Di-[mu]-benzoato-[kappa]³O,O':O';[kappa]³O:O,O'-bis[aqua­bis­(benzoato-[kappa]²O,O')(dimethylformamide-[kappa]O)europium(III)]

The title dimeric complex, [Eu₂(C₇H₅O₂)₆(C₃H₇NO)₂(H₂O)₂], is centrosymmetric, implying that pairs of equivalent Eu³⁺ ions and ligands lie trans to each other and that the two Eu³⁺ ions have exactly the same coordination environment. Each Eu³⁺ ion is nine-coordinated by two bidentate benzoate ligands, two bridging tridentate chelating benzoate ligands, and one dimethylformamide and one water molecule. The coordination polyhedron of each Eu³⁺ ion can be described with a distorted monocapped square-anti­prismatic geometry. The mol­ecular structure is stabilized by intra- and inter­molecular hydrogen bonds between the water mol­ecules and benzoate O atoms.

Key indicators

• Single-crystal X-ray study
• T = 291 K
• Mean [sigma](C-C) = 0.009 Å
• R factor = 0.045
• wR factor = 0.120
• Data-to-parameter ratio = 13.6

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......      0.978
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Eu1    --  O1      ..        6.0 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Eu1    --  O5      ..        7.7 su
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         O3
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        Eu1
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         N1
PLAT342_ALERT_3_C Low Bond Precision on  C-C Bonds ...............     0.0094 Ang
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600         92
PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF ....          2

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          3
PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF ....          ?
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Eu1    --  O4_a    ..       16.8 su
PLAT764_ALERT_4_G Overcomplete CIF Bond List Detected (Rep/Expd) .       1.13 Ratio
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          3
PLAT909_ALERT_3_G Percentage of Observed Data at Theta(Max) still          84 Perc.

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   9 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   6 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   7 ALERT type 2 Indicator that the structure model may be wrong or deficient
   6 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

---

S1. Comment

Because of their excellent luminescent properties (Chin et al., 1994; Singh et al., 2002), rare earth–carboxylic acid complexes have been widely studied and applied in many fields. Distinct structure features with various rare earths (Qiu et al., 2007; Gubina et al., 2000) or ligands (Jin et al., 1996; Wang et al., 2003) have been reported. The title compound, (I) was synthesized and its structure was determined. Similar crystal structure with benzoate as ligands have been reported recently (Ooi et al., 2010).

The centrosymmetric structure of the title complex (I) is shown in Fig. 1. The two Eu³⁺ ions are bridged by two tridentate bridging carboxylates. Each of the two Eu³⁺ ions is further coordinated by two chelating carboxlates, one DMF molecule and one water molecule, with an overall coordination number of nine. Eu—O bond distances are presented in Table 1.

In the crystal structure, intermolecular O7—H7B···O6ⁱⁱ hydrogen bonds (Table 2) link molecules into chains along the b axis (Fig. 2). The molecular structure is stabilized by intramolecular O7—H7A···O2ⁱ hydrogen bonds (Table 2).

Related literature

For luminescence properties of rare earth–carboxylic acid complexes, see: Chin et al. (1994); Singh et al. (2002). For related compounds, see: Jin et al. (1996); Gubina et al. (2000); Wang et al. (2003); Qiu et al. (2007); Ooi et al. (2010).

S2. Experimental

0.5 g Eu₂O₃ (Strem, 99.99%) was dissolved in 5 ml 37% HCl and the solution was evaporated to dryness. 10 ml water was added to the residue and the pH was adjusted to 8 by the addition of NH₃ (aq). The ensuing precipitate was filtered, washed with water and dried. This precipitate was added to a solution containing 1 g C₆H₅COOH and 20 ml DMF with stirring. The mixture was vigorously stirred and filtered. The filtrate was put in a beaker covered with parafilm and left in a dark fume cupboard at room temperature to form colorless needle crystals.

S3. Refinement

All aromatic and methyl H atoms were positioned geometrically with C—H = 0.93 and 0.96 Å, and were constrained to ride on their parent C atoms with U_iso(H) = 1.2U_eq(C) and 1.5U_eq(C), respectively. The DANG and DFIX restraints were used in order to keep the geometry of the water molecule reasonable.

Computing details

Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis PRO (Oxford Diffraction, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure of (I), with atom labels and 50% probability displacement ellipsoids for non-H atoms. The suffix A corresponds to the symmetry code [-x + 1, -y + 1, -z + 1].
	Fig. 2. The packing of (I), viewed along the a axis. C—H···O hydrogen bonds are shown as yellow dashed lines in bold.

