A triboluminescent europium(III) complex

The crystal structure of (4,4′-di­methyl-2,2′-bipyridyl)­tris­[3,3,3-tri­fluoro-1-(2-thenoyl)propan-2-onato]­europium(III), or more commonly (4,4′-dimethyl-2,2′-bipyridyl)tris(2-thenoyltrifluoro­acetonato)europium(III), [Eu(C₈H₄F₃O₂S)₃(C₁₂H₁₂N₂)], has been determined. Crystals of the complex emit vivid red light when scratched or fractured. This triboluminescent activity seems to correlate with the non-centrosymmetric crystal structure and disorder of the thienyl rings and CF₃ groups which is present here and in similar compounds. While modeling the thienyl-ring disorder, it was noted that the bond angle at the C atom replaced by S is a sensitive sign of even small rotational ring disorder. The coordination geometry of the Eu^III ion can be described as square antiprismatic, with coordination by the six O atoms of the three chelating β-diketonate ligands and the two N atoms of the neutral bipyridyl ligand.

S1. Comment

Triboluminescence, the process whereby certain materials emit light when they are fractured, has been known for nearly 400 years (Walton, 1977). Although it remains an obscure phenomenon, the effect is generally explained in terms of excitation of the molecule by an electric discharge between the surfaces of the fractured crystals and subsequent fluorescence (Sweeting et al., 1997). Recently, a novel and potentially important application of the phenomenon has been proposed for the development of real-time damage sensors in composite materials (Sage et al., 1999). Specifically, the idea is built on the observation that light emission occurs when a composite material containing the triboluminescent molecule is damaged. Monitoring the wavelength and measuring the amount of emission would then yield the information on the location and extent of the damage, respectively. Preliminary experiments have demonstrated the validity of such a concept.

In the course of our studies of lanthanide phosphors for organic electroluminescence applications (Wang et al., 2001), we synthesized a europium(III) complex, namely (4,4'-dimethyl-2,2'-bipyridyl)tris[3,3,3-trifluoro-1-(2-thenoyl)acetonato]- europium(III) [Eu(TTA)₃(DMDPY), (I)] and inadvertently observed its triboluminescence. Brilliant red sparks were displayed when crystals of the complex were cut or crushed, even with room illumination on. We report herein the solid-state structure of this complex, which has been important in understanding the observed triboluminescence. A literature search for related compounds indicates that the synthesis (Shang et al., 1997; Chen et al., 1998), triboluminescent property (Chen et al., 1999) and crystal structure (Chen et al., 1999) of a closely related compound, the 2,2'-bipyridyl adduct of tri(2-thenoyltrifluoroacetonato)europate(III), (II), have recently been reported.

Compound (I) crystallizes in the polar space group Pca2₁ with four molecules in the unit cell. The asymmetric unit contains only one molecule whose displacement ellipsoid plot is shown in Fig. 1. The Eu^III ion is eight-coordinated, by six O atoms of the three chelating β-diketonate ligands and by two N atoms of a 4,4'-dimethyl-2,2'-bipyridyl ligand. The coordination polyhedron can be best described as being square antiprismatic. The two square planes with respective deviations of 0.0486 (14) and 0.0972 (13) Å are O11/O21/N14/N124 and O12/O22/O13/O23. Corresponding values (0.0458 and 0.0124 Å, respectively) of this structural parameter are somewhat smaller in the structure of (II) (Chen et al., 1999). It appears that the methyl substituents on the 4,4'-dimethyl-2,2'-bipyridyl ligand cause the square antiprism to distort slightly. The distance from the metal ion to the 11/O21/N14/N124 plane is 1.4198 (14) Å, which is significantly longer than that to the other plane, O12/O22/O13/O23, of 1.2116 (13) Å. The dihedral angle between the two planes is 3.65 (7)°, which is somewhat larger than that (2.6°) found in the structure of (II). All observed bond lengths and angles are normal. The average Eu—O and Eu—N bond lengths are 2.37 (2) and 2.582 (8) Å, respectively. These values are unremarkably similar to those found for (II) (2.352 and 2.578 Å, respectively). The mean O—Eu—O angle within the chelate rings is 71.9 (7)°, which is close to that found in (II) (72.1°).

The observed triboluminescent activity of (I) is in line with the commonly accepted mechanism for triboluminescence, the first step being charge separation due to piezoelectricity which occurs when the non-centrosymmetric crystal is deformed or fractured (Longchambon, 1923). In this context, it is worth noting that complex (II), different from (I) only in the absence of two methyl substituents on the bipyridyl ligand, is also triboluminescent, but crystallizes in a monoclinic centrosymmetric space group P2₁/n (Chen et al., 1999). The authors ascribe the observed triboluminescence to the disorder of the thienyl rings and CF₃ groups of the β-diketonate ligands. Impurities have also been suggested to play important roles in the triboluminescent activity of some centrosymmetric materials (Rheingold & Sweeting, 1987; Sweeting et al., 1997). Both the structural disorder and impurities in crystals are believed to create the localized asymmetry that is essential to support charge separation, and could therefore explain why materials that are symmetric overall can still exhibit triboluminescence.

These facts led us to examine the disorder present in (I) very carefully. The CF₃ groups are slightly disordered in (I) due to rotation about the C—C bond. Such distortions are commonly observed in β-diketonates substituted with CF₃ groups even at reduced temparatures and are well modeled using anisotropic displacement parameters. In addition, two of the three thienyl rings show apparent disorders. For ring 3, this was evidenced, before disorder modeling, by an abnormally large S-atom displacement parameter (U_iso = 0.075 Ų) and an abnormally small (U_iso = 0.032 Ų) ortho-C-atom displacement parameter. In ring 2, the difference in displacement parameters was much smaller (U_iso = 0.056 and 0.050 Ų) and disorder was not obvious until the bond distances and angles in the ring fragments were examined and a marked difference in geometry of rings 2 and 1 was noticed. In particular, the C3—C4—C5 angle in ring (I) measured 113.7 (5)° while that in ring 2 measured 111.5 (5)°. In clearly disordered ring 3, the C3—C4—C5 angle was 98.4 (4)°. The displacement paramters of all five atoms in ring 1 ranged from U_iso = 0.042 Ų to U_iso = 0.057 Ų, with a difference of U_iso = 0.005 Ų between the S and ortho-C atom. Abnormal displacement parameters alone are not sufficient to reveal all cases of disorder.

We conducted a search of the Cambridge Structure Database (CSD; Allen & Kennard, 1993) for thiophene rings substituted at the 5 position (by our numbering). We found 378 entries containing 613 of these pendant thienyl groups, of which 130 entries (232 fragments) have a disorder flag which ususally, but not necessarily, involves the thienyl ring. In either case, we found the distributions of bond lengths and angles to be very broad and in general bimodal. This was most evident for the entries without disorder flags when looking at the bond angle at C4, the ortho-C atom, which would be substituted by S in the case of ring rotation. The distribution ranged from 91.0 to 123.0° in a roughly Gaussian shape (11° FWHM) peaking at 109° and included a sharp (2° FWHM) spike at 112.5° with over twice the intensity of the Gaussian peak. Closer examination of a few randomly selected entries revealed that most of those within the spike had little or no signs of thienyl disorder, while those with angles below 109° showed abnormal displacement parameters, increased R values and/or other abnormal bonding parameters which could indicate rotational ring disorder. Our ring 1 compared favorably with those chosen from within the spike and was declared disorder free and fit to be used as a good restraint model for the two disordered rings. If it holds true that undisordered thienyl rings have a mean ortho-C angle of 112.5° then approximatedly half of the CSD entries with a thienyl ring within the molecule have unresolved disorder. This unresolved disorder might explain some mysterious cases of triboluminescence or provide new compounds to examine in the search for further triboluminescent compounds.

