catena-Poly­[europium(III)-tri-μ-2,3-di­methoxy­benzoato]

The title compound, [Eu(C₉H₉O₄)₃]_n or [Eu(2,3-DMOBA)₃]_n, where 2,3-DMOBA is 2,3-di­methoxy­benzoate, is an infinite one-dimensional non-centrosymmetric coordination polymer. The unique Eu^III atom is bridged by six carboxyl­ate ligands; it is ennea-coordinated and has a distorted tricapped trigonal prism geometry. The Eu—O distances are in the range 2.315 (3)–2.959 (5) Å.

S1. Comment

The variety of coordinating structures of lanthanide(III) carboxylates and their potential chemical and biological applications in luminescent probes and labels are interesting themes of coordination chemistry. Lanthanide(III) carboxylates are found to form many kinds of one-, two- and three-dimensional coordination polymers, where the carboxylate ligands act as the bridges between the metal atoms. In ennea-coordinated lanthanide(III) complexes, the central metal atom is in a monocapped square antiprism or tricapped trigonal prism geometry. The geometries of these complexes are thought to depend on the size of the ligand compared with that of the metal atom, as well as on the substituted groups of the carboxylate. Here, we report the preparation and crystal structure of the title compound, (I). \sch

Compound (I) is a infinite one-dimensional non-centrosymmetric coordination polymer. The unique Eu^III atom is bridged by six carboxylate ligands (Fig. 1); each Eu^III atom is coordinated to nine O atoms of six carboxylate ligands. A distorted tricapped trigonal prism arrangement is found. Atoms O1ⁱ, O6 and O9, and atoms O2, O7ⁱ and O10ⁱ, take the tips of the upper and lower triangles of the prism, respectively, and the dihedral angle between them is 6.0° [symmetry code: (i) −x, 1/2 + y, 1/2 − z]. Atoms O1, O5 and O6ⁱ take the three cap positions (Fig. 2). A similar coordination environment has been observed previously for lanthanide(III) complexes such as cerium(III) acetate (Sadikov et al., 1967), neodymium(III) (methylthio)acetate (Kondo et al., 1982), and [Eu₃(ClCH₂CO₂)₉(H₂O)₅]_n, [Nd₃(ClCH₂CO₂)₉(H₂O)₅]_n and [La₃(ClCH₂CO₂)₉(H₂O)₅]_n (Imai et al., 1987).

All the carboxylate ligands are coordinated to the Eu^III atoms and can be classified into three different coordination modes in the crystal structure of (I). In the first of these, the carboxylate ligand is in a tridentate coordination mode: carboxyl group O1—C1—O2 is in a bridging-chelating mode, in which both O atoms chelate one Eu^III atom and one of them is also simultaneously linked to another Eu^III atom, to form a tridentate bridge. In the second, the carboxylate ligand is in a bidentate coordination mode: carboxyl group O9—C19—O10 is in a conventional bridging mode, in which two O atoms coordinate to two different Eu^III atoms to form a bidentate bridge. In the third, the carboxylate ligand is in a tetradentate coordination mode: carboxyl group O5—C10—O6 is in a bridging-chelating mode, with the O atom of the methoxy group coordinated to the Eu^III atom to form a tetradentate bridge.

In the tridentate coordination mode, the two C—O bond lengths of the carboxyl group (C1—O1 and C1—O2) are not significantly different and the C—O double bond is delocalized. In the typical form of a bridging-chelating mode, the Ln—O, Ln—O' and Ln'-O' bond lengths (Ln and Ln' are adjacent lanthanide atoms, and O' is the O atom which is simultaneously bonded to two lanthanide atoms) are about the same, and the Ln—O—C, Ln—O'-C and Ln'-O'-C bond angles are in the ranges 90–100, 90–100 and 140–150°, respectively. Many complexes containing a bridging-chelating mode are deformed from the ideal shape. In the case of (I), the Eu1—O1 bond length and C1—O2—Eu1 bond angle increase, while the C1—O1—Eu1 bond angle decreases. This deformation of the tridentate coordination ligand is thought to tend toward the form of the bidentate one.

