[μ-N,N′-Bis(2-oxidobenzyl­idene)-1,2-ethanediamine](methanol)trinitratocopper(II)europium(III)

The title complex (systematic name: {2,2′-[ethane-1,2-diyl­bis(nitrilo­methyl­idyne)]diphenolato-1κ⁴O¹,­O^1′,­O⁶,­O^6′:2κ⁴O¹,N,N′,O^1′}(methanol-1κO)trinitrato-1κ⁶O,O′-copper(II)europium(III)), [CuEu(C₁₆H₁₄N₂O₂)(NO₃)₃(CH₃OH)], is a heterodinuclear 3d–4f metal Schiff base dimer. The Cu^II ion is five-coordinated by two O atoms, two N atoms of the deprotonated Schiff base and one nitrate O atom from a neighboring dinuclear unit, giving rise to a square-pyramidal geometry, whereas the Eu^III ion is nine-coordinated by six O atoms from nitrate groups, two O atoms from the deprotonated Schiff base and one O atom from methanol. The ethylene link is disordered over two positions with a site occupancy ratio of ca 3:1. The crystal structure involves O—H...O hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.004 Å
Some non-H atoms missing
• Disorder in main residue
• R factor = 0.021
• wR factor = 0.047
• Data-to-parameter ratio = 15.1

checkCIF/PLATON results

No syntax errors found



Alert level C
CHEMW01_ALERT_1_C  The difference between the given and expected weight for
            compound is greater 1 mass unit. Check that all hydrogen
            atoms have been taken into account.
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............       0.50 Ratio
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.90
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         O9
PLAT301_ALERT_3_C Main Residue  Disorder .........................       5.00 Perc.

Alert level G
FORMU01_ALERT_2_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and the formula from the _atom_site* data.
            Atom count from _chemical_formula_sum:C17 H17 Cu1 Eu1 N5 O12
            Atom count from the _atom_site data:  C17 H18 Cu1 Eu1 N5 O12
ABSTM02_ALERT_3_G  When printed, the submitted absorption T values will be
            replaced by the scaled T values. Since the ratio of scaled T's
            is identical to the ratio of reported T values, the scaling
            does not imply a change to the absorption corrections used in
            the study.
            Ratio of Tmax expected/reported      0.905
            Tmax scaled      0.492 Tmin scaled      0.341
CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected.
CELLZ01_ALERT_1_G ALERT: Large difference may be due to a
            symmetry error - see SYMMG tests
           From the CIF: _cell_formula_units_Z    4
           From the CIF: _chemical_formula_sum  C17 H17 Cu1 Eu1 N5 O12
           TEST: Compare cell contents of formula and atom_site data

           atom    Z*formula  cif sites diff
           C         68.00     68.00    0.00
           H         68.00     72.00   -4.00
           Cu         4.00      4.00    0.00
           Eu         4.00      4.00    0.00
           N         20.00     20.00    0.00
           O         48.00     48.00    0.00
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          2

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   7 ALERT level C = Check and explain
   5 ALERT level G = General alerts; check

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

---

S1. Comment

As shown in Fig. 1, the tetradentate Schiff base ligand links Cu and Eu atoms into a dinuclear complex through two phenolate O atoms. The Eu^III centre in (I) is nine-coordinated by two O atoms from the ligand, six O atoms from three nitrate and one O atoms from the methanol, which is similar with the bonding reported for another copper-lanthanum complex of the same ligand (Kahn et al., 2000). The Cu^II center is five-coordinate by two N atoms, two O atoms from the ligand and one nitrato oxygen of neighboring dinuclear unit in a square-pyramidal geometry.

Related literature

See Kahn et al. (2000) for a similar copper–lanthanum complex of the same Schiff base.

S2. Experimental

The title complex was obtained by the treatment of copper(II) acetate monohydrate with the Schiff base in water/methanol (1:3). The first two reactants were stirred for 2 h, and the mixture was stirred for another 3 h after the addition of europium (III) nitrate hexahydrate. The reaction mixture was filtered; diethyl ether was allowed to diffuse slowly into the solution of the filtrate. Single crystals were obtained after several days. Analysis calculated for for C₁₇H₁₇Cu₁Eu₁N₅O₁₂: C 29.22, H 2.45, N 10.02%; found: C 29.38, H 2.38, N 10.00%.