S2. Experimental

To a solution prepared from KO^tBu (1.12 g, 10.0 mmol) in H₂O (20 ml) was added TTA (2.20 g, 9.9 mmol). The clear mixture was added to an aqueous solution of EuCl₃·6H₂O (1.20 g, 3.3 mmol in 20 ml H₂O) to yield a white precipitate. The mixture was stirred at 333 K for 20 min and then for 3 h at room temperature. The precipitate was filtered off, washed with water (2 × 50 ml), and dried at 313 K under vacuum for 12 h. The aqua complex of tri(2-thenoyltrifluoroacetonato)europate(III) was obtained as colorless crystals after recrystallization from acetone (2.38 g, 85% yield). Following the procedure developed by Melby (Melby et al., 1964), complex (I) was prepared by substituting the coordinated water molecule in the aqua complex with 4,4'-dimethyl-2,2'-bipyridyl as the neutral ligand. Characterization data for (I), ¹H NMR (250 MHz, CD₃Cl, δ, p.p.m.): 3.32 (s, 3H, TTA), 4.68 (s, 6H, CH₃), 6.11 (s, 3H, TTA), 6.50 (s, 3H, TTA), 7.35 (s, 2H, DMDPY), 8.50 (s, 2H, DMDPY), 9.20 (s, 2H, DMDPY), 14.8 (s, 3H, CH). FAB-MS: 1001.76 [M+H]⁺, 779.6 [M-TTA]⁺. Analysis calculated for C₃₆H₂₄EuF₉N₂O₆S₃: C 43.24, H 2.42, N 2.80%; found: C 43.04, H 2.28, N 2.81%.

S3. Refinement

H atoms were added at idealized positions, constrained to ride on the atom to which they are bonded (C—H = 0.95 or 0.98 Å) and given displacement parameters equal to 1.2 or 1.5 times U_iso of the bonded atom. Two of the three thienyl rings showed rotational disorder and were modeled as two overlapping fragments. The refined populations of the major fragments were 0.713 (4) and 0.968 (4) for rings 3 and 2, respectively. To prevent ring deformations and account for large correlations in atomic positions of overlapping sites, the split rings were restrained to have approximately the same geometry as the single ordered ring, ring 1, in the structure. Overlapping atoms were restrained to have similar displacement parameters. The eight largest residual peaks in the final difference map (0.69–0.50 e Å^-3) were located less than 1.0 Å from the Eu atom.

Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SHELXTL (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

Fig. 1. Please provide figure cation with ellispoid probability level.

(4,4'-dimethyl-2,2'-bipyridyl)tris[3,3,3-trifluoro-1-(2-thenoyl)acetonato]- europium(III)

Crystal data

[Eu(C8H4F3O2S)3(C12H12N2)]	Dx = 1.673 Mg m^−3
Mr = 999.71	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pca21	Cell parameters from 5605 reflections
a = 20.781 (2) Å	θ = 2.1–29.6°
b = 10.7159 (12) Å	µ = 1.83 mm^−1
c = 17.8255 (19) Å	T = 170 K
V = 3969.6 (7) Å^3	Block, light orange
Z = 4	0.30 × 0.30 × 0.20 mm
F(000) = 1976

Data collection

Bruker CCD area-detector diffractometer	9109 independent reflections
Radiation source: fine-focus sealed tube	7963 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.035
ω scans	θmax = 27.6°, θmin = 1.9°
Absorption correction: multi-scan (Sheldrick, 2000)	h = −26→26
Tmin = 0.610, Tmax = 0.712	k = −13→13
47819 measured reflections	l = −23→23

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.026	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.062	w = 1/[σ^2(Fo^2) + (0.0226P)^2 + 1.4129P] where P = (Fo^2 + 2Fc^2)/3
S = 1.12	(Δ/σ)max = 0.001
9109 reflections	Δρmax = 0.69 e Å^−3
588 parameters	Δρmin = −0.41 e Å^−3
530 restraints	Absolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.020 (7)