In the bidentate coordination mode, the two C—O bond lengths of the carboxyl group (C19—O9 and C19—O10) are not significantly different and the C—O double bond is probably delocalized. These angles in (I) are in the normal ranges and the difference between the two Eu—O bonds is very small. Therefore, the deformation of this mode is thought to be small.

In the tetradentate coordination mode, the Ln—O, Ln—O' and Ln'-O' bond lengths (Eu1—O5, Eu1—O6 and Eu1ⁱ—O6) are in the range 2.409 (3)–2.500 (4) Å, and the Ln—O—C and Ln—O'-C bond angles (Eu1—O5—C10 and Eu1—O6—C10) are in the range 93.9 (3)–93.9 (3)°. These data show that this mode has the ideal shape for a bridging-chelating mode. Atom O7 of the methoxy group in one of the aromatic carboxylate ligands bonds with an adjacent Eu atom, similar to what is found in the complex Nd(2—CH₃OC₆H₄COO)₃·4H₂O (Polynova et al., 1987). The Eu—O(methoxy) bond length [2.703 (4) Å] is comparable with the corresponding values for the analogous bonds in the complexes [Eu(2,2,6,6-tetramethylheptan-3,5-dione)₃]₂(2,5,8,11-tetraoxadodecane) (Drake et al., 1993), Eu(hexafluoroacetylacetonato)₃(diglyme) (Kang et al., 1997) and Eu₂(5,11,17,23-tetrabutyl-25,27-dihydroxy-26-carboxymethoxy- 28-diethylamidomethoxycalix(4)arene]₂(EtOH)₃(CH₂Cl₂)₂ (Beer et al., 1996).

S2. Experimental

2,3-Dimethoxybenzoic acid (1.5 mmol, 255 mg) was dissolved in ethanol (20 ml). The pH of the solution was adjusted to 6 with 2M NaOH solution. To the resulting solution was added Eu(NO₃)₃·6H₂O (0.5 mmol, 223 mg) in water (5 ml). The reaction was stirred for 4 h at 333 K. A white precipitate was formed and filtered. Crystals of (I) suitable for X-ray analysis were obtained from the filtrate after several days at room temperature. Analysis found: C 46.21, H 3.74%; calculated for C₂₇H₂₇EuO₁₂: C 46.63, H 3.91%.

S3. Refinement

H atoms were placed at calculated positions and refined in a riding model, with C—H distances in the range 0.93–0.96 Å and U_iso(H) = 1.2U_eq(C) (1.5 for methyl C).

Computing details

Data collection: RAPID AUTO (Rigaku, 2001); cell refinement: RAPID AUTO; data reduction: RAPID AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens, 1994); software used to prepare material for publication: SHELXTL (Siemens, 1995).

Figures

	Fig. 1. The coordination environment of the Eu^III atom in (I), showing 30% probability displacement ellipsoids and the atom-numbering scheme. H atoms have been omitted for clarity [symmetry code: (i) −x, 1/2 + y, 1/2 − z]. Please check added symmetry code.
	Fig. 2. The schematic representation of the coordination geometry of the Eu^III atom in (I) [symmetry code: (i) −x, 1/2 + y, 1/2 − z].

catena-Poly[europium(III)-tri-µ-2,3-dimethoxybenzoato]

Crystal data

[Eu(C9H9O4)3]	Dx = 1.767 Mg m^−3
Mr = 695.45	Melting point: Not measured K
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
a = 18.9555 (14) Å	Cell parameters from 20233 reflections
b = 8.0426 (4) Å	θ = 2.5–27.5°
c = 17.1475 (10) Å	µ = 2.47 mm^−1
V = 2614.2 (3) Å^3	T = 293 K
Z = 4	Block, colourless
F(000) = 1392	0.33 × 0.21 × 0.16 mm