Di-µ-benzoato- κ³O,O':O';κ³O:O,O'- bis[aquabis(benzoato-κ²O,O')(dimethylformamide- κO)europium(III)]

Crystal data

[Eu2(C7H5O2)6(C3H7NO)2(H2O)2]	F(000) = 1208
Mr = 1212.80	Dx = 1.653 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2ybc	Cell parameters from 5244 reflections
a = 11.6395 (2) Å	θ = 3.5–67.5°
b = 8.3692 (1) Å	µ = 18.84 mm^−1
c = 25.5235 (4) Å	T = 291 K
β = 101.460 (2)°	Block, colourless
V = 2436.76 (6) Å^3	0.36 × 0.32 × 0.32 mm
Z = 2

Data collection

Oxford Gemini S Ultra diffractometer	4294 independent reflections
Radiation source: Enhance Ultra (Cu) X-ray source	3860 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.035
Detector resolution: 15.9149 pixels mm^-1	θmax = 67.6°, θmin = 3.5°
ω scans	h = −13→9
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	k = −9→5
Tmin = 0.056, Tmax = 0.065	l = −30→30
8782 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.120	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0781P)^2] where P = (Fo^2 + 2Fc^2)/3
4294 reflections	(Δ/σ)max = 0.003
315 parameters	Δρmax = 1.20 e Å^−3
3 restraints	Δρmin = −1.92 e Å^−3