Special details

Experimental. The structure was solved using SHELXS in the Bruker SHELXTL software package. Refinements were performed using SHELXL and illustrations were made using XP. Solution was achieved utilizing direct methods followed by Fourier synthesis.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Eu	0.112627 (6)	0.209028 (12)	0.08773 (4)	0.03152 (4)
S1_1	−0.02018 (5)	−0.05269 (10)	−0.09221 (7)	0.0538 (3)
C2_1	−0.07264 (18)	−0.0835 (3)	−0.1638 (2)	0.0559 (10)
H2A_1	−0.0885	−0.1645	−0.1751	0.067*
C3_1	−0.08884 (18)	0.0199 (4)	−0.20225 (19)	0.0563 (11)
H3A_1	−0.1179	0.0203	−0.2434	0.068*
C4_1	−0.05799 (17)	0.1274 (3)	−0.17471 (18)	0.0467 (9)
H4A_1	−0.0638	0.2084	−0.1954	0.056*
C5_1	−0.01870 (15)	0.1029 (2)	−0.11492 (16)	0.0399 (8)
C6_1	0.02317 (16)	0.1865 (3)	−0.07155 (18)	0.0364 (7)
C7_1	0.02940 (17)	0.3118 (3)	−0.0939 (2)	0.0400 (8)
H7A_1	0.0060	0.3403	−0.1363	0.048*
C8_1	0.06836 (16)	0.3943 (3)	−0.05609 (19)	0.0349 (7)
C9_1	0.08066 (19)	0.5242 (3)	−0.0907 (2)	0.0470 (9)
F1_1	0.04129 (14)	0.5500 (2)	−0.14797 (16)	0.0736 (7)
F2_1	0.07324 (13)	0.6145 (2)	−0.04122 (16)	0.0678 (7)
F3_1	0.14097 (14)	0.5315 (3)	−0.11521 (19)	0.0794 (9)
O1_1	0.05298 (12)	0.1383 (2)	−0.01716 (14)	0.0424 (6)
O2_1	0.09858 (12)	0.3789 (2)	0.00433 (16)	0.0430 (6)
S1A_2	0.04488 (5)	−0.24921 (9)	0.13568 (8)	0.0481 (3)	0.968 (4)
C2A_2	−0.00621 (19)	−0.3667 (3)	0.1609 (4)	0.0619 (13)	0.968 (4)
H2AA_2	0.0058	−0.4522	0.1625	0.074*	0.968 (4)
C3A_2	−0.06534 (19)	−0.3246 (3)	0.1781 (4)	0.0682 (14)	0.968 (4)
H3AA_2	−0.0997	−0.3771	0.1935	0.082*	0.968 (4)
C4A_2	−0.0706 (2)	−0.1942 (4)	0.1708 (6)	0.0556 (15)	0.968 (4)
H4AA_2	−0.1089	−0.1490	0.1812	0.067*	0.968 (4)
C5A_2	−0.01458 (13)	−0.1395 (2)	0.14714 (19)	0.0396 (8)	0.968 (4)
C5B_2	−0.01458 (13)	−0.1395 (2)	0.14714 (19)	0.0396 (8)	0.032
C4B_2	0.0334 (10)	−0.227 (2)	0.151 (6)	0.043 (6)	0.032 (4)
H4BB_2	0.0778	−0.2080	0.1446	0.052*	0.032 (4)
C3B_2	0.010 (2)	−0.348 (3)	0.164 (10)	0.057 (7)	0.032 (4)
H3BB_2	0.0362	−0.4204	0.1657	0.068*	0.032 (4)
C2B_2	−0.054 (2)	−0.350 (3)	0.175 (9)	0.064 (8)	0.032 (4)
H2BB_2	−0.0783	−0.4236	0.1844	0.077*	0.032 (4)
S1B_2	−0.0876 (12)	−0.204 (3)	0.170 (5)	0.055 (7)	0.032 (4)
C6_2	0.00001 (16)	−0.0073 (3)	0.13583 (18)	0.0355 (7)
C7_2	−0.05096 (16)	0.0807 (3)	0.1372 (2)	0.0418 (8)
H7B_2	−0.0939	0.0504	0.1391	0.050*
C8_2	−0.04145 (17)	0.2072 (3)	0.1359 (2)	0.0396 (7)
C9_2	−0.09943 (19)	0.2945 (4)	0.1419 (3)	0.0573 (11)
F1_2	−0.15569 (10)	0.2379 (2)	0.1314 (2)	0.0727 (7)
F2_2	−0.10184 (14)	0.3494 (3)	0.2083 (2)	0.0974 (11)
F3_2	−0.09553 (11)	0.3854 (3)	0.0921 (3)	0.1014 (11)
O1_2	0.05815 (10)	0.0229 (2)	0.12620 (13)	0.0356 (5)
O2_2	0.01104 (11)	0.2676 (2)	0.13139 (17)	0.0464 (6)
S1A_3	0.26730 (17)	−0.0474 (2)	0.2386 (2)	0.0559 (6)	0.713 (4)
C2A_3	0.3306 (5)	−0.0787 (5)	0.2971 (8)	0.062 (2)	0.713 (4)
H2AC_3	0.3505	−0.1582	0.3012	0.074*	0.713 (4)
C3A_3	0.3491 (5)	0.0222 (6)	0.3365 (7)	0.059 (2)	0.713 (4)
H3AC_3	0.3839	0.0221	0.3709	0.070*	0.713 (4)
C4A_3	0.3110 (7)	0.1277 (7)	0.3211 (8)	0.0502 (19)	0.713 (4)
H4AC_3	0.3165	0.2060	0.3452	0.060*	0.713 (4)
C5A_3	0.26525 (15)	0.1052 (2)	0.26741 (17)	0.0409 (8)	0.713 (4)
C5B_3	0.26525 (15)	0.1052 (2)	0.26741 (17)	0.0409 (8)	0.287
C4B_3	0.2716 (12)	−0.0191 (8)	0.2508 (13)	0.047 (4)	0.287 (4)
H4BD_3	0.2486	−0.0596	0.2117	0.056*	0.287 (4)
C3B_3	0.3159 (15)	−0.0800 (9)	0.2980 (18)	0.064 (5)	0.287 (4)
H3BD_3	0.3249	−0.1668	0.2956	0.077*	0.287 (4)
C2B_3	0.3441 (15)	−0.0016 (10)	0.3469 (17)	0.065 (6)	0.287 (4)
H2BD_3	0.3740	−0.0273	0.3842	0.079*	0.287 (4)
S1B_3	0.3199 (5)	0.1495 (7)	0.3345 (6)	0.0566 (15)	0.287 (4)
C6_3	0.21914 (17)	0.1881 (3)	0.2319 (2)	0.0405 (8)
C7_3	0.2191 (2)	0.3166 (4)	0.2504 (2)	0.0560 (11)
H7C_3	0.2492	0.3461	0.2864	0.067*
C8_3	0.1778 (2)	0.3993 (4)	0.2185 (3)	0.0570 (11)
C9_3	0.1820 (3)	0.5367 (5)	0.2427 (4)	0.0941 (19)
F1_3	0.2318 (2)	0.5613 (3)	0.2867 (3)	0.162 (2)
F2_3	0.1293 (2)	0.5705 (4)	0.2783 (3)	0.1294 (16)
F3_3	0.1868 (2)	0.6129 (3)	0.1854 (3)	0.1242 (14)
O1_3	0.18061 (10)	0.1394 (2)	0.18551 (13)	0.0365 (5)
O2_3	0.13579 (14)	0.3809 (3)	0.16853 (16)	0.0492 (6)
N1_4	0.22399 (13)	0.2751 (3)	0.03832 (17)	0.0371 (6)
C2_4	0.24148 (18)	0.3959 (3)	0.0419 (2)	0.0474 (9)
H2_4	0.2113	0.4550	0.0603	0.057*
C3_4	0.30138 (19)	0.4374 (4)	0.0200 (2)	0.0528 (10)
H3_4	0.3114	0.5238	0.0225	0.063*
C4_4	0.34688 (19)	0.3539 (4)	−0.0056 (2)	0.0531 (10)
C5_4	0.32873 (19)	0.2297 (4)	−0.0092 (2)	0.0546 (10)
H5_4	0.3586	0.1690	−0.0264	0.066*
C6_4	0.26744 (16)	0.1929 (3)	0.0120 (2)	0.0366 (7)
C7_4	0.24603 (16)	0.0606 (3)	0.00579 (19)	0.0373 (7)
C8_4	0.2839 (2)	−0.0305 (4)	−0.0258 (2)	0.0487 (9)
H8_4	0.3261	−0.0104	−0.0425	0.058*
C9_4	0.2612 (2)	−0.1509 (4)	−0.0333 (2)	0.0527 (9)
C10_4	0.2000 (2)	−0.1761 (4)	−0.0067 (2)	0.0547 (10)
H10_4	0.1829	−0.2582	−0.0094	0.066*
C11_4	0.1646 (2)	−0.0812 (3)	0.0236 (2)	0.0498 (9)
H11_4	0.1226	−0.1003	0.0412	0.060*
N12_4	0.18505 (14)	0.0375 (3)	0.03029 (16)	0.0380 (6)
C13_4	0.3020 (3)	−0.2488 (4)	−0.0718 (3)	0.0745 (15)
H13A_4	0.2787	−0.3283	−0.0729	0.112*
H13B_4	0.3424	−0.2595	−0.0443	0.112*
H13C_4	0.3114	−0.2221	−0.1233	0.112*
C14_4	0.4134 (2)	0.3934 (5)	−0.0298 (3)	0.0854 (18)