Data collection

Rigaku R-AXIS RAPID image-plate diffractometer	5640 independent reflections
Radiation source: rotating anode	4984 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.000
oscillation scans	θmax = 27.5°, θmin = 2.5°
Absorption correction: empirical (using intensity measurements) (ABSCOR; Higashi, 1995)	h = −24→24
Tmin = 0.543, Tmax = 0.674	k = −10→10
5640 measured reflections	l = −21→21

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)] = 0.028	H-atom parameters constrained
wR(F^2) = 0.067	w = 1/[σ^2(Fo^2) + (0.0212P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.004
5640 reflections	Δρmax = 0.86 e Å^−3
367 parameters	Δρmin = −0.80 e Å^−3
0 restraints	Absolute structure: Flack (1983), with 2495 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.011 (15)

Special details

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
Eu1	0.01194 (1)	0.40310 (2)	0.28583 (1)	0.02322 (6)
O1	0.0782 (2)	0.0713 (6)	0.27178 (19)	0.0462 (12)
O2	0.0619 (2)	0.2178 (4)	0.3776 (2)	0.0364 (10)
O3	0.1354 (3)	0.1169 (6)	0.5053 (2)	0.0460 (11)
O4	0.2473 (3)	−0.0423 (6)	0.5598 (2)	0.0474 (12)
O5	−0.0969 (2)	0.3125 (5)	0.3565 (2)	0.0389 (10)
O6	−0.0654 (2)	0.1594 (4)	0.25658 (19)	0.0301 (9)
O7	−0.1539 (2)	−0.0733 (4)	0.20444 (19)	0.0324 (8)
O8	−0.2813 (2)	−0.2100 (5)	0.2143 (3)	0.0529 (11)
O9	0.0317 (2)	0.3494 (4)	0.15500 (18)	0.0385 (11)
O10	0.0015 (2)	0.0942 (4)	0.11301 (13)	0.0316 (9)
O11	−0.0279 (2)	0.0764 (5)	−0.0421 (2)	0.0422 (11)
O12	0.0161 (3)	0.1671 (5)	−0.18185 (18)	0.0491 (12)
C1	0.0951 (3)	0.1042 (7)	0.3419 (3)	0.0322 (11)
C2	0.1577 (3)	0.0210 (6)	0.3758 (3)	0.0318 (12)
C3	0.1749 (3)	0.0254 (7)	0.4548 (3)	0.0336 (13)
C4	0.2351 (3)	−0.0580 (7)	0.4821 (3)	0.0387 (14)
C5	0.2786 (4)	−0.1429 (7)	0.4313 (4)	0.0425 (15)
H5A	0.3187	−0.1972	0.4494	0.051*
C6	0.2612 (4)	−0.1459 (7)	0.3518 (3)	0.0404 (14)
H6A	0.2902	−0.2022	0.3169	0.048*
C7	0.2017 (4)	−0.0665 (6)	0.3249 (3)	0.0356 (13)
H7A	0.1905	−0.0711	0.2721	0.043*
C8	0.1042 (5)	0.0288 (10)	0.5697 (4)	0.060 (2)
H8A	0.0565	0.0659	0.5769	0.090*
H8B	0.1308	0.0502	0.6162	0.090*
H8C	0.1044	−0.0883	0.5589	0.090*
C9	0.3065 (4)	−0.1269 (9)	0.5918 (4)	0.0526 (18)
H9A	0.3067	−0.1139	0.6474	0.079*