Special details

Experimental. CrysAlisPro (Oxford Diffraction, 2010). Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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	0.58936 (2)	0.32204 (3)	0.555114 (10)	0.02985 (13)
O1	0.7648 (3)	0.4223 (4)	0.62602 (15)	0.0471 (8)
O5	0.5539 (3)	0.2337 (5)	0.64080 (14)	0.0455 (8)
O8	0.7148 (3)	0.0976 (5)	0.55948 (16)	0.0499 (9)
O2	0.6119 (3)	0.5789 (4)	0.59914 (14)	0.0426 (8)
O7	0.5164 (4)	0.2066 (5)	0.46868 (15)	0.0460 (8)
O4	0.4078 (3)	0.4576 (4)	0.53174 (15)	0.0450 (8)
O6	0.4632 (3)	0.0941 (4)	0.57245 (14)	0.0442 (8)
O3	0.7419 (3)	0.4010 (5)	0.50855 (15)	0.0530 (10)
C1	0.7736 (4)	0.6905 (6)	0.65945 (19)	0.0347 (11)
N1	0.8798 (4)	−0.0405 (6)	0.5577 (2)	0.0521 (11)
C8	0.7618 (4)	0.5287 (6)	0.42852 (19)	0.0379 (10)
C15	0.4233 (4)	0.0286 (6)	0.6587 (2)	0.0414 (11)
C14	0.6945 (4)	0.4870 (6)	0.47094 (19)	0.0366 (10)
C16	0.4494 (5)	0.0601 (8)	0.7132 (2)	0.0546 (14)
H16	0.5050	0.1374	0.7265	0.065*
C9	0.8819 (5)	0.5075 (8)	0.4393 (2)	0.0503 (14)
H9	0.9175	0.4610	0.4716	0.060*
C22	0.8222 (5)	0.0822 (7)	0.5720 (3)	0.0530 (13)
H22	0.8650	0.1618	0.5926	0.064*
C21	0.4839 (4)	0.1220 (6)	0.62194 (19)	0.0378 (10)
C20	0.3412 (5)	−0.0855 (8)	0.6391 (3)	0.0540 (14)
H20	0.3239	−0.1083	0.6027	0.065*
C6	0.8917 (6)	0.6821 (7)	0.6827 (3)	0.0544 (16)
H6	0.9329	0.5878	0.6808	0.065*
C7	0.7149 (4)	0.5550 (6)	0.62677 (18)	0.0366 (10)
C10	0.9505 (6)	0.5531 (9)	0.4038 (3)	0.0681 (19)
H10	1.0315	0.5405	0.4122	0.082*
C19	0.2840 (6)	−0.1669 (8)	0.6742 (4)	0.070 (2)
H19	0.2274	−0.2430	0.6611	0.084*
C18	0.3111 (6)	−0.1349 (10)	0.7283 (3)	0.070 (2)
H18	0.2733	−0.1902	0.7516	0.084*
C13	0.7090 (6)	0.5896 (8)	0.3796 (2)	0.0622 (17)
H13	0.6281	0.6020	0.3713	0.075*
C17	0.3936 (6)	−0.0219 (9)	0.7476 (3)	0.0668 (18)
H17	0.4120	−0.0005	0.7841	0.080*
C24	1.0054 (6)	−0.0566 (11)	0.5768 (4)	0.088 (3)
H24B	1.0207	−0.1451	0.6011	0.132*
H24A	1.0358	0.0396	0.5949	0.132*
H24C	1.0428	−0.0750	0.5470	0.132*
C5	0.9487 (7)	0.8130 (9)	0.7088 (3)	0.071 (2)
H5	1.0283	0.8074	0.7237	0.085*
C4	0.8876 (7)	0.9514 (9)	0.7128 (3)	0.077 (2)
H4	0.9261	1.0399	0.7300	0.093*
C12	0.7762 (8)	0.6330 (10)	0.3423 (3)	0.085 (3)
H12	0.7403	0.6717	0.3089	0.102*
C23	0.8170 (8)	−0.1668 (8)	0.5251 (4)	0.078 (2)
H23B	0.8175	−0.2616	0.5463	0.118*
H23A	0.8545	−0.1886	0.4956	0.118*
H23C	0.7376	−0.1339	0.5119	0.118*
C2	0.7126 (6)	0.8298 (7)	0.6634 (3)	0.0581 (16)
H2	0.6336	0.8371	0.6475	0.070*
C11	0.8975 (8)	0.6176 (10)	0.3556 (3)	0.082 (2)
H11	0.9431	0.6514	0.3317	0.098*
