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

The non-porous three-dimensional structure of poly[(μ5-2-amino-benzene-1,4-di-carboxyl-ato)(μ6-oxalato)(oxomium)europium(III)], [Eu(C8H5NO4)(C2O4)(H3O)] n or [EuIII(NH2-BDC)(ox)(H3O)] n (NH2-BDC2- = 2-amino-terephthalate and ox2- = oxalate) is constructed from two-dimensional layers of EuIII-carboxyl-ate-oxalate, which are connected by NH2-BDC2- pillars. The basic structural unit of the layer is an edge-sharing dimer of TPRS-{EuIIIO9}, which is assembled through the ox2- moiety. The intra-layer void is partially occupied by TPR-{EuIIIO6} motifs. Weak C-H⋯O and strong, classical intra-molecular N-H⋯O and inter-molecular O-H⋯O hydrogen-bonding inter-actions, as well as weak π-π stacking inter-actions, affix the organic pillars within the framework. The two-dimensional layer can be simplified to a uninodal 4-connected sql/Shubnikov tetra-gonal plane net with point symbol {44.62}. © Thammakan et al. 2019.

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 EuIII ion and the amino group, is reported. Weak inter­molecular inter­actions and the framework topology are also described.

Structural commentary

[Eu(NH2–BDC)(ox)(H3O)] crystallizes in the monoclinic space group P21/c. Its asymmetric unit comprises one EuIII 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-{EuIIIO9}. Eu1B, on the other hand, adopts a sixfold coordination of trigonal anti-prismatic geometry, i.e. TPR-{EuIIIO6}, 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 EuIII—O bond distances ranging between 2.375 (2) and 2.562 (2) Å, are consistent with the values observed for other EuIII 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] where ATPA2− = 2-amino­terepthalate and DEF = di­ethyl­formamide (Kariem et al., 2016 ▸). In addition to the disorder at the EuIII 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,  + y,  − z; (iii) −x, − + y,  − z; (iv) x,  − y, − + z; (v) x,  − y,  + z; (vi) 1 − x, − + y,  − z; (vii) 1 − x, 1 − y, 1 − z; (viii) 1 − x,  − y,  + z.]

As a result of the disorder of the EuIII ion, the modes of coordinations for both NH2–BDC2− and ox2− are diverse. If all of the possible sites of EuIII 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]·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} 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.

Supra­molecular features

The structure of I features a three-dimensional framework, which can be regarded as being built up of two-dimensional layers of EuIII-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-{EuIIIO9} (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-{EuIIIO6} motifs of Eu1B are situated. Each of the TPR-{EuIIIO6} 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 EuIII–oxalate–carboxyl­ate layers (a) with TPR-{EuIIIO6} motifs and (b) without TPR-{EuIIIO6} 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) ; (ii) .

Figure 5

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

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-{EuIIIO6} motifs results in unknown topology. This is also the case for the three-dimensional framework with or without the TPR-{EuIIIO6} motifs.

Figure 6

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

Photoluminescent property

A room temperature photoluminescent spectrum of I was collected (Jasco FB-8500 spectro­fluoro­meter, λexcitation = 337 nm). It exhibits none of the characteristic f–f emission of EuIII. 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 ▸).

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 ▸).

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.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. The EuIII 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[F 2 > 2σ(F 2)], wR(F 2), 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
Δρmax, Δρmin (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 ▸).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989019014713/jj2217sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989019014713/jj2217Isup2.hkl

CCDC references: 1962371, 1962371

Additional supporting information: crystallographic information; 3D view; checkCIF report

[Eu(C8H5NO4)(C2O4)(H3O)]	F(000) = 832
Mr = 436.32	Dx = 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

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

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(Fo2) + (0.0305P)2 + 0.0276P] where P = (Fo2 + 2Fc2)/3
S = 1.09	(Δ/σ)max = 0.001
2882 reflections	Δρmax = 0.61 e Å−3
222 parameters	Δρmin = −0.54 e Å−3

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.

	x	y	z	Uiso*/Ueq	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)*

	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)