H9B	0.3491	−0.0810	0.5705	0.079*
H9C	0.3037	−0.2429	0.5790	0.079*
C10	−0.1098 (3)	0.1952 (6)	0.3095 (3)	0.0274 (11)
C11	−0.1783 (3)	0.1038 (7)	0.3165 (2)	0.0284 (10)
C12	−0.1984 (3)	−0.0174 (7)	0.2632 (3)	0.0327 (12)
C13	−0.2651 (3)	−0.0917 (8)	0.2698 (3)	0.0401 (13)
C14	−0.3098 (4)	−0.0464 (8)	0.3303 (4)	0.0476 (16)
H14A	−0.3536	−0.0973	0.3356	0.057*
C15	−0.2891 (4)	0.0742 (9)	0.3825 (3)	0.0484 (16)
H15A	−0.3193	0.1054	0.4227	0.058*
C16	−0.2240 (4)	0.1490 (7)	0.3755 (3)	0.0391 (15)
H16A	−0.2106	0.2308	0.4109	0.047*
C17	−0.1752 (4)	−0.0157 (8)	0.1264 (3)	0.0468 (16)
H17A	−0.2234	−0.0464	0.1170	0.070*
H17B	−0.1455	−0.0662	0.0878	0.070*
H17C	−0.1706	0.1030	0.1236	0.070*
C18	−0.3433 (4)	−0.3042 (8)	0.2262 (5)	0.060 (2)
H18A	−0.3498	−0.3794	0.1834	0.090*
H18B	−0.3832	−0.2308	0.2296	0.090*
H18C	−0.3392	−0.3663	0.2738	0.090*
C19	0.0210 (3)	0.2425 (5)	0.1022 (2)	0.0263 (11)
C20	0.0361 (3)	0.2994 (6)	0.0193 (2)	0.0278 (12)
C21	0.0169 (4)	0.2092 (6)	−0.0469 (3)	0.0318 (12)
C22	0.0389 (4)	0.2645 (7)	−0.1205 (3)	0.0360 (13)
C23	0.0793 (3)	0.4041 (7)	−0.1287 (2)	0.0355 (12)
H23A	0.0946	0.4362	−0.1780	0.043*
C24	0.0976 (4)	0.4985 (6)	−0.0639 (3)	0.0381 (15)
H24A	0.1235	0.5960	−0.0691	0.046*
C25	0.0758 (4)	0.4423 (6)	0.0094 (3)	0.0378 (15)
H25A	0.0886	0.5033	0.0533	0.045*
C26	0.0062 (5)	−0.0834 (6)	−0.0407 (3)	0.061 (2)
H26A	−0.0275	−0.1672	−0.0263	0.092*
H26B	0.0439	−0.0817	−0.0034	0.092*
H26C	0.0248	−0.1079	−0.0915	0.092*
C27	0.0394 (4)	0.2127 (11)	−0.2567 (3)	0.059 (2)
H27A	0.0207	0.1365	−0.2945	0.088*
H27B	0.0900	0.2096	−0.2582	0.088*
H27C	0.0234	0.3232	−0.2684	0.088*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Eu1	0.02751 (12)	0.02260 (8)	0.01956 (8)	0.00044 (11)	0.00105 (11)	−0.00003 (8)
O1	0.035 (2)	0.080 (3)	0.0237 (17)	−0.023 (2)	−0.0042 (16)	−0.0009 (18)
O2	0.041 (3)	0.0279 (16)	0.0404 (19)	0.0065 (18)	−0.0070 (19)	0.0033 (14)
O3	0.052 (3)	0.051 (2)	0.0350 (18)	0.016 (2)	−0.0019 (18)	−0.0012 (18)
O4	0.041 (3)	0.068 (3)	0.0326 (18)	0.012 (2)	−0.015 (2)	−0.0073 (16)
O5	0.044 (3)	0.0386 (18)	0.0340 (17)	−0.0019 (19)	0.0101 (19)	−0.0136 (15)
O6	0.030 (2)	0.0298 (16)	0.0308 (17)	0.0056 (16)	0.0064 (16)	−0.0009 (13)
O7	0.032 (2)	0.0352 (17)	0.0302 (16)	0.0023 (16)	0.0044 (16)	0.0001 (14)
