentate NH₂–BDC²⁻ and the ligated H₃O⁺ moieties outline the other. The Eu^III—O bond distances ranging between 2.375 (2) and 2.562 (2) Å, are consistent with the values observed for other Eu^III coordination frameworks, e.g. [(CH₃)₂NH₂]₂[Eu₆(μ₃-OH)₈(BDC–NH₂)₆(H₂O)₆] (Yi et al., 2016 ) and [Eu₂(ATPA)₃(DEF)₂]_n where ATPA²⁻ = 2-aminoterepthalate and DEF = diethylformamide (Kariem et al., 2016 ). In addition to the disorder at the Eu^III positions, there is an additional disorder at the amino group of NH₂–BDC²⁻, which distributes over three crystallographic sites with site occupancies of 0.26 (N1), 0.44 (N2) and 0.31 (N3), respectively.

Figure 1
Views of (a) an extended asymmetric unit of I drawn using 60% probability ellipsoids and the coordination environments about (b) Eu1A and (c) Eu1B. [Symmetry codes: (i) −x, 1 − y, −z; (ii) 1 − x, $[{1\over 2}]$ + y, $[{1\over 2}]$ − z; (iii) −x, − $[{1\over 2}]$ + y, $[{1\over 2}]$ − z; (iv) x, $[{3\over 2}]$ − y, − $[{1\over 2}]$ + z; (v) x, $[{1\over 2}]$ − y, $[{1\over 2}]$ + z; (vi) 1 − x, − $[{1\over 2}]$ + y, $[{1\over 2}]$ − z; (vii) 1 − x, 1 − y, 1 − z; (viii) 1 − x, $[{3\over 2}]$ − y, $[{1\over 2}]$ + z.]

As a result of the disorder of the Eu^III ion, the modes of coordinations for both NH₂–BDC²⁻ and ox²⁻ are diverse. If all of the possible sites of Eu^III are concurrently included, the μ₅-η¹:η¹:η²:η² mode can be assigned to NH₂-BDC²⁻ as it connects three Eu1A and two Eu1B moieties together (Fig. 2). In a similar fashion, three Eu1A and three Eu1B moieties may be simultaneously linked by ox²⁻ using the μ₆-η²:η²:η²:η² mode for coordination. It is worth noting that the μ₅-η¹:η¹:η²:η² mode of NH₂-BDC²⁻ and the μ₆-η²:η²:η²:η² mode of ox²⁻ are unprecedented. If only the dominating Eu1A is regarded, the adopted coordination modes would be μ₃-η¹:η¹:η¹:η¹ and μ₃-η¹:η¹:η¹:η² for NH₂–BDC²⁻ and ox²⁻, respectively. Likewise, there are only sixteen structures containing ox²⁻ with a μ₃-η¹:η¹:η¹:η² mode and only two LnCPs comprising NH₂–BDC²⁻ with a μ₃-η¹:η¹:η¹:η¹ mode, i.e. [Yb₂(OH)(atpt)_2.5(phen)₂]_n·1.75nH₂O where atpt²⁻ = 2-aminoterephthalate and phen = 1,10-phenanthroline (Liu et al., 2004 ), and {[Ho₂(μ₃-ATA)₂(μ₄-ATA)(H₂O)₄]·2DMF·0.5H₂O}_n where ATA²⁻ = 2-aminoterephthalate (Almáši et al., 2014 ).

Figure 2
Depictions of coordination modes adopted by NH₂—BDC²⁻ and ox²⁻; (a) with (b) without Eu1B.