S3. Refinement

H atoms bound to C atoms were placed in calculated positions and treated as riding on their parent atoms, with C—H = 0.93 Å (aromatic C), C—H = 0.97 Å (methylene C), and with U_iso(H) = 1.2Ueq(C) or C—H = 0.96 Å (methly C) and with U_iso(H) = 1.5Ueq(C). The H atoms of hydroxy were initially located in a difference Fourier map but they were treated as riding on their parent atoms with O—H=0.85 Å, U_iso(H) = 1.5Ueq(O) In complex (I), the diaminopropane is disordered and was refined with a split model over two positions, and with an occupancy of 0.72 (2) for C8, C9, and 0.28 (2) for C8', C9'.

Computing details

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. The molecular structure of (I), showing 30% probability displacement ellipsoids. Disordered atoms (C8', C9') have been omitted for clarity.

{2,2'-[ethane-1,2-diylbis(nitrilomethylidyne)]diphenolato- 1κ⁴O¹,O^1',O⁶,O^6': 2κ⁴O¹,N,N',O^1'}(methanol- 1κO)trinitrato-1κ⁶O,O'-copper(II)europium(III)

Crystal data

[CuEu(C16H14N2O2)(NO3)3(CH4O)]	F(000) = 1372
Mr = 699.87	Dx = 2.041 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 18713 reflections
a = 12.223 (4) Å	θ = 6.0–54.9°
b = 10.363 (3) Å	µ = 3.74 mm^−1
c = 18.414 (5) Å	T = 296 K
β = 102.451 (12)°	Block, black
V = 2277.6 (12) Å^3	0.33 × 0.20 × 0.19 mm
Z = 4

Data collection

Rigaku R-AXIS RAPID diffractometer	5201 independent reflections
Radiation source: fine-focus sealed tube	4693 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.030
Detector resolution: 10.000 pixels mm^-1	θmax = 27.5°, θmin = 3.0°
ω scans	h = −15→15
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −13→13
Tmin = 0.376, Tmax = 0.543	l = −23→22
21558 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)] = 0.021	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.047	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0142P)^2 + 1.9917P] where P = (Fo^2 + 2Fc^2)/3
5201 reflections	(Δ/σ)max = 0.003
345 parameters	Δρmax = 0.31 e Å^−3
2 restraints	Δρmin = −0.59 e Å^−3