O8	0.040 (3)	0.047 (2)	0.072 (3)	−0.014 (2)	0.003 (3)	−0.013 (2)
O9	0.052 (3)	0.0408 (17)	0.0228 (15)	−0.0076 (18)	0.0060 (17)	−0.0034 (12)
O10	0.051 (3)	0.0249 (11)	0.0184 (10)	−0.003 (2)	0.0046 (15)	0.0098 (10)
O11	0.049 (3)	0.041 (2)	0.0364 (16)	−0.012 (2)	0.0008 (18)	−0.0034 (15)
O12	0.068 (3)	0.060 (2)	0.0194 (14)	−0.009 (3)	0.000 (2)	−0.0046 (14)
C1	0.025 (3)	0.034 (2)	0.037 (2)	−0.009 (3)	−0.001 (2)	0.008 (2)
C2	0.029 (4)	0.032 (2)	0.034 (3)	−0.006 (2)	−0.005 (2)	−0.0005 (19)
C3	0.032 (4)	0.043 (2)	0.026 (2)	−0.001 (3)	−0.002 (2)	0.0024 (19)
C4	0.031 (4)	0.048 (3)	0.037 (2)	0.002 (3)	−0.003 (3)	−0.003 (2)
C5	0.027 (4)	0.045 (3)	0.055 (3)	0.002 (3)	−0.002 (3)	−0.001 (2)
C6	0.038 (4)	0.035 (3)	0.048 (3)	0.004 (3)	0.005 (3)	−0.004 (2)
C7	0.044 (4)	0.030 (2)	0.032 (2)	−0.001 (2)	0.001 (2)	−0.0037 (18)
C8	0.056 (5)	0.073 (4)	0.052 (4)	0.003 (4)	0.016 (4)	−0.018 (3)
C9	0.047 (5)	0.060 (4)	0.051 (3)	0.008 (4)	−0.019 (3)	0.008 (3)
C10	0.033 (3)	0.024 (2)	0.025 (2)	0.004 (2)	0.002 (2)	−0.0045 (16)
C11	0.031 (3)	0.0267 (19)	0.0271 (18)	0.006 (3)	0.009 (2)	0.0016 (19)
C12	0.029 (3)	0.035 (2)	0.034 (3)	0.004 (2)	0.004 (2)	0.0041 (19)
C13	0.032 (3)	0.040 (2)	0.048 (3)	−0.002 (3)	0.001 (2)	−0.004 (3)
C14	0.031 (4)	0.051 (3)	0.061 (4)	−0.010 (3)	0.008 (3)	0.001 (3)
C15	0.039 (4)	0.056 (4)	0.050 (3)	−0.001 (3)	0.018 (3)	−0.002 (3)
C16	0.043 (4)	0.037 (3)	0.037 (3)	0.002 (3)	0.005 (3)	−0.006 (2)
C17	0.050 (5)	0.059 (3)	0.032 (3)	0.014 (3)	−0.009 (3)	−0.005 (2)
C18	0.038 (4)	0.045 (3)	0.098 (6)	−0.005 (3)	−0.007 (4)	−0.004 (3)
C19	0.029 (4)	0.0262 (19)	0.0234 (18)	−0.001 (2)	0.004 (2)	0.0026 (14)
C20	0.037 (4)	0.0258 (19)	0.0202 (19)	0.005 (2)	0.003 (2)	0.0010 (16)
C21	0.036 (3)	0.031 (2)	0.029 (2)	0.002 (3)	−0.003 (3)	0.0048 (16)
C22	0.038 (4)	0.045 (3)	0.024 (2)	0.001 (3)	−0.003 (2)	−0.0035 (19)
C23	0.044 (4)	0.037 (2)	0.025 (2)	0.002 (3)	0.005 (2)	0.002 (2)
C24	0.056 (5)	0.028 (2)	0.030 (3)	−0.009 (3)	0.008 (3)	0.0032 (19)
C25	0.054 (5)	0.034 (3)	0.026 (2)	−0.007 (3)	−0.001 (3)	−0.0013 (17)
C26	0.107 (7)	0.033 (2)	0.045 (2)	−0.012 (5)	0.004 (4)	−0.012 (2)
C27	0.063 (5)	0.088 (5)	0.024 (2)	−0.016 (4)	0.011 (3)	−0.008 (3)