C3	0.7697 (7)	0.9596 (8)	0.6914 (3)	0.078 (2)
H3	0.7280	1.0519	0.6955	0.093*
H7B	0.527 (8)	0.112 (5)	0.458 (4)	0.117*
H7A	0.470 (7)	0.253 (10)	0.443 (3)	0.117*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Eu1	0.03041 (19)	0.0315 (2)	0.02777 (18)	0.00101 (9)	0.00612 (12)	−0.00123 (9)
O1	0.0428 (19)	0.048 (2)	0.048 (2)	0.0050 (16)	0.0030 (15)	−0.0044 (17)
O5	0.050 (2)	0.047 (2)	0.0392 (18)	−0.0082 (17)	0.0086 (15)	−0.0080 (17)
O8	0.050 (2)	0.042 (2)	0.057 (2)	0.0100 (17)	0.0084 (17)	−0.0019 (18)
O2	0.0427 (18)	0.0357 (19)	0.0443 (18)	0.0032 (14)	−0.0039 (14)	−0.0070 (15)
O7	0.061 (2)	0.0381 (19)	0.0350 (18)	0.0043 (18)	−0.0003 (16)	−0.0049 (15)
O4	0.0327 (17)	0.053 (2)	0.051 (2)	0.0026 (15)	0.0118 (15)	−0.0110 (17)
O6	0.060 (2)	0.0393 (19)	0.0350 (18)	−0.0067 (16)	0.0138 (16)	0.0023 (15)
O3	0.0423 (19)	0.073 (3)	0.046 (2)	0.0038 (19)	0.0142 (16)	0.012 (2)
C1	0.037 (3)	0.040 (3)	0.025 (2)	0.0001 (19)	0.0017 (19)	−0.0030 (18)
N1	0.048 (2)	0.048 (3)	0.061 (3)	0.009 (2)	0.013 (2)	0.002 (2)
C8	0.037 (2)	0.045 (3)	0.035 (2)	0.004 (2)	0.0158 (19)	−0.004 (2)
C15	0.039 (3)	0.041 (3)	0.046 (3)	0.006 (2)	0.012 (2)	0.011 (2)
C14	0.029 (2)	0.044 (3)	0.038 (2)	−0.003 (2)	0.0085 (19)	−0.006 (2)
C16	0.064 (3)	0.062 (4)	0.040 (3)	0.000 (3)	0.015 (3)	0.006 (3)
C9	0.038 (3)	0.067 (4)	0.049 (3)	−0.004 (3)	0.016 (2)	−0.008 (3)
C22	0.055 (3)	0.044 (3)	0.058 (3)	−0.001 (3)	0.005 (3)	−0.001 (3)
C21	0.040 (3)	0.038 (3)	0.036 (2)	0.006 (2)	0.010 (2)	0.006 (2)
C20	0.052 (3)	0.058 (4)	0.054 (3)	−0.005 (3)	0.017 (3)	0.004 (3)
C6	0.049 (3)	0.058 (4)	0.049 (3)	0.005 (2)	−0.010 (3)	−0.010 (3)
C7	0.036 (2)	0.044 (3)	0.030 (2)	0.004 (2)	0.0063 (18)	−0.001 (2)
C10	0.059 (4)	0.078 (5)	0.078 (5)	−0.005 (3)	0.040 (4)	−0.005 (4)
C19	0.056 (4)	0.064 (4)	0.093 (6)	−0.011 (3)	0.022 (4)	0.019 (4)
C18	0.063 (4)	0.080 (5)	0.074 (5)	0.010 (4)	0.029 (4)	0.032 (4)
C13	0.069 (4)	0.076 (4)	0.046 (3)	0.036 (3)	0.022 (3)	0.012 (3)
C17	0.079 (4)	0.079 (5)	0.048 (3)	0.008 (4)	0.026 (3)	0.018 (3)
C24	0.061 (4)	0.100 (6)	0.101 (6)	0.029 (4)	0.011 (4)	0.014 (5)
C5	0.060 (4)	0.078 (5)	0.063 (4)	−0.008 (3)	−0.014 (3)	−0.008 (3)
C4	0.093 (5)	0.060 (4)	0.062 (4)	−0.017 (4)	−0.026 (4)	−0.009 (3)
C12	0.128 (7)	0.085 (5)	0.054 (4)	0.053 (5)	0.047 (4)	0.025 (4)
C23	0.083 (5)	0.060 (4)	0.095 (6)	0.006 (3)	0.024 (5)	−0.022 (4)
C2	0.054 (4)	0.059 (4)	0.053 (4)	0.008 (3)	−0.010 (3)	−0.013 (3)
C11	0.107 (6)	0.068 (5)	0.091 (6)	0.018 (4)	0.072 (5)	0.016 (4)
C3	0.099 (5)	0.051 (4)	0.066 (4)	0.012 (4)	−0.026 (4)	−0.027 (3)