3. Supramolecular features

The structure of I features a three-dimensional framework, which can be regarded as being built up of two-dimensional layers of Eu^III-carboxylate-oxalate connected by the NH₂–BDC²⁻ organic pillars (Fig. 3). The basic building motif of the layer is the edge-sharing dimer of TPRS-{Eu^IIIO₉} (Fig. 4), which is fused together through two O8 atoms from two ox²⁻ groups and two O1—C1—O2 bridges of two NH₂-BDC²⁻. Each {Eu₂^IIIO₁₆} dimer of Eu1A is tied to the other four equivalent dimers through four ox²⁻ linkers in the bc plane. The as-described arrangement of these {Eu₂^IIIO₁₆} dimers creates voids characterized as the twelve-membered rings, in which the partially occupied TPR-{Eu^IIIO₆} motifs of Eu1B are situated. Each of the TPR-{Eu^IIIO₆} motifs are affixed within the layer through four O atoms from four surrounding ox²⁻ groups and an O4 atom from NH₂–BDC²⁻. These layers are further connected by the NH₂–BDC²⁻ organic pillars along the a-axis direction providing the non-porous three-dimensional framework. The roles of ox²⁻ and NH₂–BCD²⁻ in the framework of I are, therefore, to create the layer framework and to tether the layers, respectively.

Figure 3
The three-dimensional framework structure of I.

Figure 4
Polyhedral and space-filling representations of the Eu^III–oxalate–carboxylate layers (a) with TPR-{Eu^IIIO₆} motifs and (b) without TPR-{Eu^IIIO₆} motif.

The NH₂–BDC²⁻ pillar is apparently organized through intramolecular hydrogen-bonding interactions from both strong N—H⋯O and weak C—H⋯O interactions (Table 1), and through the face-to-face antiparallel displaced π–π interactions (Banerjee et al., 2019 ) established between the phenyl rings of two adjacent NH₂–BDC²⁻ pillars (Fig. 5). In addition to the intramolecular hydrogen-bonding interactions, two H atoms from the H₃O⁺ molecule are also involved in providing additional strong O—H⋯O intermolecular hydrogen-bonding interactions.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O9W—H9WA⋯O2ⁱ	1.11 (5)	1.81 (5)	2.904 (4)	171 (5)
O9W—H9WB⋯O5ⁱⁱ	1.10 (5)	1.87 (5)	2.943 (4)	163 (4)
C6—H6⋯O3	0.93	2.47	2.781 (6)	100
N1—H1B⋯O2	0.86	2.03	2.736 (16)	139
Symmetry codes: (i) -x+1, -y+1, -z; (ii) $[x+1, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Figure 5
Views of (a) the hydrogen-bonding interactions and (b) the π–π interactions.

4. Topology

The topology of the two-dimensional layer of I was analysed using TOPOS software (Blatov, 2004 ). If only the dominating motif, i.e. the edge-sharing dimer of Eu1A, is taken as a node, which is connected to the other equivalent dimer via the ox²⁻ linker, the two-dimensional layer of Eu1 can be simplified to a uninodal 4-connected sql/Shubnikov tetragonal plane net with a point symbol {4⁴.6²} (Blatov et al., 2014 ) (Fig. 6). The inclusion of the partially occupied TPR-{Eu^IIIO₆} motifs results in unknown topology. This is also the case for the three-dimensional framework with or without the TPR-{Eu^IIIO₆} motifs.

Figure 6
The simplified two- and three-dimensional topologies of I.

5. Photoluminescent property

A room temperature photoluminescent spectrum of I was collected (Jasco FB-8500 spectrofluorometer, λ_excitation = 337 nm). It exhibits none of the characteristic f–f emission of Eu^III. Even the broad emission characteristic of the ligand-centered π–π emission was not observed. This may be attributed to a proton-induced fluorescence-quenching mechanism facilitated by the presence of H₃O⁺ in close proximity to the phenyl ring of NH₂-BDC²⁻ (Tobita & Shizuka, 1980 ; Shizuka & Tobita, 1982 ). The quenching consequently hinders the sensitization, which is important according to the antenna model (Einkauf et al., 2017 ).

6. Database survey

Based on a survey of the Cambridge Structural Database (version 5.40, Nov 2018 with the update of May 2019; Groom et al., 2016 ), no LnCP containing both NH₂-BDC²⁻ and ox²⁻ has previously been reported. However, there are three closely relevant structures which have similar unit-cell parameters, i.e. catena-[(μ-tetracyanoborate)tetraaquabis(nitrato)lanthanum] (Zottnick et al., 2017 ), catena-[hemikis(piperazinedium)(μ-benzene-1,2,4,5-tetracarboxylato)diaquapraseodymium(III)] (Liang et al., 2017 ) and η⁵-indenyl)dichlorotris(tetrahydrofuran-O)gadolinium tetrahydrofuran solvate (Fuxing et al., 1992 ).