Geometric parameters (Å, º)

Eu1—O1	2.959 (5)	C6—H6A	0.93
Eu1—O1^i	2.392 (4)	C7—H7A	0.93
Eu1—O2	2.365 (4)	C8—H8A	0.96
Eu1—O5	2.500 (4)	C8—H8B	0.96
Eu1—O6	2.498 (4)	C8—H8C	0.96
Eu1—O6^i	2.409 (3)	C9—H9A	0.96
Eu1—O7^i	2.703 (4)	C9—H9B	0.96
Eu1—O9	2.315 (3)	C9—H9C	0.96
Eu1—O10^i	2.332 (3)	C10—C11	1.497 (8)
Eu1—Eu1^ii	4.2291 (2)	C11—C16	1.380 (7)
O1—C1	1.272 (6)	C11—C12	1.389 (7)
O1—Eu1^ii	2.392 (4)	C12—C13	1.404 (9)
O2—C1	1.267 (7)	C13—C14	1.389 (8)
O3—C3	1.361 (7)	C14—C15	1.376 (9)
O3—C8	1.440 (8)	C14—H14A	0.93
O4—C4	1.360 (6)	C15—C16	1.379 (10)
O4—C9	1.422 (8)	C15—H15A	0.93
O5—C10	1.264 (6)	C16—H16A	0.93
O6—C10	1.271 (6)	C17—H17A	0.96
O6—Eu1^ii	2.409 (3)	C17—H17B	0.96
O7—C12	1.388 (6)	C17—H17C	0.96
O7—C17	1.472 (6)	C18—H18A	0.96
O7—Eu1^ii	2.703 (4)	C18—H18B	0.96
O8—C13	1.380 (7)	C18—H18C	0.96
O8—C18	1.413 (8)	C19—C20	1.521 (6)
O9—C19	1.265 (5)	C20—C25	1.384 (7)
O10—C19	1.262 (6)	C20—C21	1.396 (6)
O10—Eu1^ii	2.332 (3)	C21—C22	1.402 (7)
O11—C21	1.367 (7)	C22—C23	1.366 (8)
O11—C26	1.438 (7)	C23—C24	1.390 (7)
O12—C22	1.381 (6)	C23—H23A	0.93
O12—C27	1.406 (6)	C24—C25	1.398 (7)
C1—C2	1.481 (8)	C24—H24A	0.93
C2—C3	1.393 (7)	C25—H25A	0.93
C2—C7	1.398 (8)	C26—H26A	0.96
C3—C4	1.404 (8)	C26—H26B	0.96
C4—C5	1.380 (8)	C26—H26C	0.96
C5—C6	1.402 (8)	C27—H27A	0.96
C5—H5A	0.93	C27—H27B	0.96
C6—C7	1.376 (9)	C27—H27C	0.96
O9—Eu1—O10^i	149.50 (11)	C2—C3—C4	120.2 (5)
O9—Eu1—O2	117.54 (14)	O4—C4—C5	124.3 (6)
O10^i—Eu1—O2	87.94 (12)	O4—C4—C3	114.9 (5)
O9—Eu1—O1^i	79.69 (14)	C5—C4—C3	120.8 (5)
O10^i—Eu1—O1^i	81.75 (13)	C4—C5—C6	118.8 (6)
O2—Eu1—O1^i	156.45 (15)	C4—C5—H5A	120.6
O9—Eu1—O6^i	78.41 (12)	C6—C5—H5A	120.6
O10^i—Eu1—O6^i	72.93 (12)	C7—C6—C5	120.7 (6)
O2—Eu1—O6^i	124.87 (15)	C7—C6—H6A	119.7
O1^i—Eu1—O6^i	72.06 (16)	C5—C6—H6A	119.7
O9—Eu1—O6	75.77 (12)	C6—C7—C2	120.9 (5)