Geometric parameters (Å, º)

Eu1—O8	2.368 (4)	C16—C17	1.374 (8)
Eu1—O4	2.368 (3)	C16—H16	0.9300
Eu1—O7	2.404 (4)	C9—C10	1.377 (8)
Eu1—O2	2.416 (3)	C9—H9	0.9300
Eu1—O3	2.416 (3)	C22—H22	0.9300
Eu1—O5	2.420 (4)	C20—C19	1.395 (9)
Eu1—O6	2.500 (3)	C20—H20	0.9300
Eu1—O1	2.584 (4)	C6—C5	1.380 (10)
Eu1—C21	2.837 (5)	C6—H6	0.9300
Eu1—C7	2.867 (5)	C10—C11	1.371 (11)
Eu1—O4^i	2.889 (4)	C10—H10	0.9300
Eu1—C14	3.011 (5)	C19—C18	1.380 (12)
O1—C7	1.255 (6)	C19—H19	0.9300
O5—C21	1.271 (6)	C18—C17	1.368 (11)
O8—C22	1.235 (7)	C18—H18	0.9300
O2—C7	1.280 (6)	C13—C12	1.394 (9)
O7—H7B	0.86 (2)	C13—H13	0.9300
O7—H7A	0.86 (2)	C17—H17	0.9300
O4—C14^i	1.267 (5)	C24—H24B	0.9600
O4—Eu1^i	2.889 (4)	C24—H24A	0.9600
O6—C21	1.260 (6)	C24—H24C	0.9600
O3—C14	1.238 (6)	C5—C4	1.373 (10)
C1—C2	1.379 (8)	C5—H5	0.9300
C1—C6	1.388 (8)	C4—C3	1.374 (10)
C1—C7	1.490 (7)	C4—H4	0.9300
N1—C22	1.316 (7)	C12—C11	1.392 (12)
N1—C23	1.450 (9)	C12—H12	0.9300
N1—C24	1.453 (8)	C23—H23B	0.9600
C8—C13	1.376 (8)	C23—H23A	0.9600
C8—C9	1.382 (7)	C23—H23C	0.9600
C8—C14	1.498 (6)	C2—C3	1.393 (9)
C15—C20	1.373 (8)	C2—H2	0.9300
C15—C16	1.388 (8)	C11—H11	0.9300
C15—C21	1.501 (7)	C3—H3	0.9300
C14—O4^i	1.267 (5)
O8—Eu1—O4	154.52 (13)	C13—C8—C9	118.7 (5)
O8—Eu1—O7	80.01 (13)	C13—C8—C14	122.6 (5)
O4—Eu1—O7	80.00 (13)	C9—C8—C14	118.6 (5)
O8—Eu1—O2	132.46 (13)	C20—C15—C16	119.7 (5)
O4—Eu1—O2	72.54 (12)	C20—C15—C21	120.9 (5)
O7—Eu1—O2	140.39 (13)	C16—C15—C21	119.4 (5)
O8—Eu1—O3	74.58 (14)	O3—C14—O4^i	121.6 (4)
O4—Eu1—O3	116.81 (13)	O3—C14—C8	118.7 (4)
O7—Eu1—O3	79.55 (15)	O4^i—C14—C8	119.8 (4)
O2—Eu1—O3	87.86 (14)	O3—C14—Eu1	50.3 (2)
O8—Eu1—O5	85.94 (14)	O4^i—C14—Eu1	72.3 (3)
O4—Eu1—O5	94.03 (13)	C8—C14—Eu1	165.4 (3)
O7—Eu1—O5	127.89 (13)	C17—C16—C15	120.5 (6)
O2—Eu1—O5	82.75 (13)	C17—C16—H16	119.7
O3—Eu1—O5	143.29 (13)	C15—C16—H16	119.7
O8—Eu1—O6	76.39 (14)	C10—C9—C8	121.9 (6)
O4—Eu1—O6	83.33 (13)	C10—C9—H9	119.0
O7—Eu1—O6	75.10 (13)	C8—C9—H9	119.0
O2—Eu1—O6	127.60 (12)	O8—C22—N1	123.7 (6)
O3—Eu1—O6	144.16 (14)	O8—C22—H22	118.2
O5—Eu1—O6	52.81 (12)	N1—C22—H22	118.2
O8—Eu1—O1	80.26 (13)	O6—C21—O5	119.8 (4)
O4—Eu1—O1	124.21 (12)	O6—C21—C15	120.7 (5)
O7—Eu1—O1	149.22 (13)	O5—C21—C15	119.5 (4)
O2—Eu1—O1	52.24 (11)	O6—C21—Eu1	61.7 (3)
O3—Eu1—O1	72.56 (13)	O5—C21—Eu1	58.1 (2)
O5—Eu1—O1	73.68 (12)	C15—C21—Eu1	175.2 (4)
O6—Eu1—O1	122.27 (12)	C15—C20—C19	119.5 (6)
O8—Eu1—C21	80.78 (14)	C15—C20—H20	120.3
O4—Eu1—C21	87.89 (13)	C19—C20—H20	120.3