H14A_4	0.4377	0.3200	−0.0462	0.128*
H14B_4	0.4356	0.4330	0.0125	0.128*
H14C_4	0.4100	0.4529	−0.0713	0.128*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Eu	0.02751 (7)	0.03397 (7)	0.03309 (7)	−0.00574 (5)	−0.00421 (9)	0.00092 (10)
S1_1	0.0554 (6)	0.0535 (6)	0.0526 (6)	−0.0235 (5)	−0.0092 (5)	0.0050 (5)
C2_1	0.053 (2)	0.067 (3)	0.048 (2)	−0.027 (2)	0.0040 (19)	−0.0110 (19)
C3_1	0.042 (2)	0.087 (3)	0.040 (2)	−0.014 (2)	−0.0027 (17)	−0.014 (2)
C4_1	0.042 (2)	0.064 (2)	0.0337 (18)	−0.0025 (18)	−0.0068 (15)	−0.0030 (17)
C5_1	0.0328 (17)	0.054 (2)	0.0325 (17)	−0.0072 (15)	0.0001 (13)	−0.0026 (15)
C6_1	0.0341 (17)	0.0445 (18)	0.0307 (16)	−0.0052 (14)	0.0006 (13)	−0.0022 (14)
C7_1	0.0402 (19)	0.0447 (19)	0.0351 (17)	−0.0009 (15)	−0.0052 (15)	0.0054 (15)
C8_1	0.0312 (16)	0.0365 (17)	0.0372 (17)	0.0011 (13)	0.0049 (13)	0.0030 (14)
C9_1	0.043 (2)	0.042 (2)	0.056 (2)	−0.0014 (16)	0.0028 (18)	0.0125 (17)
F1_1	0.0927 (19)	0.0586 (15)	0.0696 (16)	−0.0042 (14)	−0.0192 (15)	0.0268 (13)
F2_1	0.0859 (18)	0.0393 (12)	0.0783 (17)	−0.0030 (12)	0.0011 (14)	−0.0018 (12)
F3_1	0.0553 (16)	0.0724 (18)	0.110 (3)	−0.0050 (14)	0.0301 (16)	0.0333 (17)
O1_1	0.0479 (14)	0.0400 (13)	0.0392 (13)	−0.0120 (11)	−0.0144 (11)	0.0041 (10)
O2_1	0.0438 (14)	0.0362 (13)	0.0489 (15)	−0.0083 (11)	−0.0105 (12)	0.0057 (11)
S1A_2	0.0515 (6)	0.0372 (5)	0.0556 (7)	0.0005 (4)	0.0076 (5)	0.0018 (4)
C2A_2	0.079 (3)	0.035 (2)	0.072 (3)	−0.010 (2)	0.018 (3)	−0.001 (2)
C3A_2	0.076 (3)	0.044 (2)	0.084 (3)	−0.019 (2)	0.024 (3)	−0.008 (3)
C4A_2	0.050 (3)	0.045 (2)	0.071 (3)	−0.014 (2)	0.018 (4)	−0.003 (3)
C5A_2	0.0422 (19)	0.0391 (17)	0.0376 (18)	−0.0069 (14)	0.0037 (14)	−0.0008 (15)
C5B_2	0.0422 (19)	0.0391 (17)	0.0376 (18)	−0.0069 (14)	0.0037 (14)	−0.0008 (15)
C4B_2	0.051 (10)	0.038 (9)	0.041 (15)	−0.006 (8)	0.016 (15)	0.009 (15)
C3B_2	0.070 (12)	0.038 (8)	0.063 (14)	−0.015 (10)	0.015 (14)	0.001 (14)
C2B_2	0.072 (13)	0.047 (10)	0.074 (18)	−0.026 (11)	0.019 (17)	−0.002 (17)
S1B_2	0.044 (10)	0.053 (11)	0.069 (17)	−0.032 (8)	0.003 (15)	−0.019 (13)
C6_2	0.0356 (17)	0.0414 (16)	0.0294 (16)	−0.0059 (13)	0.0012 (13)	0.0015 (14)
C7_2	0.0317 (16)	0.0430 (18)	0.051 (2)	−0.0050 (14)	−0.0013 (15)	0.0066 (16)
C8_2	0.0355 (17)	0.0434 (18)	0.0399 (19)	0.0023 (14)	−0.0003 (15)	0.0040 (16)
C9_2	0.038 (2)	0.048 (2)	0.086 (3)	−0.0030 (16)	0.004 (2)	0.015 (2)
F1_2	0.0319 (11)	0.0591 (14)	0.127 (2)	−0.0005 (10)	−0.0016 (13)	0.0108 (14)
F2_2	0.0705 (19)	0.082 (2)	0.140 (3)	0.0235 (16)	0.0074 (18)	−0.044 (2)
F3_2	0.0517 (12)	0.0805 (17)	0.172 (3)	0.0088 (12)	−0.003 (3)	0.065 (3)
O1_2	0.0306 (11)	0.0389 (12)	0.0373 (12)	−0.0036 (9)	−0.0004 (10)	0.0033 (10)
O2_2	0.0343 (13)	0.0402 (13)	0.0648 (17)	−0.0038 (10)	0.0028 (12)	0.0033 (12)
S1A_3	0.0574 (13)	0.0578 (11)	0.0526 (13)	0.0199 (10)	−0.0107 (9)	−0.0074 (9)
C2A_3	0.040 (5)	0.084 (4)	0.061 (5)	0.025 (3)	0.000 (4)	0.009 (4)
C3A_3	0.038 (4)	0.097 (5)	0.041 (4)	0.000 (4)	−0.007 (3)	0.013 (4)
C4A_3	0.044 (5)	0.074 (4)	0.033 (6)	−0.007 (4)	−0.008 (3)	−0.001 (3)
C5A_3	0.0335 (17)	0.059 (2)	0.0300 (16)	0.0010 (15)	−0.0016 (13)	−0.0058 (15)
C5B_3	0.0335 (17)	0.059 (2)	0.0300 (16)	0.0010 (15)	−0.0016 (13)	−0.0058 (15)
C4B_3	0.044 (8)	0.060 (6)	0.037 (9)	0.004 (7)	−0.001 (6)	0.006 (7)
C3B_3	0.052 (11)	0.081 (7)	0.059 (9)	0.019 (7)	0.006 (8)	0.013 (7)
C2B_3	0.050 (10)	0.102 (8)	0.045 (10)	0.007 (9)	−0.006 (8)	0.024 (8)
S1B_3	0.037 (3)	0.095 (4)	0.038 (3)	−0.002 (3)	−0.0173 (18)	−0.002 (2)
C6_3	0.0327 (17)	0.054 (2)	0.0344 (17)	0.0009 (15)	0.0003 (14)	−0.0031 (15)
C7_3	0.053 (2)	0.058 (2)	0.057 (3)	0.0033 (18)	−0.023 (2)	−0.0212 (19)
C8_3	0.054 (2)	0.053 (2)	0.063 (3)	0.0076 (18)	−0.023 (2)	−0.025 (2)
C9_3	0.097 (4)	0.068 (3)	0.117 (5)	0.030 (3)	−0.055 (4)	−0.046 (3)
F1_3	0.161 (4)	0.088 (2)	0.237 (5)	0.043 (2)	−0.131 (4)	−0.098 (3)
F2_3	0.140 (3)	0.106 (3)	0.142 (4)	0.057 (3)	−0.025 (3)	−0.074 (3)
F3_3	0.141 (3)	0.0477 (17)	0.184 (4)	−0.0061 (19)	−0.050 (3)	−0.030 (2)
O1_3	0.0326 (12)	0.0421 (13)	0.0347 (12)	−0.0033 (10)	−0.0061 (9)	−0.0015 (10)
O2_3	0.0428 (14)	0.0488 (15)	0.0560 (16)	0.0038 (13)	−0.0096 (14)	−0.0126 (12)
N1_4	0.0327 (14)	0.0340 (15)	0.0447 (16)	−0.0084 (11)	0.0026 (12)	0.0025 (12)
C2_4	0.0385 (19)	0.0375 (19)	0.066 (3)	−0.0059 (15)	0.0004 (18)	−0.0013 (18)
C3_4	0.049 (2)	0.042 (2)	0.067 (3)	−0.0186 (17)	0.0014 (19)	0.0024 (19)
C4_4	0.046 (2)	0.057 (2)	0.056 (2)	−0.0232 (18)	0.0082 (18)	−0.0110 (19)
C5_4	0.045 (2)	0.056 (2)	0.063 (3)	−0.0113 (17)	0.016 (2)	−0.019 (2)
C6_4	0.0352 (17)	0.0393 (17)	0.0351 (17)	−0.0096 (13)	0.0000 (14)	0.0007 (14)
C7_4	0.0413 (18)	0.0376 (17)	0.0332 (17)	−0.0057 (14)	0.0024 (14)	0.0007 (14)
C8_4	0.048 (2)	0.047 (2)	0.051 (2)	−0.0018 (16)	0.0101 (19)	0.0041 (18)
C9_4	0.066 (3)	0.044 (2)	0.048 (2)	0.0023 (19)	0.0124 (19)	−0.0001 (17)
C10_4	0.073 (3)	0.038 (2)	0.052 (2)	−0.0099 (18)	0.017 (2)	−0.0045 (17)
C11_4	0.060 (2)	0.045 (2)	0.045 (2)	−0.0155 (17)	0.0162 (18)	−0.0037 (16)
N12_4	0.0423 (16)	0.0376 (14)	0.0343 (14)	−0.0090 (12)	0.0045 (12)	−0.0049 (11)
C13_4	0.092 (4)	0.042 (2)	0.089 (4)	0.005 (2)	0.031 (3)	−0.002 (2)
C14_4	0.063 (3)	0.086 (4)	0.107 (4)	−0.037 (3)	0.042 (3)	−0.029 (3)