O10^i—Eu1—O6	127.04 (13)	C6—C7—H7A	119.5
O2—Eu1—O6	82.76 (13)	C2—C7—H7A	119.5
O1^i—Eu1—O6	86.65 (15)	O3—C8—H8A	109.5
O6^i—Eu1—O6	149.02 (4)	O3—C8—H8B	109.5
O9—Eu1—O5	123.28 (14)	H8A—C8—H8B	109.5
O10^i—Eu1—O5	75.03 (12)	O3—C8—H8C	109.5
O2—Eu1—O5	79.87 (15)	H8A—C8—H8C	109.5
O1^i—Eu1—O5	77.04 (15)	H8B—C8—H8C	109.5
O6^i—Eu1—O5	137.94 (13)	O4—C9—H9A	109.5
O6—Eu1—O5	52.02 (11)	O4—C9—H9B	109.5
O9—Eu1—O7^i	84.93 (14)	H9A—C9—H9B	109.5
O10^i—Eu1—O7^i	90.94 (12)	O4—C9—H9C	109.5
O2—Eu1—O7^i	66.72 (13)	H9A—C9—H9C	109.5
O1^i—Eu1—O7^i	134.17 (14)	H9B—C9—H9C	109.5
O6^i—Eu1—O7^i	62.60 (12)	O5—C10—O6	119.7 (5)
O6—Eu1—O7^i	130.67 (11)	O5—C10—C11	119.0 (5)
O5—Eu1—O7^i	144.27 (12)	O6—C10—C11	121.3 (4)
O9—Eu1—C10	99.11 (13)	O5—C10—Eu1	60.1 (3)
O10^i—Eu1—C10	100.97 (13)	O6—C10—Eu1	60.0 (3)
O2—Eu1—C10	82.00 (14)	C11—C10—Eu1	172.7 (3)
O1^i—Eu1—C10	79.29 (16)	C16—C11—C12	119.7 (5)
O6^i—Eu1—C10	151.25 (14)	C16—C11—C10	118.2 (5)
O6—Eu1—C10	26.14 (12)	C12—C11—C10	122.0 (4)
O5—Eu1—C10	25.98 (12)	O7—C12—C11	122.6 (5)
O7^i—Eu1—C10	146.12 (13)	O7—C12—C13	117.9 (5)
O9—Eu1—O1	71.58 (11)	C11—C12—C13	119.5 (5)
O10^i—Eu1—O1	134.54 (10)	O8—C13—C14	124.1 (6)
O2—Eu1—O1	46.85 (11)	O8—C13—C12	116.0 (5)
O1^i—Eu1—O1	141.19 (11)	C14—C13—C12	119.9 (6)
O6^i—Eu1—O1	124.65 (12)	C15—C14—C13	119.8 (6)
O6—Eu1—O1	61.65 (12)	C15—C14—H14A	120.1
O5—Eu1—O1	97.28 (12)	C13—C14—H14A	120.1
O7^i—Eu1—O1	69.26 (11)	C14—C15—C16	120.5 (6)
C10—Eu1—O1	80.09 (13)	C14—C15—H15A	119.8
O9—Eu1—C1	94.31 (14)	C16—C15—H15A	119.8
O10^i—Eu1—C1	110.10 (13)	C15—C16—C11	120.7 (5)
O2—Eu1—C1	23.23 (13)	C15—C16—H16A	119.7
O1^i—Eu1—C1	161.92 (16)	C11—C16—H16A	119.7
O6^i—Eu1—C1	123.75 (14)	O7—C17—H17A	109.5
O6—Eu1—C1	75.32 (13)	O7—C17—H17B	109.5
O5—Eu1—C1	92.53 (14)	H17A—C17—H17B	109.5
O7^i—Eu1—C1	61.21 (12)	O7—C17—H17C	109.5
C10—Eu1—C1	84.92 (14)	H17A—C17—H17C	109.5