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	Occ. (<1)
C1	0.1201 (2)	0.7351 (3)	0.60899 (13)	0.0310 (5)
C2	0.0762 (2)	0.6757 (3)	0.66454 (15)	0.0413 (6)
H1	0.0794	0.5863	0.6690	0.050*
C3	0.0284 (2)	0.7464 (3)	0.71266 (16)	0.0464 (7)
H2	−0.0004	0.7041	0.7490	0.056*
C4	0.0225 (3)	0.8791 (3)	0.70797 (17)	0.0535 (8)
H3	−0.0088	0.9266	0.7412	0.064*
C5	0.0635 (3)	0.9394 (3)	0.65357 (18)	0.0510 (8)
H4	0.0589	1.0288	0.6498	0.061*
C6	0.1127 (2)	0.8705 (3)	0.60289 (15)	0.0377 (6)
C7	0.1553 (3)	0.9448 (3)	0.54848 (17)	0.0450 (7)
H5	0.1532	1.0343	0.5522	0.054*
C8	0.2543 (9)	0.9774 (6)	0.4478 (4)	0.0442 (17)	0.72 (2)
H6	0.2241	1.0643	0.4428	0.053*
H7	0.3337	0.9824	0.4701	0.053*
C9	0.2369 (9)	0.9143 (5)	0.3736 (4)	0.0434 (19)	0.72 (2)
H9	0.1617	0.9311	0.3452	0.052*
H8	0.2901	0.9473	0.3460	0.052*
C10	0.2881 (2)	0.7069 (3)	0.33908 (15)	0.0438 (7)
H10	0.3171	0.7489	0.3028	0.053*
C11	0.2860 (2)	0.5681 (3)	0.33729 (14)	0.0344 (5)
C12	0.3126 (3)	0.5076 (3)	0.27460 (16)	0.0462 (7)
H11	0.3385	0.5580	0.2401	0.055*
C13	0.3018 (3)	0.3784 (3)	0.26293 (16)	0.0521 (8)
H12	0.3207	0.3408	0.2214	0.063*
C14	0.2622 (3)	0.3039 (3)	0.31397 (17)	0.0500 (7)
H13	0.2518	0.2158	0.3058	0.060*
C15	0.2379 (2)	0.3589 (3)	0.37687 (16)	0.0426 (6)
H14	0.2125	0.3068	0.4109	0.051*
C16	0.2507 (2)	0.4903 (2)	0.39041 (13)	0.0310 (5)
C17	0.4417 (3)	0.7572 (3)	0.61542 (19)	0.0522 (8)
H15	0.3802	0.7787	0.6380	0.078*
H16	0.4551	0.8272	0.5843	0.078*
H17	0.5077	0.7424	0.6535	0.078*
Cu2	0.20183 (3)	0.71765 (3)	0.471852 (16)	0.03015 (7)
Eu1	0.279281 (10)	0.471486 (11)	0.579103 (6)	0.02628 (4)
N1	0.1952 (2)	0.8978 (2)	0.49601 (13)	0.0397 (5)
N2	0.2534 (2)	0.7769 (2)	0.38641 (13)	0.0413 (5)
N3	0.40354 (19)	0.4886 (2)	0.73120 (12)	0.0404 (5)
N4	0.08119 (18)	0.3280 (2)	0.59421 (13)	0.0378 (5)
N5	0.4077 (2)	0.2526 (2)	0.54166 (14)	0.0434 (6)
O1	0.16860 (14)	0.66089 (16)	0.56505 (9)	0.0309 (4)
O2	0.22848 (16)	0.53808 (16)	0.45385 (10)	0.0343 (4)
O3	0.41493 (16)	0.64166 (19)	0.57093 (12)	0.0463 (5)
H18	0.4580	0.6326	0.5407	0.056*
O4	0.32467 (16)	0.5670 (2)	0.70399 (10)	0.0430 (5)
O5	0.4574 (2)	0.5002 (3)	0.79437 (11)	0.0645 (7)
O6	0.42138 (17)	0.3997 (2)	0.68870 (11)	0.0470 (5)
O7	0.15586 (16)	0.3634 (2)	0.64981 (10)	0.0414 (4)
O8	0.00002 (18)	0.2658 (2)	0.60258 (14)	0.0623 (7)
O9	0.09572 (17)	0.3610 (2)	0.53148 (11)	0.0503 (5)
O10	0.31744 (18)	0.23862 (19)	0.56357 (13)	0.0491 (5)
O11	0.4658 (2)	0.1628 (2)	0.53211 (17)	0.0735 (8)
O12	0.43392 (16)	0.36900 (18)	0.52960 (11)	0.0417 (4)
C8'	0.202 (2)	0.9864 (16)	0.4356 (11)	0.045 (4)	0.28 (2)
C9'	0.293 (2)	0.9273 (15)	0.4025 (15)	0.054 (6)	0.28 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0286 (11)	0.0361 (14)	0.0289 (12)	0.0057 (10)	0.0078 (10)	−0.0022 (10)