Geometric parameters (Å, º)

Eu—O2_2	2.336 (2)	S1A_3—C5A_3	1.714 (3)
Eu—O1_3	2.364 (2)	C2A_3—C3A_3	1.345 (4)
Eu—O1_1	2.368 (2)	C2A_3—H2AC_3	0.9500
Eu—O2_1	2.369 (3)	C3A_3—C4A_3	1.407 (5)
Eu—O2_3	2.387 (3)	C3A_3—H3AC_3	0.9500
Eu—O1_2	2.394 (2)	C4A_3—C5A_3	1.370 (4)
Eu—N1_4	2.575 (3)	C4A_3—H4AC_3	0.9500
Eu—N12_4	2.587 (3)	C5A_3—C6_3	1.452 (4)
S1_1—C2_1	1.711 (3)	C4B_3—C3B_3	1.408 (5)
S1_1—C5_1	1.716 (2)	C4B_3—H4BD_3	0.9500
C2_1—C3_1	1.346 (4)	C3B_3—C2B_3	1.345 (4)
C2_1—H2A_1	0.9500	C3B_3—H3BD_3	0.9500
C3_1—C4_1	1.407 (4)	C2B_3—S1B_3	1.710 (4)
C3_1—H3A_1	0.9500	C2B_3—H2BD_3	0.9500
C4_1—C5_1	1.368 (4)	C6_3—O1_3	1.264 (4)
C4_1—H4A_1	0.9500	C6_3—C7_3	1.416 (5)
C5_1—C6_1	1.469 (4)	C7_3—C8_3	1.359 (6)
C6_1—O1_1	1.261 (4)	C7_3—H7C_3	0.9500
C6_1—C7_1	1.407 (5)	C8_3—O2_3	1.263 (5)
C7_1—C8_1	1.375 (5)	C8_3—C9_3	1.537 (6)
C7_1—H7A_1	0.9500	C9_3—F3_3	1.312 (8)
C8_1—O2_1	1.258 (4)	C9_3—F2_3	1.318 (8)
C8_1—C9_1	1.544 (5)	C9_3—F1_3	1.325 (6)
C9_1—F2_1	1.318 (5)	N1_4—C2_4	1.346 (4)
C9_1—F3_1	1.330 (5)	N1_4—C6_4	1.346 (4)
C9_1—F1_1	1.338 (5)	C2_4—C3_4	1.378 (5)
S1A_2—C2A_2	1.707 (3)	C2_4—H2_4	0.9500
S1A_2—C5A_2	1.718 (2)	C3_4—C4_4	1.379 (6)
C2A_2—C3A_2	1.345 (4)	C3_4—H3_4	0.9500
C2A_2—H2AA_2	0.9500	C4_4—C5_4	1.385 (6)
C3A_2—C4A_2	1.408 (4)	C4_4—C14_4	1.508 (5)
C3A_2—H3AA_2	0.9500	C5_4—C6_4	1.386 (5)
C4A_2—C5A_2	1.370 (4)	C5_4—H5_4	0.9500
C4A_2—H4AA_2	0.9500	C6_4—C7_4	1.490 (4)
C5A_2—C6_2	1.463 (4)	C7_4—N12_4	1.363 (4)
C4B_2—C3B_2	1.408 (5)	C7_4—C8_4	1.375 (5)
C4B_2—H4BB_2	0.9500	C8_4—C9_4	1.381 (5)
C3B_2—C2B_2	1.345 (4)	C8_4—H8_4	0.9500
C3B_2—H3BB_2	0.9500	C9_4—C10_4	1.383 (6)
C2B_2—S1B_2	1.710 (4)	C9_4—C13_4	1.515 (6)
C2B_2—H2BB_2	0.9500	C10_4—C11_4	1.367 (5)
C6_2—O1_2	1.263 (4)	C10_4—H10_4	0.9500
C6_2—C7_2	1.418 (5)	C11_4—N12_4	1.345 (4)
C7_2—C8_2	1.370 (5)	C11_4—H11_4	0.9500
C7_2—H7B_2	0.9500	C13_4—H13A_4	0.9800
C8_2—O2_2	1.271 (4)	C13_4—H13B_4	0.9800
C8_2—C9_2	1.529 (5)	C13_4—H13C_4	0.9800
C9_2—F3_2	1.320 (5)	C14_4—H14A_4	0.9800
C9_2—F2_2	1.323 (6)	C14_4—H14B_4	0.9800
C9_2—F1_2	1.330 (5)	C14_4—H14C_4	0.9800
S1A_3—C2A_3	1.711 (3)
O2_2—Eu—O1_3	112.28 (9)	F3_2—C9_2—C8_2	110.9 (4)
O2_2—Eu—O1_1	82.88 (9)	F2_2—C9_2—C8_2	111.4 (4)
O1_3—Eu—O1_1	142.54 (8)	F1_2—C9_2—C8_2	113.8 (3)
O2_2—Eu—O2_1	83.75 (9)	C6_2—O1_2—Eu	134.8 (2)
O1_3—Eu—O2_1	141.17 (8)	C8_2—O2_2—Eu	131.3 (2)
O1_1—Eu—O2_1	71.70 (8)	C2A_3—S1A_3—C5A_3	91.36 (15)
O2_2—Eu—O2_3	76.93 (9)	C3A_3—C2A_3—S1A_3	112.3 (3)
O1_3—Eu—O2_3	71.23 (9)	C3A_3—C2A_3—H2AC_3	123.8
O1_1—Eu—O2_3	146.00 (9)	S1A_3—C2A_3—H2AC_3	123.8
O2_1—Eu—O2_3	79.08 (8)	C2A_3—C3A_3—C4A_3	112.6 (3)
O2_2—Eu—O1_2	72.60 (8)	C2A_3—C3A_3—H3AC_3	123.7
O1_3—Eu—O1_2	78.95 (7)	C4A_3—C3A_3—H3AC_3	123.7
O1_1—Eu—O1_2	73.25 (8)	C5A_3—C4A_3—C3A_3	112.6 (3)
O2_1—Eu—O1_2	139.64 (8)	C5A_3—C4A_3—H4AC_3	123.7
O2_3—Eu—O1_2	124.43 (9)	C3A_3—C4A_3—H4AC_3	123.7
O2_2—Eu—N1_4	148.44 (8)	C4A_3—C5A_3—C6_3	130.9 (3)
O1_3—Eu—N1_4	78.58 (9)	C4A_3—C5A_3—S1A_3	111.1 (2)
O1_1—Eu—N1_4	106.76 (9)	C6_3—C5A_3—S1A_3	118.0 (2)