7. Synthesis and crystallization

To synthesize I, 2-aminoterephthalic acid (0.2 mmol, 0.0332 g), oxalic acid (0.2 mmol, 0.0180 g) and 1,4-diazabicyclo[2.2.2]octane (0.4 mmol, 0.0448 g) were dissolved in 8.0 mL of DMF/H₂O (1 m:7 mL) to prepare solution A. Separately, solution B was prepared by dissolving Eu₂O₃ (0.1 mmol, 0.0180 g) in 1.0 mL of concentrated HNO₃ aqueous solution, which was then adjusted to pH 7 using a 10 M NaOH aqueous solution. Solution B was then gradually introduced into solution A, and the mixture was then transferred to a 22 mL Teflon-lined stainless-steel autoclave. The reaction was carried out under an autogenous pressure generated at 393 K for 7 days. Yellow crystals of I were then recovered by filtration. FT–IR of I (KBr; cm⁻¹): 3361, 2987, 1617, 1313, 1053, 798.

8. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The Eu^III ion was refined as being disordered over two crystallographic sites resulting in refined occupancies of 0.855 (Eu1A) and 0.145 (Eu1B). The disorder of the amino group over three crystallographic sites could be clearly seen in the electron-density map and was refined using the SUMP command providing occupancies of 0.259 (N1), 0.440 (N2) and 0.305 (N3). EADP constraints were necessary to make the anisotropic refinements of the disordered N atoms stable. The three H atoms on the ligated H₃O⁺ (O9W) were evident in the electron-density map and therefore assigned as such. The SADI restraint was nonetheless applied on the refinements of the three O—H bonds. H atoms could be positioned from the electron-density maps and were refined as riding with U_iso(H) = 1.2U_eq(C, N) or 1.5U_eq(O). Bond restraints o N—H and O—H were applied in the refunements.

Table 2
Experimental details

Crystal data
Chemical formula	[Eu(C₈H₅NO₄)(C₂O₄)(H₃O)]
M_r	436.32
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	11.8348 (3), 11.3208 (3), 10.6531 (3)
β (°)	110.275 (3)
V (Å³)	1338.86 (7)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	4.73
Crystal size (mm)	0.2 × 0.05 × 0.05

Data collection
Diffractometer	Rigaku OD SuperNova, single source at offset/far, HyPix3000
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2018 )
T_min, T_max	0.753, 0.789
No. of measured, independent and observed [I > 2σ(I)] reflections	15479, 2882, 2458
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.647

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.067, 1.09
No. of reflections	2882
No. of parameters	222
No. of restraints	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.61, −0.54
Computer programs: CrysAlis PRO (Rigaku OD, 2018), SHELXT (Sheldrick, 2015b ), SHELXL (Sheldrick, 2015a ) and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC references: 1962371; 1962371

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2056989019014713/jj2217sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019014713/jj2217Isup2.hkl

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Rigaku OD, 2018); cell refinement: CrysAlis PRO (Rigaku OD, 2018); data reduction: CrysAlis PRO (Rigaku OD, 2018); program(s) used to solve structure: SHELXT (Sheldrick, 2015b); program(s) used to refine structure: SHELXL (Sheldrick, 2015a); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Poly[(µ₆-oxalato)(oxomium)(µ₅-2-aminobenzene-1,4-dicarboxylato)europium(III)] top

Crystal data top

[Eu(C₈H₅NO₄)(C₂O₄)(H₃O)]	F(000) = 832
M_r = 436.32	D_x = 2.165 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.8348 (3) Å	Cell parameters from 9488 reflections
b = 11.3208 (3) Å	θ = 1.8–27.3°
c = 10.6531 (3) Å	µ = 4.73 mm⁻¹
β = 110.275 (3)°	T = 293 K
V = 1338.86 (7) Å³	Block, clear light yellow
Z = 4	0.2 × 0.05 × 0.05 mm