C2	0.0475 (15)	0.0414 (15)	0.0398 (14)	0.0083 (13)	0.0203 (12)	0.0055 (12)
C3	0.0469 (16)	0.059 (2)	0.0399 (15)	0.0091 (14)	0.0239 (13)	0.0027 (14)
C4	0.0624 (19)	0.059 (2)	0.0455 (16)	0.0185 (16)	0.0265 (15)	−0.0091 (15)
C5	0.067 (2)	0.0382 (16)	0.0532 (18)	0.0131 (15)	0.0241 (16)	−0.0060 (14)
C6	0.0430 (14)	0.0349 (14)	0.0372 (14)	0.0042 (12)	0.0130 (12)	−0.0036 (11)
C7	0.0645 (19)	0.0242 (13)	0.0484 (16)	−0.0005 (12)	0.0167 (15)	−0.0026 (12)
C8	0.050 (4)	0.029 (2)	0.060 (3)	−0.008 (3)	0.028 (3)	0.002 (2)
C9	0.066 (5)	0.031 (2)	0.041 (3)	0.002 (3)	0.026 (3)	0.008 (2)
C10	0.0550 (17)	0.0459 (16)	0.0376 (14)	0.0043 (14)	0.0254 (13)	0.0102 (13)
C11	0.0353 (13)	0.0424 (15)	0.0273 (12)	0.0026 (11)	0.0109 (10)	0.0014 (11)
C12	0.0509 (16)	0.060 (2)	0.0321 (14)	0.0063 (14)	0.0184 (12)	0.0022 (13)
C13	0.0574 (18)	0.067 (2)	0.0340 (14)	0.0060 (16)	0.0144 (14)	−0.0165 (15)
C14	0.0586 (18)	0.0465 (17)	0.0452 (16)	−0.0046 (14)	0.0116 (14)	−0.0187 (14)
C15	0.0552 (17)	0.0373 (15)	0.0382 (14)	−0.0068 (13)	0.0162 (13)	−0.0059 (12)
C16	0.0326 (12)	0.0361 (14)	0.0240 (11)	0.0000 (10)	0.0056 (10)	−0.0041 (10)
C17	0.0521 (17)	0.0452 (17)	0.0592 (19)	−0.0135 (14)	0.0119 (15)	−0.0148 (15)
Cu2	0.03982 (16)	0.02575 (15)	0.02774 (14)	−0.00171 (13)	0.01360 (12)	0.00176 (12)
Eu1	0.03128 (7)	0.02506 (7)	0.02520 (6)	−0.00126 (5)	0.01204 (5)	0.00007 (5)
N1	0.0573 (14)	0.0278 (11)	0.0368 (12)	−0.0056 (11)	0.0164 (11)	0.0005 (10)
N2	0.0560 (14)	0.0316 (12)	0.0436 (13)	0.0033 (11)	0.0272 (11)	0.0079 (10)
N3	0.0397 (12)	0.0537 (15)	0.0298 (11)	0.0027 (11)	0.0117 (10)	0.0038 (11)
N4	0.0332 (11)	0.0355 (12)	0.0457 (13)	−0.0022 (9)	0.0106 (10)	0.0097 (10)
N5	0.0463 (13)	0.0380 (13)	0.0491 (14)	0.0035 (11)	0.0173 (11)	−0.0083 (11)
O1	0.0397 (9)	0.0275 (9)	0.0291 (8)	0.0044 (7)	0.0157 (7)	0.0013 (7)
O2	0.0518 (11)	0.0280 (9)	0.0265 (8)	−0.0031 (8)	0.0162 (8)	−0.0011 (7)
O3	0.0473 (11)	0.0414 (11)	0.0589 (12)	−0.0149 (9)	0.0310 (10)	−0.0169 (10)
O4	0.0463 (11)	0.0488 (12)	0.0336 (9)	0.0112 (9)	0.0082 (8)	−0.0057 (9)
O5	0.0611 (14)	0.101 (2)	0.0282 (10)	0.0171 (13)	0.0023 (10)	−0.0018 (12)
O6	0.0515 (12)	0.0453 (12)	0.0432 (11)	0.0133 (10)	0.0081 (9)	−0.0024 (10)
O7	0.0412 (10)	0.0502 (12)	0.0345 (10)	−0.0073 (9)	0.0115 (8)	0.0065 (9)
O8	0.0444 (12)	0.0700 (16)	0.0719 (15)	−0.0220 (11)	0.0114 (11)	0.0244 (13)
O9	0.0476 (11)	0.0671 (15)	0.0355 (10)	−0.0177 (10)	0.0075 (9)	0.0069 (10)
O10	0.0553 (12)	0.0333 (10)	0.0674 (14)	−0.0063 (9)	0.0328 (11)	−0.0066 (10)
O11	0.0754 (16)	0.0431 (13)	0.113 (2)	0.0172 (12)	0.0450 (16)	−0.0089 (14)
O12	0.0458 (10)	0.0358 (10)	0.0498 (11)	−0.0023 (9)	0.0244 (9)	−0.0041 (9)
C8'	0.043 (10)	0.040 (7)	0.059 (9)	−0.004 (7)	0.026 (8)	0.009 (6)
C9'	0.068 (12)	0.034 (6)	0.068 (13)	−0.001 (7)	0.030 (11)	0.010 (7)