O2_1—Eu—N1_4	71.62 (9)	C3B_3—C4B_3—H4BD_3	123.7
O2_3—Eu—N1_4	79.22 (10)	C2B_3—C3B_3—C4B_3	112.5 (3)
O1_2—Eu—N1_4	138.77 (8)	C2B_3—C3B_3—H3BD_3	123.7
O2_2—Eu—N12_4	148.06 (8)	C4B_3—C3B_3—H3BD_3	123.7
O1_3—Eu—N12_4	73.73 (8)	C3B_3—C2B_3—S1B_3	112.3 (3)
O1_1—Eu—N12_4	76.38 (9)	C3B_3—C2B_3—H2BD_3	123.8
O2_1—Eu—N12_4	111.69 (9)	S1B_3—C2B_3—H2BD_3	123.8
O2_3—Eu—N12_4	132.04 (9)	O1_3—C6_3—C7_3	123.6 (3)
O1_2—Eu—N12_4	78.26 (8)	O1_3—C6_3—C5A_3	116.8 (3)
N1_4—Eu—N12_4	62.44 (9)	C7_3—C6_3—C5A_3	119.6 (3)
C2_1—S1_1—C5_1	91.32 (14)	C8_3—C7_3—C6_3	122.5 (3)
C3_1—C2_1—S1_1	112.4 (2)	C8_3—C7_3—H7C_3	118.7
C3_1—C2_1—H2A_1	123.8	C6_3—C7_3—H7C_3	118.7
S1_1—C2_1—H2A_1	123.8	O2_3—C8_3—C7_3	129.1 (4)
C2_1—C3_1—C4_1	112.5 (3)	O2_3—C8_3—C9_3	112.8 (4)
C2_1—C3_1—H3A_1	123.7	C7_3—C8_3—C9_3	118.1 (4)
C4_1—C3_1—H3A_1	123.7	F3_3—C9_3—F2_3	105.4 (5)
C5_1—C4_1—C3_1	112.7 (3)	F3_3—C9_3—F1_3	106.2 (6)
C5_1—C4_1—H4A_1	123.6	F2_3—C9_3—F1_3	108.1 (5)
C3_1—C4_1—H4A_1	123.6	F3_3—C9_3—C8_3	112.4 (5)
C4_1—C5_1—C6_1	130.3 (3)	F2_3—C9_3—C8_3	110.6 (6)
C4_1—C5_1—S1_1	111.1 (2)	F1_3—C9_3—C8_3	113.7 (4)
C6_1—C5_1—S1_1	118.6 (2)	C6_3—O1_3—Eu	136.9 (2)
O1_1—C6_1—C7_1	124.3 (3)	C8_3—O2_3—Eu	133.3 (3)
O1_1—C6_1—C5_1	116.4 (3)	C2_4—N1_4—C6_4	117.7 (3)
C7_1—C6_1—C5_1	119.2 (3)	C2_4—N1_4—Eu	119.4 (2)
C8_1—C7_1—C6_1	121.9 (3)	C6_4—N1_4—Eu	122.8 (2)
C8_1—C7_1—H7A_1	119.0	N1_4—C2_4—C3_4	122.7 (4)
C6_1—C7_1—H7A_1	119.0	N1_4—C2_4—H2_4	118.6
O2_1—C8_1—C7_1	129.0 (3)	C3_4—C2_4—H2_4	118.6
O2_1—C8_1—C9_1	112.2 (3)	C2_4—C3_4—C4_4	120.2 (4)
C7_1—C8_1—C9_1	118.8 (3)	C2_4—C3_4—H3_4	119.9
F2_1—C9_1—F3_1	106.7 (3)	C4_4—C3_4—H3_4	119.9
F2_1—C9_1—F1_1	106.7 (3)	C3_4—C4_4—C5_4	116.9 (3)
F3_1—C9_1—F1_1	108.3 (4)	C3_4—C4_4—C14_4	122.7 (4)
F2_1—C9_1—C8_1	112.1 (3)	C5_4—C4_4—C14_4	120.4 (4)
F3_1—C9_1—C8_1	109.9 (3)	C4_4—C5_4—C6_4	120.7 (4)
F1_1—C9_1—C8_1	113.0 (3)	C4_4—C5_4—H5_4	119.6
C6_1—O1_1—Eu	137.1 (2)	C6_4—C5_4—H5_4	119.6
C8_1—O2_1—Eu	134.4 (2)	N1_4—C6_4—C5_4	121.7 (3)
C2A_2—S1A_2—C5A_2	91.49 (14)	N1_4—C6_4—C7_4	116.6 (3)
C3A_2—C2A_2—S1A_2	112.4 (2)	C5_4—C6_4—C7_4	121.7 (3)
C3A_2—C2A_2—H2AA_2	123.8	N12_4—C7_4—C8_4	122.3 (3)
S1A_2—C2A_2—H2AA_2	123.8	N12_4—C7_4—C6_4	115.3 (3)
C2A_2—C3A_2—C4A_2	112.5 (3)	C8_4—C7_4—C6_4	122.3 (3)
C2A_2—C3A_2—H3AA_2	123.8	C7_4—C8_4—C9_4	120.5 (4)
C4A_2—C3A_2—H3AA_2	123.8	C7_4—C8_4—H8_4	119.7
C5A_2—C4A_2—C3A_2	112.8 (3)	C9_4—C8_4—H8_4	119.7
C5A_2—C4A_2—H4AA_2	123.6	C8_4—C9_4—C10_4	117.6 (4)
C3A_2—C4A_2—H4AA_2	123.6	C8_4—C9_4—C13_4	120.0 (4)
C4A_2—C5A_2—C6_2	129.3 (3)	C10_4—C9_4—C13_4	122.3 (4)
C4A_2—C5A_2—S1A_2	110.8 (2)	C11_4—C10_4—C9_4	119.0 (4)
C6_2—C5A_2—S1A_2	119.8 (2)	C11_4—C10_4—H10_4	120.5
C3B_2—C4B_2—H4BB_2	123.7	C9_4—C10_4—H10_4	120.5
C2B_2—C3B_2—C4B_2	112.5 (3)	N12_4—C11_4—C10_4	124.6 (4)
C2B_2—C3B_2—H3BB_2	123.7	N12_4—C11_4—H11_4	117.7
C4B_2—C3B_2—H3BB_2	123.7	C10_4—C11_4—H11_4	117.7
C3B_2—C2B_2—S1B_2	112.3 (3)	C11_4—N12_4—C7_4	115.9 (3)
C3B_2—C2B_2—H2BB_2	123.8	C11_4—N12_4—Eu	121.5 (2)