O7—Eu1—C21	101.45 (15)	C5—C6—C1	120.5 (6)
O2—Eu1—C21	105.40 (14)	C5—C6—H6	119.8
O3—Eu1—C21	154.81 (14)	C1—C6—H6	119.8
O5—Eu1—C21	26.48 (14)	O1—C7—O2	121.0 (5)
O6—Eu1—C21	26.34 (13)	O1—C7—C1	121.3 (4)
O1—Eu1—C21	98.42 (13)	O2—C7—C1	117.7 (4)
O8—Eu1—C7	106.16 (14)	O1—C7—Eu1	64.3 (3)
O4—Eu1—C7	98.69 (13)	O2—C7—Eu1	56.8 (2)
O7—Eu1—C7	154.32 (14)	C1—C7—Eu1	173.3 (3)
O2—Eu1—C7	26.30 (12)	C11—C10—C9	118.9 (7)
O3—Eu1—C7	78.27 (14)	C11—C10—H10	120.5
O5—Eu1—C7	77.76 (13)	C9—C10—H10	120.5
O6—Eu1—C7	130.46 (12)	C18—C19—C20	120.3 (7)
O1—Eu1—C7	25.97 (12)	C18—C19—H19	119.9
C21—Eu1—C7	104.14 (14)	C20—C19—H19	119.9
O8—Eu1—O4^i	116.21 (12)	C17—C18—C19	119.9 (6)
O4—Eu1—O4^i	69.30 (12)	C17—C18—H18	120.0
O7—Eu1—O4^i	66.92 (12)	C19—C18—H18	120.0
O2—Eu1—O4^i	76.82 (11)	C8—C13—C12	120.5 (6)
O3—Eu1—O4^i	47.66 (11)	C8—C13—H13	119.8
O5—Eu1—O4^i	156.69 (11)	C12—C13—H13	119.8
O6—Eu1—O4^i	136.02 (11)	C18—C17—C16	120.1 (7)
O1—Eu1—O4^i	101.67 (11)	C18—C17—H17	119.9
C21—Eu1—O4^i	155.54 (12)	C16—C17—H17	119.9
C7—Eu1—O4^i	88.47 (12)	N1—C24—H24B	109.5
O8—Eu1—C14	93.62 (13)	N1—C24—H24A	109.5
O4—Eu1—C14	93.99 (13)	H24B—C24—H24A	109.5
O7—Eu1—C14	69.44 (14)	N1—C24—H24C	109.5
O2—Eu1—C14	84.36 (13)	H24B—C24—H24C	109.5
O3—Eu1—C14	23.22 (13)	H24A—C24—H24C	109.5
O5—Eu1—C14	162.04 (12)	C4—C5—C6	119.9 (7)
O6—Eu1—C14	144.35 (12)	C4—C5—H5	120.1
O1—Eu1—C14	88.52 (12)	C6—C5—H5	120.1
C21—Eu1—C14	170.15 (14)	C5—C4—C3	120.2 (6)
C7—Eu1—C14	85.15 (13)	C5—C4—H4	119.9
O4^i—Eu1—C14	24.70 (11)	C3—C4—H4	119.9
C7—O1—Eu1	89.7 (3)	C11—C12—C13	119.2 (7)
C21—O5—Eu1	95.4 (3)	C11—C12—H12	120.4
C22—O8—Eu1	132.7 (4)	C13—C12—H12	120.4
C7—O2—Eu1	96.9 (3)	N1—C23—H23B	109.5
Eu1—O7—H7B	128 (6)	N1—C23—H23A	109.5
Eu1—O7—H7A	126 (6)	H23B—C23—H23A	109.5
H7B—O7—H7A	106 (5)	N1—C23—H23C	109.5
C14^i—O4—Eu1	166.2 (3)	H23B—C23—H23C	109.5
C14^i—O4—Eu1^i	83.0 (3)	H23A—C23—H23C	109.5
Eu1—O4—Eu1^i	110.70 (12)	C1—C2—C3	119.8 (6)
C21—O6—Eu1	92.0 (3)	C1—C2—H2	120.1
C14—O3—Eu1	106.4 (3)	C3—C2—H2	120.1
C2—C1—C6	119.4 (5)	C10—C11—C12	120.7 (6)
C2—C1—C7	119.9 (5)	C10—C11—H11	119.7
C6—C1—C7	120.5 (5)	C12—C11—H11	119.7
C22—N1—C23	120.1 (5)	C4—C3—C2	120.1 (7)
C22—N1—C24	120.9 (6)	C4—C3—H3	119.9
C23—N1—C24	118.9 (6)	C2—C3—H3	119.9
O8—Eu1—O1—C7	175.9 (3)	O8—Eu1—C14—O4^i	157.2 (3)
O4—Eu1—O1—C7	−11.9 (3)	O4—Eu1—C14—O4^i	1.5 (3)
O7—Eu1—O1—C7	125.1 (3)	O7—Eu1—C14—O4^i	79.3 (3)
O2—Eu1—O1—C7	−2.1 (3)	O2—Eu1—C14—O4^i	−70.5 (3)
O3—Eu1—O1—C7	99.1 (3)	O3—Eu1—C14—O4^i	−168.3 (5)