Geometric parameters (Å, º)

C1—O1	1.343 (3)	C15—C16	1.387 (4)
C1—C2	1.396 (4)	C15—H14	0.9300
C1—C6	1.408 (4)	C16—O2	1.349 (3)
C2—C3	1.373 (4)	C17—O3	1.448 (3)
C2—H1	0.9300	C17—H15	0.9600
C3—C4	1.379 (5)	C17—H16	0.9600
C3—H2	0.9300	C17—H17	0.9600
C4—C5	1.364 (5)	Cu2—N2	1.918 (2)
C4—H3	0.9300	Cu2—N1	1.925 (2)
C5—C6	1.409 (4)	Cu2—O2	1.9301 (18)
C5—H4	0.9300	Cu2—O1	1.9382 (17)
C6—C7	1.447 (4)	Cu2—O8	2.557 (19)
C7—N1	1.270 (4)	Eu1—O2	2.3589 (18)
C7—H5	0.9300	Eu1—O1	2.3662 (17)
C8—C9	1.488 (8)	Eu1—O3	2.4474 (19)
C8—N1	1.505 (7)	Eu1—O4	2.455 (2)
C8—H6	0.9700	Eu1—O7	2.4643 (19)
C8—H7	0.9700	Eu1—O6	2.476 (2)
C9—N2	1.450 (5)	Eu1—O10	2.486 (2)
C9—H9	0.9700	Eu1—O9	2.503 (2)
C9—H8	0.9700	Eu1—O12	2.5050 (19)
C10—N2	1.275 (4)	N3—O5	1.213 (3)
C10—C11	1.439 (4)	N3—O6	1.258 (3)
C10—H10	0.9300	N3—O4	1.278 (3)
C11—C16	1.405 (4)	N4—O8	1.221 (3)
C11—C12	1.412 (4)	N4—O9	1.253 (3)
C12—C13	1.357 (5)	N4—O7	1.270 (3)
C12—H11	0.9300	N5—O11	1.206 (3)
C13—C14	1.382 (5)	N5—O10	1.262 (3)
C13—H12	0.9300	N5—O12	1.280 (3)
C14—C15	1.380 (4)	O3—H18	0.8500
C14—H13	0.9300	C8'—C9'	1.51 (3)
O1—C1—C2	118.6 (2)	O2—Eu1—O4	139.18 (7)
O1—C1—C6	123.4 (2)	O1—Eu1—O4	77.08 (6)
C2—C1—C6	118.0 (2)	O3—Eu1—O4	75.39 (7)
C3—C2—C1	121.4 (3)	O2—Eu1—O7	125.98 (6)
C3—C2—H1	119.3	O1—Eu1—O7	91.96 (7)
C1—C2—H1	119.3	O3—Eu1—O7	149.33 (7)
C2—C3—C4	121.0 (3)	O4—Eu1—O7	74.26 (7)
C2—C3—H2	119.5	O2—Eu1—O6	151.09 (7)
C4—C3—H2	119.5	O1—Eu1—O6	128.50 (6)
C5—C4—C3	118.7 (3)	O3—Eu1—O6	84.33 (8)
C5—C4—H3	120.6	O4—Eu1—O6	51.72 (7)
C3—C4—H3	120.6	O7—Eu1—O6	80.47 (7)
C4—C5—C6	122.1 (3)	O2—Eu1—O10	100.83 (7)
C4—C5—H4	119.0	O1—Eu1—O10	155.46 (7)
C6—C5—H4	119.0	O3—Eu1—O10	123.09 (7)
C1—C6—C5	118.8 (3)	O4—Eu1—O10	119.28 (7)