Data collection top

Rigaku OD SuperNova, single source at offset/far, HyPix3000 diffractometer	2458 reflections with I > 2σ(I)
Radiation source: micro-focus sealed X-ray tube	R_int = 0.050
ω scans	θ_max = 27.4°, θ_min = 1.8°
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2018)	h = −14→15
T_min = 0.753, T_max = 0.789	k = −11→14
15479 measured reflections	l = −13→13
2882 independent reflections

Refinement top

Refinement on F²	4 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.028	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.067	w = 1/[σ²(F_o²) + (0.0305P)² + 0.0276P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max = 0.001
2882 reflections	Δρ_max = 0.61 e Å⁻³
222 parameters	Δρ_min = −0.54 e Å⁻³

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)
Eu1A	0.07429 (2)	0.61284 (2)	0.15674 (2)	0.01311 (9)	0.8558 (8)
O6	0.0486 (2)	0.7311 (2)	0.3456 (2)	0.0298 (6)
O8	−0.0221 (2)	0.89620 (19)	0.4069 (3)	0.0248 (6)
O5	−0.0175 (2)	0.8135 (2)	0.0928 (2)	0.0314 (6)
O2	0.1449 (2)	0.4078 (2)	−0.1090 (3)	0.0315 (7)
O7	−0.0772 (2)	0.9814 (2)	0.1603 (2)	0.0298 (6)
O4	0.7236 (2)	0.1331 (2)	0.1432 (3)	0.0356 (7)
O1	0.2130 (2)	0.5301 (3)	0.0649 (3)	0.0385 (7)
O3	0.7668 (2)	0.2640 (2)	0.3050 (3)	0.0366 (7)
C10	0.0008 (3)	0.8307 (3)	0.3236 (4)	0.0212 (8)
C1	0.2274 (3)	0.4463 (4)	−0.0068 (4)	0.0278 (9)
C9	−0.0344 (3)	0.8795 (3)	0.1784 (4)	0.0229 (9)
C8	0.6941 (3)	0.2224 (4)	0.1960 (4)	0.0290 (9)
C2	0.3499 (3)	0.3911 (3)	0.0360 (4)	0.0319 (10)
C5	0.5750 (3)	0.2802 (4)	0.1344 (4)	0.0353 (10)
C6	0.5557 (4)	0.3900 (4)	0.1808 (5)	0.0502 (14)
H6	0.619345	0.426877	0.246414	0.060*
C3	0.3677 (4)	0.2839 (4)	−0.0150 (5)	0.0513 (13)
C7	0.4454 (4)	0.4470 (4)	0.1332 (5)	0.0480 (12)
C4	0.4805 (4)	0.2271 (4)	0.0321 (5)	0.0528 (13)
N2	0.4834 (8)	0.1125 (8)	−0.0128 (12)	0.066 (3)	0.439 (6)
H2A	0.512716	0.113790	−0.078500	0.080*	0.439 (6)
H2B	0.531521	0.063870	0.047841	0.080*	0.439 (6)
N3	0.4511 (10)	0.5604 (13)	0.1717 (14)	0.066 (3)	0.312 (6)
H3A	0.407927	0.583997	0.230300	0.080*	0.312 (6)
H3B	0.527520	0.590092	0.221251	0.080*	0.312 (6)
N1	0.2993 (12)	0.2381 (15)	−0.1365 (15)	0.066 (3)	0.261 (6)
H1A	0.286630	0.164575	−0.125872	0.080*	0.261 (6)
H1B	0.231669	0.274954	−0.165662	0.080*	0.261 (6)
Eu1B	0.82330 (16)	0.39654 (13)	0.47691 (17)	0.0427 (7)	0.1442 (8)
O9W	0.8080 (3)	0.5707 (3)	0.3580 (3)	0.0593 (9)
H9WA	0.816 (5)	0.581 (4)	0.258 (4)	0.089*
H9WB	0.881 (4)	0.620 (4)	0.433 (5)	0.089*
H9WC	0.725 (4)	0.578 (6)	0.383 (7)	0.15 (3)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Eu1A	0.01489 (13)	0.00998 (14)	0.01356 (13)	−0.00037 (7)	0.00379 (9)	−0.00035 (8)
O6	0.0446 (16)	0.0207 (15)	0.0244 (14)	0.0096 (12)	0.0121 (12)	0.0042 (12)
O8	0.0355 (15)	0.0197 (15)	0.0206 (15)	0.0018 (11)	0.0114 (13)	−0.0022 (11)
O5	0.0494 (17)	0.0224 (16)	0.0230 (14)	0.0099 (13)	0.0133 (13)	0.0000 (12)
O2	0.0215 (14)	0.0420 (19)	0.0291 (16)	−0.0002 (12)	0.0064 (12)	−0.0073 (13)
O7	0.0425 (16)	0.0182 (15)	0.0244 (14)	0.0085 (12)	0.0060 (12)	0.0020 (12)
O4	0.0320 (16)	0.0368 (18)	0.0329 (17)	0.0101 (12)	0.0045 (13)	−0.0070 (13)
O1	0.0243 (14)	0.048 (2)	0.0420 (17)	0.0037 (13)	0.0095 (13)	−0.0161 (15)
O3	0.0306 (15)	0.0333 (18)	0.0357 (17)	0.0088 (13)	−0.0014 (13)	−0.0089 (14)
C10	0.0242 (19)	0.014 (2)	0.026 (2)	−0.0034 (16)	0.0088 (16)	−0.0023 (17)
C1	0.025 (2)	0.030 (2)	0.029 (2)	−0.0008 (18)	0.0107 (18)	−0.0008 (19)
C9	0.026 (2)	0.021 (2)	0.017 (2)	0.0012 (16)	0.0008 (17)	0.0012 (16)
C8	0.028 (2)	0.027 (2)	0.028 (2)	0.0023 (18)	0.0054 (18)	−0.0028 (19)
C2	0.025 (2)	0.033 (3)	0.035 (2)	0.0063 (17)	0.0074 (19)	−0.0015 (19)
C5	0.030 (2)	0.035 (3)	0.036 (2)	0.0084 (18)	0.005 (2)	−0.004 (2)
C6	0.031 (3)	0.044 (3)	0.056 (3)	0.013 (2)	−0.010 (2)	−0.020 (2)
C3	0.031 (2)	0.048 (3)	0.058 (3)	0.009 (2)	−0.006 (2)	−0.017 (3)
C7	0.035 (2)	0.046 (3)	0.052 (3)	0.015 (2)	0.001 (2)	−0.016 (3)
C4	0.042 (3)	0.053 (3)	0.049 (3)	0.018 (2)	−0.003 (2)	−0.019 (3)
N2	0.033 (4)	0.064 (5)	0.081 (6)	0.026 (3)	−0.007 (4)	−0.040 (4)
N3	0.033 (4)	0.064 (5)	0.081 (6)	0.026 (3)	−0.007 (4)	−0.040 (4)
N1	0.033 (4)	0.064 (5)	0.081 (6)	0.026 (3)	−0.007 (4)	−0.040 (4)
Eu1B	0.0590 (12)	0.0319 (11)	0.0319 (10)	−0.0013 (7)	0.0090 (8)	−0.0028 (7)
O9W	0.076 (3)	0.056 (2)	0.044 (2)	−0.014 (2)	0.0174 (19)	0.0008 (19)