O5—Eu1—O1—C7	−95.5 (3)	O5—Eu1—C14—O4^i	−114.8 (4)
O6—Eu1—O1—C7	−117.1 (3)	O6—Eu1—C14—O4^i	85.6 (3)
C21—Eu1—O1—C7	−105.1 (3)	O1—Eu1—C14—O4^i	−122.7 (3)
O4^i—Eu1—O1—C7	60.9 (3)	C7—Eu1—C14—O4^i	−96.9 (3)
C14—Eu1—O1—C7	81.9 (3)	O8—Eu1—C14—C8	10.2 (13)
O8—Eu1—O5—C21	−77.4 (3)	O4—Eu1—C14—C8	−145.4 (13)
O4—Eu1—O5—C21	77.0 (3)	O7—Eu1—C14—C8	−67.7 (13)
O7—Eu1—O5—C21	−3.4 (4)	O2—Eu1—C14—C8	142.6 (13)
O2—Eu1—O5—C21	148.8 (3)	O3—Eu1—C14—C8	44.8 (12)
O3—Eu1—O5—C21	−134.7 (3)	O5—Eu1—C14—C8	98.2 (13)
O6—Eu1—O5—C21	−1.4 (3)	O6—Eu1—C14—C8	−61.3 (13)
O1—Eu1—O5—C21	−158.4 (3)	O1—Eu1—C14—C8	90.4 (13)
C7—Eu1—O5—C21	175.1 (3)	C7—Eu1—C14—C8	116.2 (13)
O4^i—Eu1—O5—C21	120.0 (3)	O4^i—Eu1—C14—C8	−146.9 (14)
C14—Eu1—O5—C21	−166.6 (4)	C20—C15—C16—C17	0.0 (9)
O4—Eu1—O8—C22	169.1 (5)	C21—C15—C16—C17	178.9 (5)
O7—Eu1—O8—C22	130.3 (5)	C13—C8—C9—C10	3.4 (10)
O2—Eu1—O8—C22	−23.8 (6)	C14—C8—C9—C10	−175.5 (6)
O3—Eu1—O8—C22	48.5 (5)	Eu1—O8—C22—N1	−159.4 (4)
O5—Eu1—O8—C22	−100.1 (5)	C23—N1—C22—O8	0.5 (10)
O6—Eu1—O8—C22	−152.8 (5)	C24—N1—C22—O8	−175.8 (6)
O1—Eu1—O8—C22	−26.0 (5)	Eu1—O6—C21—O5	−2.5 (5)
C21—Eu1—O8—C22	−126.2 (5)	Eu1—O6—C21—C15	175.2 (4)
C7—Eu1—O8—C22	−24.1 (5)	Eu1—O5—C21—O6	2.6 (5)
O4^i—Eu1—O8—C22	72.3 (5)	Eu1—O5—C21—C15	−175.1 (4)
C14—Eu1—O8—C22	61.9 (5)	C20—C15—C21—O6	−2.2 (8)
O8—Eu1—O2—C7	−0.7 (4)	C16—C15—C21—O6	179.0 (5)
O4—Eu1—O2—C7	173.6 (3)	C20—C15—C21—O5	175.5 (5)
O7—Eu1—O2—C7	−138.2 (3)	C16—C15—C21—O5	−3.3 (8)
O3—Eu1—O2—C7	−67.4 (3)	O8—Eu1—C21—O6	−77.9 (3)
O5—Eu1—O2—C7	77.0 (3)	O4—Eu1—C21—O6	79.2 (3)
O6—Eu1—O2—C7	106.9 (3)	O7—Eu1—C21—O6	−0.2 (3)
O1—Eu1—O2—C7	2.1 (3)	O2—Eu1—C21—O6	150.4 (3)
C21—Eu1—O2—C7	90.8 (3)	O3—Eu1—C21—O6	−89.9 (4)
O4^i—Eu1—O2—C7	−114.3 (3)	O5—Eu1—C21—O6	−177.4 (5)
C14—Eu1—O2—C7	−90.5 (3)	O1—Eu1—C21—O6	−156.5 (3)
O8—Eu1—O4—C14^i	78.9 (14)	C7—Eu1—C21—O6	177.6 (3)
O7—Eu1—O4—C14^i	117.7 (14)	O4^i—Eu1—C21—O6	58.5 (5)
O2—Eu1—O4—C14^i	−91.2 (14)	O8—Eu1—C21—O5	99.5 (3)
O3—Eu1—O4—C14^i	−169.5 (14)	O4—Eu1—C21—O5	−103.4 (3)
O5—Eu1—O4—C14^i	−10.1 (14)	O7—Eu1—C21—O5	177.2 (3)
O6—Eu1—O4—C14^i	41.7 (14)	O2—Eu1—C21—O5	−32.2 (3)
O1—Eu1—O4—C14^i	−83.1 (14)	O3—Eu1—C21—O5	87.5 (5)
C21—Eu1—O4—C14^i	15.6 (14)	O6—Eu1—C21—O5	177.4 (5)
C7—Eu1—O4—C14^i	−88.3 (14)	O1—Eu1—C21—O5	20.9 (3)
O4^i—Eu1—O4—C14^i	−173.4 (15)	C7—Eu1—C21—O5	−5.0 (3)
C14—Eu1—O4—C14^i	−174.0 (13)	O4^i—Eu1—C21—O5	−124.1 (3)
O8—Eu1—O4—Eu1^i	−107.7 (3)	C16—C15—C20—C19	0.7 (9)
O7—Eu1—O4—Eu1^i	−68.97 (14)	C21—C15—C20—C19	−178.1 (5)