C1—C6—C7	124.0 (2)	O7—Eu1—O10	76.76 (7)
C5—C6—C7	117.2 (3)	O6—Eu1—O10	71.70 (7)
N1—C7—C6	125.2 (2)	O2—Eu1—O9	76.36 (6)
N1—C7—H5	117.4	O1—Eu1—O9	83.86 (7)
C6—C7—H5	117.4	O3—Eu1—O9	151.18 (7)
C9—C8—N1	108.0 (5)	O4—Eu1—O9	121.14 (7)
C9—C8—H6	110.1	O7—Eu1—O9	51.14 (6)
N1—C8—H6	110.1	O6—Eu1—O9	124.49 (7)
C9—C8—H7	110.1	O10—Eu1—O9	72.05 (7)
N1—C8—H7	110.1	O2—Eu1—O12	80.12 (7)
H6—C8—H7	108.4	O1—Eu1—O12	140.39 (6)
N2—C9—C8	107.2 (5)	O3—Eu1—O12	73.07 (7)
N2—C9—H9	110.3	O4—Eu1—O12	118.43 (7)
C8—C9—H9	110.3	O7—Eu1—O12	126.55 (7)
N2—C9—H8	110.3	O6—Eu1—O12	73.59 (7)
C8—C9—H8	110.3	O10—Eu1—O12	51.07 (6)
H9—C9—H8	108.5	O9—Eu1—O12	111.60 (7)
N2—C10—C11	125.3 (2)	C7—N1—C8	123.4 (3)
N2—C10—H10	117.4	C7—N1—Cu2	126.17 (19)
C11—C10—H10	117.4	C8—N1—Cu2	110.2 (3)
C16—C11—C12	118.3 (3)	C10—N2—C9	120.2 (3)
C16—C11—C10	124.3 (2)	C10—N2—Cu2	126.5 (2)
C12—C11—C10	117.2 (2)	C9—N2—Cu2	112.9 (2)
C13—C12—C11	122.4 (3)	O5—N3—O6	122.6 (2)
C13—C12—H11	118.8	O5—N3—O4	121.4 (2)
C11—C12—H11	118.8	O6—N3—O4	116.1 (2)
C12—C13—C14	118.7 (3)	O8—N4—O9	122.7 (2)
C12—C13—H12	120.7	O8—N4—O7	120.9 (2)
C14—C13—H12	120.7	O9—N4—O7	116.4 (2)
C15—C14—C13	120.7 (3)	O11—N5—O10	122.8 (3)
C15—C14—H13	119.7	O11—N5—O12	121.6 (3)
C13—C14—H13	119.7	O10—N5—O12	115.6 (2)
C14—C15—C16	121.4 (3)	C1—O1—Cu2	124.30 (15)
C14—C15—H14	119.3	C1—O1—Eu1	136.48 (15)
C16—C15—H14	119.3	Cu2—O1—Eu1	97.16 (7)
O2—C16—C15	118.7 (2)	C16—O2—Cu2	125.12 (16)
O2—C16—C11	122.8 (2)	C16—O2—Eu1	132.82 (16)
C15—C16—C11	118.5 (2)	Cu2—O2—Eu1	97.62 (7)
N2—Cu2—N1	85.22 (10)	C17—O3—Eu1	129.40 (17)
N2—Cu2—O2	94.04 (9)	C17—O3—H18	111.5
N1—Cu2—O2	172.68 (10)	Eu1—O3—H18	118.9
N2—Cu2—O1	172.90 (9)	N3—O4—Eu1	96.31 (15)
N1—Cu2—O1	93.58 (8)	N3—O6—Eu1	95.84 (15)