Geometric parameters (Å, º) top

Eu1A—Eu1Aⁱ	4.0868 (4)	O4—C8	1.264 (4)
Eu1A—O6	2.521 (2)	O4—Eu1B^vii	2.468 (3)
Eu1A—O8ⁱⁱ	2.562 (2)	O1—C1	1.266 (4)
Eu1A—O8ⁱⁱⁱ	2.508 (3)	O3—C8	1.272 (4)
Eu1A—O5	2.508 (2)	O3—Eu1B	2.281 (3)
Eu1A—O2ⁱ	2.476 (2)	C10—C9	1.558 (5)
Eu1A—O7ⁱⁱ	2.444 (3)	C1—C2	1.497 (5)
Eu1A—O4^iv	2.604 (3)	C8—C5	1.484 (5)
Eu1A—O1	2.375 (2)	C2—C3	1.375 (5)
Eu1A—O3^iv	2.470 (3)	C2—C7	1.393 (6)
O6—C10	1.247 (4)	C5—C6	1.386 (6)
O6—Eu1B^v	2.445 (3)	C5—C4	1.398 (6)
O8—C10	1.256 (4)	C6—C7	1.386 (6)
O5—C9	1.247 (4)	C3—C4	1.408 (6)
O5—Eu1B^iv	2.811 (3)	C3—N1	1.368 (14)
O2—C1	1.261 (4)	C7—N3	1.343 (13)
O7—C9	1.247 (4)	C4—N2	1.387 (8)
O7—Eu1B^vi	2.349 (3)	Eu1B—O9W	2.317 (4)