O2—Eu1—O4—Eu1^i	82.15 (14)	C2—C1—C6—C5	−1.3 (11)
O3—Eu1—O4—Eu1^i	3.84 (19)	C7—C1—C6—C5	174.0 (7)
O5—Eu1—O4—Eu1^i	163.24 (13)	Eu1—O1—C7—O2	3.6 (5)
O6—Eu1—O4—Eu1^i	−144.95 (14)	Eu1—O1—C7—C1	−175.9 (4)
O1—Eu1—O4—Eu1^i	90.26 (16)	Eu1—O2—C7—O1	−3.9 (5)
C21—Eu1—O4—Eu1^i	−170.98 (15)	Eu1—O2—C7—C1	175.7 (4)
C7—Eu1—O4—Eu1^i	85.03 (14)	C2—C1—C7—O1	−173.9 (5)
O4^i—Eu1—O4—Eu1^i	0.0	C6—C1—C7—O1	10.8 (8)
C14—Eu1—O4—Eu1^i	−0.67 (15)	C2—C1—C7—O2	6.5 (7)
O8—Eu1—O6—C21	96.7 (3)	C6—C1—C7—O2	−168.7 (5)
O4—Eu1—O6—C21	−98.8 (3)	O8—Eu1—C7—O1	−4.2 (3)
O7—Eu1—O6—C21	179.8 (3)	O4—Eu1—C7—O1	170.1 (3)
O2—Eu1—O6—C21	−36.9 (3)	O7—Eu1—C7—O1	−104.9 (4)
O3—Eu1—O6—C21	133.4 (3)	O2—Eu1—C7—O1	176.3 (5)
O5—Eu1—O6—C21	1.5 (3)	O3—Eu1—C7—O1	−74.2 (3)
O1—Eu1—O6—C21	27.8 (3)	O5—Eu1—C7—O1	77.8 (3)
C7—Eu1—O6—C21	−3.0 (4)	O6—Eu1—C7—O1	81.5 (3)
O4^i—Eu1—O6—C21	−149.5 (3)	C21—Eu1—C7—O1	80.1 (3)
C14—Eu1—O6—C21	173.7 (3)	O4^i—Eu1—C7—O1	−121.1 (3)
O8—Eu1—O3—C14	144.0 (4)	C14—Eu1—C7—O1	−96.6 (3)
O4—Eu1—O3—C14	−11.5 (4)	O8—Eu1—C7—O2	179.5 (3)
O7—Eu1—O3—C14	61.6 (4)	O4—Eu1—C7—O2	−6.2 (3)
O2—Eu1—O3—C14	−80.7 (4)	O7—Eu1—C7—O2	78.8 (4)
O5—Eu1—O3—C14	−155.5 (3)	O3—Eu1—C7—O2	109.5 (3)
O6—Eu1—O3—C14	107.0 (4)	O5—Eu1—C7—O2	−98.5 (3)
O1—Eu1—O3—C14	−131.6 (4)	O6—Eu1—C7—O2	−94.8 (3)
C21—Eu1—O3—C14	156.3 (3)	O1—Eu1—C7—O2	−176.3 (5)
C7—Eu1—O3—C14	−105.4 (4)	C21—Eu1—C7—O2	−96.2 (3)
O4^i—Eu1—O3—C14	−6.6 (3)	O4^i—Eu1—C7—O2	62.6 (3)
Eu1—O3—C14—O4^i	13.2 (6)	C14—Eu1—C7—O2	87.1 (3)
Eu1—O3—C14—C8	−168.3 (4)	C8—C9—C10—C11	−1.8 (11)
C13—C8—C14—O3	164.0 (6)	C15—C20—C19—C18	−1.1 (10)
C9—C8—C14—O3	−17.0 (8)	C20—C19—C18—C17	0.6 (11)
C13—C8—C14—O4^i	−17.4 (8)	C9—C8—C13—C12	−1.7 (10)
C9—C8—C14—O4^i	161.5 (5)	C14—C8—C13—C12	177.2 (6)
C13—C8—C14—Eu1	125.8 (12)	C19—C18—C17—C16	0.2 (11)
C9—C8—C14—Eu1	−55.2 (15)	C15—C16—C17—C18	−0.5 (10)
O8—Eu1—C14—O3	−34.6 (4)	C1—C6—C5—C4	1.4 (13)
O4—Eu1—C14—O3	169.7 (4)	C6—C5—C4—C3	0.7 (14)
O7—Eu1—C14—O3	−112.5 (4)	C8—C13—C12—C11	−1.6 (12)
O2—Eu1—C14—O3	97.8 (4)	C6—C1—C2—C3	−0.9 (10)
O5—Eu1—C14—O3	53.4 (6)	C7—C1—C2—C3	−176.2 (6)
O6—Eu1—C14—O3	−106.1 (4)	C9—C10—C11—C12	−1.6 (12)
O1—Eu1—C14—O3	45.6 (4)	C13—C12—C11—C10	3.3 (13)
C7—Eu1—C14—O3	71.3 (4)	C5—C4—C3—C2	−2.9 (13)
O4^i—Eu1—C14—O3	168.3 (5)	C1—C2—C3—C4	3.0 (12)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7B···O6^ii	0.86 (2)	1.90 (2)	2.756 (5)	174 (9)
O7—H7A···O2^i	0.86 (2)	1.90 (4)	2.724 (5)	159 (9)

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