S1B_2—C2B_2—H2BB_2	123.8	C7_4—N12_4—Eu	122.6 (2)
O1_2—C6_2—C7_2	123.1 (3)	C9_4—C13_4—H13A_4	109.5
O1_2—C6_2—C5A_2	117.7 (3)	C9_4—C13_4—H13B_4	109.5
C7_2—C6_2—C5A_2	119.1 (3)	H13A_4—C13_4—H13B_4	109.5
C8_2—C7_2—C6_2	123.4 (3)	C9_4—C13_4—H13C_4	109.5
C8_2—C7_2—H7B_2	118.3	H13A_4—C13_4—H13C_4	109.5
C6_2—C7_2—H7B_2	118.3	H13B_4—C13_4—H13C_4	109.5
O2_2—C8_2—C7_2	129.0 (3)	C4_4—C14_4—H14A_4	109.5
O2_2—C8_2—C9_2	111.6 (3)	C4_4—C14_4—H14B_4	109.5
C7_2—C8_2—C9_2	119.4 (3)	H14A_4—C14_4—H14B_4	109.5
F3_2—C9_2—F2_2	106.0 (4)	C4_4—C14_4—H14C_4	109.5
F3_2—C9_2—F1_2	107.2 (4)	H14A_4—C14_4—H14C_4	109.5
F2_2—C9_2—F1_2	107.1 (4)	H14B_4—C14_4—H14C_4	109.5
C5_1—S1_1—C2_1—C3_1	−0.9 (3)	C4A_3—C5A_3—C6_3—C7_3	2.4 (13)
S1_1—C2_1—C3_1—C4_1	0.8 (5)	S1A_3—C5A_3—C6_3—C7_3	−175.5 (4)
C2_1—C3_1—C4_1—C5_1	−0.2 (5)	O1_3—C6_3—C7_3—C8_3	−1.0 (7)
C3_1—C4_1—C5_1—C6_1	178.0 (4)	C5A_3—C6_3—C7_3—C8_3	179.2 (4)
C3_1—C4_1—C5_1—S1_1	−0.4 (4)	C6_3—C7_3—C8_3—O2_3	−2.1 (8)
C2_1—S1_1—C5_1—C4_1	0.7 (3)	C6_3—C7_3—C8_3—C9_3	180.0 (5)
C2_1—S1_1—C5_1—C6_1	−177.9 (3)	O2_3—C8_3—C9_3—F3_3	−50.0 (7)
C4_1—C5_1—C6_1—O1_1	178.0 (4)	C7_3—C8_3—C9_3—F3_3	128.3 (5)
S1_1—C5_1—C6_1—O1_1	−3.7 (4)	O2_3—C8_3—C9_3—F2_3	67.6 (7)
C4_1—C5_1—C6_1—C7_1	−4.1 (6)	C7_3—C8_3—C9_3—F2_3	−114.2 (5)
S1_1—C5_1—C6_1—C7_1	174.2 (3)	O2_3—C8_3—C9_3—F1_3	−170.6 (6)
O1_1—C6_1—C7_1—C8_1	−1.6 (6)	C7_3—C8_3—C9_3—F1_3	7.6 (9)
C5_1—C6_1—C7_1—C8_1	−179.3 (3)	C7_3—C6_3—O1_3—Eu	18.3 (6)
C6_1—C7_1—C8_1—O2_1	−6.9 (6)	C5A_3—C6_3—O1_3—Eu	−161.9 (2)
C6_1—C7_1—C8_1—C9_1	170.9 (3)	O2_2—Eu—O1_3—C6_3	−87.0 (3)
O2_1—C8_1—C9_1—F2_1	−49.3 (4)	O1_1—Eu—O1_3—C6_3	164.7 (3)
C7_1—C8_1—C9_1—F2_1	132.6 (3)	O2_1—Eu—O1_3—C6_3	21.8 (4)
O2_1—C8_1—C9_1—F3_1	69.2 (4)	O2_3—Eu—O1_3—C6_3	−20.4 (3)
C7_1—C8_1—C9_1—F3_1	−109.0 (4)	O1_2—Eu—O1_3—C6_3	−152.8 (3)
O2_1—C8_1—C9_1—F1_1	−169.8 (3)	N1_4—Eu—O1_3—C6_3	62.0 (3)
C7_1—C8_1—C9_1—F1_1	12.0 (5)	N12_4—Eu—O1_3—C6_3	126.3 (3)
C7_1—C6_1—O1_1—Eu	14.8 (5)	C7_3—C8_3—O2_3—Eu	−10.7 (8)
C5_1—C6_1—O1_1—Eu	−167.4 (2)	C9_3—C8_3—O2_3—Eu	167.3 (4)
O2_2—Eu—O1_1—C6_1	72.1 (3)	O2_2—Eu—O2_3—C8_3	135.2 (4)
O1_3—Eu—O1_1—C6_1	−170.1 (3)	O1_3—Eu—O2_3—C8_3	15.8 (4)
O2_1—Eu—O1_1—C6_1	−13.6 (3)	O1_1—Eu—O2_3—C8_3	−169.7 (4)
O2_3—Eu—O1_1—C6_1	18.5 (4)	O2_1—Eu—O2_3—C8_3	−138.8 (4)
O1_2—Eu—O1_1—C6_1	146.1 (3)	O1_2—Eu—O2_3—C8_3	77.3 (4)
N1_4—Eu—O1_1—C6_1	−77.1 (3)	N1_4—Eu—O2_3—C8_3	−65.6 (4)
N12_4—Eu—O1_1—C6_1	−132.3 (3)	N12_4—Eu—O2_3—C8_3	−29.3 (4)
C7_1—C8_1—O2_1—Eu	2.7 (6)	O2_2—Eu—N1_4—C2_4	10.4 (4)
C9_1—C8_1—O2_1—Eu	−175.3 (2)	O1_3—Eu—N1_4—C2_4	−103.8 (3)
O2_2—Eu—O2_1—C8_1	−79.9 (3)	O1_1—Eu—N1_4—C2_4	114.4 (3)
O1_3—Eu—O2_1—C8_1	161.9 (3)	O2_1—Eu—N1_4—C2_4	50.9 (3)
O1_1—Eu—O2_1—C8_1	4.7 (3)	O2_3—Eu—N1_4—C2_4	−31.0 (3)
O2_3—Eu—O2_1—C8_1	−157.7 (3)	O1_2—Eu—N1_4—C2_4	−162.0 (2)
O1_2—Eu—O2_1—C8_1	−26.3 (4)	N12_4—Eu—N1_4—C2_4	178.7 (3)
N1_4—Eu—O2_1—C8_1	120.1 (3)	O2_2—Eu—N1_4—C6_4	−172.9 (2)
N12_4—Eu—O2_1—C8_1	71.2 (3)	O1_3—Eu—N1_4—C6_4	72.9 (3)
C5A_2—S1A_2—C2A_2—C3A_2	−0.8 (5)	O1_1—Eu—N1_4—C6_4	−68.8 (3)