O6—Eu1A—Eu1Aⁱ	147.91 (6)	Eu1B^vi—O7—Eu1A^ix	99.74 (10)
O6—Eu1A—O8ⁱⁱ	129.40 (8)	C8—O4—Eu1A^x	91.4 (2)
O6—Eu1A—O4^iv	68.33 (9)	C8—O4—Eu1B^vii	134.7 (3)
O8ⁱⁱⁱ—Eu1A—Eu1Aⁱ	36.75 (5)	Eu1B^vii—O4—Eu1A^x	92.50 (9)
O8ⁱⁱ—Eu1A—Eu1Aⁱ	35.85 (6)	C1—O1—Eu1A	143.2 (2)
O8ⁱⁱⁱ—Eu1A—O6	137.05 (8)	C8—O3—Eu1A^x	97.5 (2)
O8ⁱⁱⁱ—Eu1A—O8ⁱⁱ	72.60 (9)	C8—O3—Eu1B	153.3 (3)
O8ⁱⁱ—Eu1A—O4^iv	111.70 (8)	Eu1B—O3—Eu1A^x	109.19 (11)
O8ⁱⁱⁱ—Eu1A—O4^iv	145.39 (9)	O6—C10—O8	126.6 (3)
O5—Eu1A—Eu1Aⁱ	108.73 (6)	O6—C10—C9	117.1 (3)
O5—Eu1A—O6	64.84 (8)	O8—C10—C9	116.3 (3)
O5—Eu1A—O8ⁱⁱⁱ	75.76 (8)	O2—C1—O1	123.6 (3)
O5—Eu1A—O8ⁱⁱ	138.85 (8)	O2—C1—C2	119.8 (4)
O5—Eu1A—O4^iv	109.32 (8)	O1—C1—C2	116.6 (3)
O2ⁱ—Eu1A—Eu1Aⁱ	69.48 (6)	O5—C9—C10	117.2 (3)
O2ⁱ—Eu1A—O6	78.84 (8)	O7—C9—O5	126.9 (4)
O2ⁱ—Eu1A—O8ⁱⁱⁱ	73.70 (9)	O7—C9—C10	115.9 (3)
O2ⁱ—Eu1A—O8ⁱⁱ	73.49 (8)	O4—C8—Eu1A^x	63.02 (19)
O2ⁱ—Eu1A—O5	72.87 (8)	O4—C8—O3	119.9 (3)
O2ⁱ—Eu1A—O4^iv	140.91 (9)	O4—C8—C5	121.5 (3)
O7ⁱⁱ—Eu1A—Eu1Aⁱ	98.87 (6)	O3—C8—Eu1A^x	56.94 (18)
O7ⁱⁱ—Eu1A—O6	70.07 (9)	O3—C8—C5	118.6 (4)
O7ⁱⁱ—Eu1A—O8ⁱⁱ	64.12 (8)	C5—C8—Eu1A^x	174.2 (3)
O7ⁱⁱ—Eu1A—O8ⁱⁱⁱ	134.20 (8)	C3—C2—C1	120.9 (4)
O7ⁱⁱ—Eu1A—O5	130.79 (9)	C3—C2—C7	119.9 (4)
O7ⁱⁱ—Eu1A—O2ⁱ	80.22 (9)	C7—C2—C1	119.1 (4)
O7ⁱⁱ—Eu1A—O4^iv	69.26 (8)	C6—C5—C8	119.1 (4)
O7ⁱⁱ—Eu1A—O3^iv	119.41 (9)	C6—C5—C4	118.5 (4)
O4^iv—Eu1A—Eu1Aⁱ	137.47 (6)	C4—C5—C8	122.4 (4)
O1—Eu1A—Eu1Aⁱ	65.16 (6)	C5—C6—C7	122.5 (4)
O1—Eu1A—O6	146.09 (8)	C2—C3—C4	121.2 (4)
O1—Eu1A—O8ⁱⁱ	69.59 (9)	N1—C3—C2	125.9 (7)
O1—Eu1A—O8ⁱⁱⁱ	70.84 (8)	N1—C3—C4	109.9 (7)
O1—Eu1A—O5	122.76 (9)	C6—C7—C2	118.6 (4)
O1—Eu1A—O2ⁱ	134.63 (9)	N3—C7—C2	127.1 (6)
O1—Eu1A—O7ⁱⁱ	105.55 (9)	N3—C7—C6	113.1 (6)
O1—Eu1A—O4^iv	78.60 (9)	C5—C4—C3	119.0 (4)