O2—Cu2—O1	86.27 (7)	N4—O7—Eu1	96.93 (14)
O2—Eu1—O1	68.07 (6)	N4—O9—Eu1	95.52 (14)
O2—Eu1—O3	76.59 (7)	N5—O10—Eu1	97.13 (15)
O1—Eu1—O3	76.97 (7)	N5—O12—Eu1	95.71 (14)
O1—C1—C2—C3	178.1 (3)	O10—Eu1—O2—C16	−23.4 (2)
C6—C1—C2—C3	−0.9 (4)	O9—Eu1—O2—C16	−91.8 (2)
C1—C2—C3—C4	−0.3 (5)	O12—Eu1—O2—C16	23.5 (2)
C2—C3—C4—C5	1.1 (5)	O1—Eu1—O2—Cu2	23.20 (7)
C3—C4—C5—C6	−0.8 (5)	O3—Eu1—O2—Cu2	−57.94 (8)
O1—C1—C6—C5	−177.8 (3)	O4—Eu1—O2—Cu2	−10.21 (13)
C2—C1—C6—C5	1.1 (4)	O7—Eu1—O2—Cu2	98.92 (9)
O1—C1—C6—C7	0.6 (4)	O6—Eu1—O2—Cu2	−108.02 (13)
C2—C1—C6—C7	179.5 (3)	O10—Eu1—O2—Cu2	−179.67 (7)
C4—C5—C6—C1	−0.3 (5)	O9—Eu1—O2—Cu2	112.00 (9)
C4—C5—C6—C7	−178.8 (3)	O12—Eu1—O2—Cu2	−132.73 (8)
C1—C6—C7—N1	6.4 (5)	O2—Eu1—O3—C17	125.7 (2)
C5—C6—C7—N1	−175.1 (3)	O1—Eu1—O3—C17	55.5 (2)
N1—C8—C9—N2	−43.7 (12)	O4—Eu1—O3—C17	−24.3 (2)
N2—C10—C11—C16	−3.7 (5)	O7—Eu1—O3—C17	−15.8 (3)
N2—C10—C11—C12	171.0 (3)	O6—Eu1—O3—C17	−76.2 (2)
C16—C11—C12—C13	2.2 (4)	O10—Eu1—O3—C17	−140.0 (2)
C10—C11—C12—C13	−172.8 (3)	O9—Eu1—O3—C17	105.1 (3)
C11—C12—C13—C14	0.7 (5)	O12—Eu1—O3—C17	−150.8 (3)
C12—C13—C14—C15	−2.3 (5)	O5—N3—O4—Eu1	177.3 (2)
C13—C14—C15—C16	1.0 (5)	O6—N3—O4—Eu1	−2.7 (2)
C14—C15—C16—O2	−178.3 (3)	O2—Eu1—O4—N3	−140.82 (15)
C14—C15—C16—C11	1.9 (4)	O1—Eu1—O4—N3	−172.43 (16)
C12—C11—C16—O2	176.8 (2)	O3—Eu1—O4—N3	−92.76 (16)
C10—C11—C16—O2	−8.7 (4)	O7—Eu1—O4—N3	91.77 (16)
C12—C11—C16—C15	−3.4 (4)	O6—Eu1—O4—N3	1.58 (14)
C10—C11—C16—C15	171.2 (3)	O10—Eu1—O4—N3	27.29 (18)
C6—C7—N1—C8	−170.4 (5)	O9—Eu1—O4—N3	113.04 (16)
C6—C7—N1—Cu2	3.7 (5)	O12—Eu1—O4—N3	−31.66 (17)
C9—C8—N1—C7	−151.1 (7)	O5—N3—O6—Eu1	−177.3 (2)
C9—C8—N1—Cu2	34.0 (10)	O4—N3—O6—Eu1	2.7 (2)
N2—Cu2—N1—C7	173.2 (3)	O2—Eu1—O6—N3	122.81 (17)