O1—Eu1—C1	24.49 (12)	H17B—C17—H17C	109.5
O9—Eu1—Eu1^ii	63.79 (9)	O8—C18—H18A	109.5
O10^i—Eu1—Eu1^ii	146.23 (8)	O8—C18—H18B	109.5
O2—Eu1—Eu1^ii	68.71 (9)	H18A—C18—H18B	109.5
O1^i—Eu1—Eu1^ii	109.95 (12)	O8—C18—H18C	109.5
O6^i—Eu1—Eu1^ii	140.43 (8)	H18A—C18—H18C	109.5
O6—Eu1—Eu1^ii	29.89 (9)	H18B—C18—H18C	109.5
O5—Eu1—Eu1^ii	77.02 (8)	O10—C19—O9	125.7 (4)
O7^i—Eu1—Eu1^ii	101.02 (7)	O10—C19—C20	118.5 (4)
C10—Eu1—Eu1^ii	53.35 (9)	O9—C19—C20	115.8 (4)
O1—Eu1—Eu1^ii	33.30 (8)	C25—C20—C21	118.3 (5)
C1—Eu1—Eu1^ii	52.68 (10)	C25—C20—C19	117.8 (4)
C1—O1—Eu1^ii	133.5 (4)	C21—C20—C19	123.7 (4)
C1—O1—Eu1	80.9 (4)	O11—C21—C20	121.3 (4)
Eu1^ii—O1—Eu1	103.92 (16)	O11—C21—C22	119.2 (5)
C1—O2—Eu1	109.4 (3)	C20—C21—C22	119.3 (5)
C3—O3—C8	116.6 (5)	C23—C22—O12	124.3 (5)
C4—O4—C9	117.9 (5)	C23—C22—C21	121.3 (5)
C10—O5—Eu1	94.0 (3)	O12—C22—C21	114.4 (5)
C10—O6—Eu1^ii	133.5 (3)	C22—C23—C24	120.4 (5)
C10—O6—Eu1	93.9 (3)	C22—C23—H23A	119.8
Eu1^ii—O6—Eu1	119.00 (17)	C24—C23—H23A	119.8
C12—O7—C17	113.0 (4)	C23—C24—C25	118.0 (5)
C12—O7—Eu1^ii	125.6 (3)	C23—C24—H24A	121.0
C17—O7—Eu1^ii	110.6 (3)	C25—C24—H24A	121.0
C13—O8—C18	117.0 (5)	C20—C25—C24	122.6 (5)
C19—O9—Eu1	142.6 (3)	C20—C25—H25A	118.7
C19—O10—Eu1^ii	139.8 (3)	C24—C25—H25A	118.7
C21—O11—C26	114.8 (5)	O11—C26—H26A	109.5
C22—O12—C27	116.6 (5)	O11—C26—H26B	109.5
O2—C1—O1	118.8 (5)	H26A—C26—H26B	109.5
O2—C1—C2	122.3 (5)	O11—C26—H26C	109.5
O1—C1—C2	118.6 (5)	H26A—C26—H26C	109.5
O2—C1—Eu1	47.4 (3)	H26B—C26—H26C	109.5
O1—C1—Eu1	74.6 (4)	O12—C27—H27A	109.5
C2—C1—Eu1	154.1 (4)	O12—C27—H27B	109.5
C3—C2—C7	118.7 (5)	H27A—C27—H27B	109.5
C3—C2—C1	123.9 (5)	O12—C27—H27C	109.5
C7—C2—C1	117.4 (5)	H27A—C27—H27C	109.5
O3—C3—C2	120.2 (5)	H27B—C27—H27C	109.5
O3—C3—C4	119.6 (5)

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