O1—Eu1A—O3^iv	75.28 (9)	N2—C4—C5	124.2 (5)
O3^iv—Eu1A—Eu1Aⁱ	130.96 (7)	N2—C4—C3	116.0 (5)
O3^iv—Eu1A—O6	78.21 (9)	O6^v—Eu1B—O5^x	70.24 (9)
O3^iv—Eu1A—O8ⁱⁱⁱ	104.11 (8)	O6^v—Eu1B—O4^xi	71.76 (10)
O3^iv—Eu1A—O8ⁱⁱ	143.79 (9)	O7^xii—Eu1B—O6^v	72.95 (10)
O3^iv—Eu1A—O5	69.54 (8)	O7^xii—Eu1B—O5^x	101.31 (10)
O3^iv—Eu1A—O2ⁱ	141.55 (9)	O7^xii—Eu1B—O4^xi	73.14 (10)
O3^iv—Eu1A—O4^iv	51.17 (8)	O4^xi—Eu1B—O5^x	141.46 (10)
C10—O6—Eu1A	120.2 (2)	O3—Eu1B—O6^v	99.37 (11)
C10—O6—Eu1B^v	143.1 (2)	O3—Eu1B—O5^x	66.84 (9)
C10—O8—Eu1A^viii	126.6 (2)	O3—Eu1B—O7^xii	167.83 (13)
C10—O8—Eu1A^ix	118.0 (2)	O3—Eu1B—O4^xi	114.01 (12)
C9—O5—Eu1A	120.6 (2)	O3—Eu1B—O9W	100.09 (12)
C9—O5—Eu1B^iv	110.2 (2)	O9W—Eu1B—O6^v	146.74 (13)
C1—O2—Eu1Aⁱ	130.7 (2)	O9W—Eu1B—O5^x	93.23 (12)
C9—O7—Eu1A^ix	123.2 (2)	O9W—Eu1B—O7^xii	82.84 (12)
C9—O7—Eu1B^vi	137.1 (2)	O9W—Eu1B—O4^xi	122.82 (13)

Symmetry codes: (i) −x, −y+1, −z; (ii) −x, y−1/2, −z+1/2; (iii) x, −y+3/2, z−1/2; (iv) −x+1, y+1/2, −z+1/2; (v) −x+1, −y+1, −z+1; (vi) x−1, −y+3/2, z−1/2; (vii) x, −y+1/2, z−1/2; (viii) x, −y+3/2, z+1/2; (ix) −x, y+1/2, −z+1/2; (x) −x+1, y−1/2, −z+1/2; (xi) x, −y+1/2, z+1/2; (xii) 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
O9W—H9WA···O2^xiii	1.11 (5)	1.81 (5)	2.904 (4)	171 (5)
O9W—H9WB···O5^xii	1.10 (5)	1.87 (5)	2.943 (4)	163 (4)
C6—H6···O3	0.93	2.47	2.781 (6)	100
N1—H1B···O2	0.86	2.03	2.736 (16)	139

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

Funding information

Funding for this research was co-provided by: Chiang Mai University and Thailand Research Fund (grant No. RSA6280003 to Apinpus Rujiwatra); Science Achievement Scholarship of Thailand (to Supaphorn Thammakan).

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