S1A_2—C2A_2—C3A_2—C4A_2	0.3 (7)	O2_1—Eu—N1_4—C6_4	−132.4 (3)
C2A_2—C3A_2—C4A_2—C5A_2	0.6 (9)	O2_3—Eu—N1_4—C6_4	145.7 (3)
C3A_2—C4A_2—C5A_2—C6_2	−177.3 (5)	O1_2—Eu—N1_4—C6_4	14.7 (3)
C3A_2—C4A_2—C5A_2—S1A_2	−1.2 (9)	N12_4—Eu—N1_4—C6_4	−4.6 (2)
C2A_2—S1A_2—C5A_2—C4A_2	1.1 (6)	C6_4—N1_4—C2_4—C3_4	−0.1 (6)
C2A_2—S1A_2—C5A_2—C6_2	177.7 (3)	Eu—N1_4—C2_4—C3_4	176.8 (3)
C4B_2—C3B_2—C2B_2—S1B_2	−1 (9)	N1_4—C2_4—C3_4—C4_4	−1.3 (7)
C4A_2—C5A_2—C6_2—O1_2	168.0 (7)	C2_4—C3_4—C4_4—C5_4	1.2 (6)
S1A_2—C5A_2—C6_2—O1_2	−7.9 (4)	C2_4—C3_4—C4_4—C14_4	−179.5 (5)
C4A_2—C5A_2—C6_2—C7_2	−11.2 (8)	C3_4—C4_4—C5_4—C6_4	0.2 (6)
S1A_2—C5A_2—C6_2—C7_2	173.0 (3)	C14_4—C4_4—C5_4—C6_4	−179.2 (5)
O1_2—C6_2—C7_2—C8_2	−6.9 (6)	C2_4—N1_4—C6_4—C5_4	1.5 (5)
C5A_2—C6_2—C7_2—C8_2	172.2 (3)	Eu—N1_4—C6_4—C5_4	−175.2 (3)
C6_2—C7_2—C8_2—O2_2	2.1 (6)	C2_4—N1_4—C6_4—C7_4	−177.7 (3)
C6_2—C7_2—C8_2—C9_2	−176.6 (4)	Eu—N1_4—C6_4—C7_4	5.5 (4)
O2_2—C8_2—C9_2—F3_2	46.1 (5)	C4_4—C5_4—C6_4—N1_4	−1.6 (6)
C7_2—C8_2—C9_2—F3_2	−135.0 (4)	C4_4—C5_4—C6_4—C7_4	177.6 (4)
O2_2—C8_2—C9_2—F2_2	−71.7 (4)	N1_4—C6_4—C7_4—N12_4	−2.2 (5)
C7_2—C8_2—C9_2—F2_2	107.2 (4)	C5_4—C6_4—C7_4—N12_4	178.5 (3)
O2_2—C8_2—C9_2—F1_2	167.1 (4)	N1_4—C6_4—C7_4—C8_4	174.7 (3)
C7_2—C8_2—C9_2—F1_2	−14.0 (6)	C5_4—C6_4—C7_4—C8_4	−4.5 (6)
C7_2—C6_2—O1_2—Eu	−11.8 (5)	N12_4—C7_4—C8_4—C9_4	−0.5 (6)
C5A_2—C6_2—O1_2—Eu	169.1 (2)	C6_4—C7_4—C8_4—C9_4	−177.2 (4)
O2_2—Eu—O1_2—C6_2	21.3 (3)	C7_4—C8_4—C9_4—C10_4	−1.3 (6)
O1_3—Eu—O1_2—C6_2	139.1 (3)	C7_4—C8_4—C9_4—C13_4	176.8 (4)
O1_1—Eu—O1_2—C6_2	−66.3 (3)	C8_4—C9_4—C10_4—C11_4	1.8 (6)
O2_1—Eu—O1_2—C6_2	−35.7 (3)	C13_4—C9_4—C10_4—C11_4	−176.3 (4)
O2_3—Eu—O1_2—C6_2	81.1 (3)	C9_4—C10_4—C11_4—N12_4	−0.5 (7)
N1_4—Eu—O1_2—C6_2	−162.9 (3)	C10_4—C11_4—N12_4—C7_4	−1.2 (6)
N12_4—Eu—O1_2—C6_2	−145.5 (3)	C10_4—C11_4—N12_4—Eu	179.4 (3)
C7_2—C8_2—O2_2—Eu	21.2 (6)	C8_4—C7_4—N12_4—C11_4	1.7 (5)
C9_2—C8_2—O2_2—Eu	−160.0 (3)	C6_4—C7_4—N12_4—C11_4	178.7 (3)
O1_3—Eu—O2_2—C8_2	−94.6 (3)	C8_4—C7_4—N12_4—Eu	−178.9 (3)
O1_1—Eu—O2_2—C8_2	49.9 (3)	C6_4—C7_4—N12_4—Eu	−2.0 (4)
O2_1—Eu—O2_2—C8_2	122.1 (3)	O2_2—Eu—N12_4—C11_4	−9.0 (4)
O2_3—Eu—O2_2—C8_2	−157.7 (3)	O1_3—Eu—N12_4—C11_4	97.2 (3)
O1_2—Eu—O2_2—C8_2	−24.8 (3)	O1_1—Eu—N12_4—C11_4	−60.0 (3)
N1_4—Eu—O2_2—C8_2	160.5 (3)	O2_1—Eu—N12_4—C11_4	−123.6 (3)
N12_4—Eu—O2_2—C8_2	0.3 (4)	O2_3—Eu—N12_4—C11_4	141.6 (3)
C5A_3—S1A_3—C2A_3—C3A_3	0.1 (11)	O1_2—Eu—N12_4—C11_4	15.4 (3)
S1A_3—C2A_3—C3A_3—C4A_3	1.2 (17)	N1_4—Eu—N12_4—C11_4	−177.4 (3)
C2A_3—C3A_3—C4A_3—C5A_3	−2 (2)	O2_2—Eu—N12_4—C7_4	171.7 (2)
C3A_3—C4A_3—C5A_3—C6_3	−175.8 (9)	O1_3—Eu—N12_4—C7_4	−82.1 (3)
C3A_3—C4A_3—C5A_3—S1A_3	2.2 (17)	O1_1—Eu—N12_4—C7_4	120.7 (3)
C2A_3—S1A_3—C5A_3—C4A_3	−1.3 (11)	O2_1—Eu—N12_4—C7_4	57.1 (3)
C2A_3—S1A_3—C5A_3—C6_3	177.0 (6)	O2_3—Eu—N12_4—C7_4	−37.7 (3)
C4B_3—C3B_3—C2B_3—S1B_3	−2 (4)	O1_2—Eu—N12_4—C7_4	−163.9 (3)
C4A_3—C5A_3—C6_3—O1_3	−177.4 (12)	N1_4—Eu—N12_4—C7_4	3.3 (2)
S1A_3—C5A_3—C6_3—O1_3	4.7 (5)