Eu1A—Eu1Ai	4.0868 (4)	O4—C8	1.264 (4)
Eu1A—O6	2.521 (2)	O4—Eu1Bvii	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—O4iv	2.604 (3)	C8—C5	1.484 (5)
Eu1A—O1	2.375 (2)	C2—C3	1.375 (5)
Eu1A—O3iv	2.470 (3)	C2—C7	1.393 (6)
O6—C10	1.247 (4)	C5—C6	1.386 (6)
O6—Eu1Bv	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—Eu1Biv	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—Eu1Bvi	2.349 (3)	Eu1B—O9W	2.317 (4)
O6—Eu1A—Eu1Ai	147.91 (6)	Eu1Bvi—O7—Eu1Aix	99.74 (10)
O6—Eu1A—O8ii	129.40 (8)	C8—O4—Eu1Ax	91.4 (2)
O6—Eu1A—O4iv	68.33 (9)	C8—O4—Eu1Bvii	134.7 (3)
O8iii—Eu1A—Eu1Ai	36.75 (5)	Eu1Bvii—O4—Eu1Ax	92.50 (9)
O8ii—Eu1A—Eu1Ai	35.85 (6)	C1—O1—Eu1A	143.2 (2)
O8iii—Eu1A—O6	137.05 (8)	C8—O3—Eu1Ax	97.5 (2)
O8iii—Eu1A—O8ii	72.60 (9)	C8—O3—Eu1B	153.3 (3)
O8ii—Eu1A—O4iv	111.70 (8)	Eu1B—O3—Eu1Ax	109.19 (11)
O8iii—Eu1A—O4iv	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—O4iv	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—Eu1Ax	63.02 (19)
O2i—Eu1A—O5	72.87 (8)	O4—C8—O3	119.9 (3)
O2i—Eu1A—O4iv	140.91 (9)	O4—C8—C5	121.5 (3)
O7ii—Eu1A—Eu1Ai	98.87 (6)	O3—C8—Eu1Ax	56.94 (18)
O7ii—Eu1A—O6	70.07 (9)	O3—C8—C5	118.6 (4)
O7ii—Eu1A—O8ii	64.12 (8)	C5—C8—Eu1Ax	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—O4iv	69.26 (8)	C6—C5—C8	119.1 (4)
O7ii—Eu1A—O3iv	119.41 (9)	C6—C5—C4	118.5 (4)
O4iv—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—O4iv	78.60 (9)	C5—C4—C3	119.0 (4)
O1—Eu1A—O3iv	75.28 (9)	N2—C4—C5	124.2 (5)
O3iv—Eu1A—Eu1Ai	130.96 (7)	N2—C4—C3	116.0 (5)
O3iv—Eu1A—O6	78.21 (9)	O6v—Eu1B—O5x	70.24 (9)
O3iv—Eu1A—O8iii	104.11 (8)	O6v—Eu1B—O4xi	71.76 (10)
O3iv—Eu1A—O8ii	143.79 (9)	O7xii—Eu1B—O6v	72.95 (10)
O3iv—Eu1A—O5	69.54 (8)	O7xii—Eu1B—O5x	101.31 (10)
O3iv—Eu1A—O2i	141.55 (9)	O7xii—Eu1B—O4xi	73.14 (10)
O3iv—Eu1A—O4iv	51.17 (8)	O4xi—Eu1B—O5x	141.46 (10)
C10—O6—Eu1A	120.2 (2)	O3—Eu1B—O6v	99.37 (11)
C10—O6—Eu1Bv	143.1 (2)	O3—Eu1B—O5x	66.84 (9)
C10—O8—Eu1Aviii	126.6 (2)	O3—Eu1B—O7xii	167.83 (13)
C10—O8—Eu1Aix	118.0 (2)	O3—Eu1B—O4xi	114.01 (12)
C9—O5—Eu1A	120.6 (2)	O3—Eu1B—O9W	100.09 (12)
C9—O5—Eu1Biv	110.2 (2)	O9W—Eu1B—O6v	146.74 (13)
C1—O2—Eu1Ai	130.7 (2)	O9W—Eu1B—O5x	93.23 (12)
C9—O7—Eu1Aix	123.2 (2)	O9W—Eu1B—O7xii	82.84 (12)
C9—O7—Eu1Bvi	137.1 (2)	O9W—Eu1B—O4xi	122.82 (13)

D—H···A	D—H	H···A	D···A	D—H···A
O9W—H9WA···O2xiii	1.11 (5)	1.81 (5)	2.904 (4)	171 (5)
O9W—H9WB···O5xii	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