O1—Cu2—N1—C7	−13.8 (3)	O1—Eu1—O6—N3	5.87 (19)
N2—Cu2—N1—C8	−12.0 (4)	O3—Eu1—O6—N3	74.25 (16)
O1—Cu2—N1—C8	161.0 (4)	O4—Eu1—O6—N3	−1.60 (14)
C11—C10—N2—C9	−166.5 (5)	O7—Eu1—O6—N3	−79.02 (16)
C11—C10—N2—Cu2	5.7 (5)	O10—Eu1—O6—N3	−158.11 (17)
C8—C9—N2—C10	−151.6 (7)	O9—Eu1—O6—N3	−106.50 (16)
C8—C9—N2—Cu2	35.1 (10)	O12—Eu1—O6—N3	148.23 (17)
N1—Cu2—N2—C10	174.0 (3)	O8—N4—O7—Eu1	178.6 (2)
O2—Cu2—N2—C10	1.3 (3)	O9—N4—O7—Eu1	−1.6 (2)
N1—Cu2—N2—C9	−13.2 (5)	O2—Eu1—O7—N4	17.35 (18)
O2—Cu2—N2—C9	174.1 (5)	O1—Eu1—O7—N4	81.45 (15)
C2—C1—O1—Cu2	164.73 (18)	O3—Eu1—O7—N4	148.83 (15)
C6—C1—O1—Cu2	−16.4 (3)	O4—Eu1—O7—N4	157.44 (16)
C2—C1—O1—Eu1	−35.6 (3)	O6—Eu1—O7—N4	−149.81 (16)
C6—C1—O1—Eu1	143.3 (2)	O10—Eu1—O7—N4	−76.52 (16)
N1—Cu2—O1—C1	19.80 (19)	O9—Eu1—O7—N4	0.94 (14)
O2—Cu2—O1—C1	−167.54 (19)	O12—Eu1—O7—N4	−88.56 (16)
N1—Cu2—O1—Eu1	−146.22 (9)	O8—N4—O9—Eu1	−178.7 (2)
O2—Cu2—O1—Eu1	26.44 (7)	O7—N4—O9—Eu1	1.6 (2)
O2—Eu1—O1—C1	173.8 (2)	O2—Eu1—O9—N4	−167.35 (17)
O3—Eu1—O1—C1	−105.6 (2)	O1—Eu1—O9—N4	−98.47 (16)
O4—Eu1—O1—C1	−27.9 (2)	O3—Eu1—O9—N4	−146.72 (15)
O7—Eu1—O1—C1	45.5 (2)	O4—Eu1—O9—N4	−27.60 (19)
O6—Eu1—O1—C1	−33.9 (2)	O7—Eu1—O9—N4	−0.95 (15)
O10—Eu1—O1—C1	107.0 (2)	O6—Eu1—O9—N4	34.82 (19)
O9—Eu1—O1—C1	96.0 (2)	O10—Eu1—O9—N4	86.29 (17)
O12—Eu1—O1—C1	−147.2 (2)	O12—Eu1—O9—N4	119.27 (16)
O2—Eu1—O1—Cu2	−23.08 (6)	O11—N5—O10—Eu1	173.6 (3)
O3—Eu1—O1—Cu2	57.52 (7)	O12—N5—O10—Eu1	−6.8 (2)
O4—Eu1—O1—Cu2	135.25 (8)	O2—Eu1—O10—N5	71.73 (17)
O7—Eu1—O1—Cu2	−151.39 (7)	O1—Eu1—O10—N5	131.96 (17)
O6—Eu1—O1—Cu2	129.24 (8)	O3—Eu1—O10—N5	−9.2 (2)
O10—Eu1—O1—Cu2	−89.87 (16)	O4—Eu1—O10—N5	−100.39 (17)
O9—Eu1—O1—Cu2	−100.81 (8)	O7—Eu1—O10—N5	−163.56 (18)
O12—Eu1—O1—Cu2	15.99 (13)	O6—Eu1—O10—N5	−79.37 (17)
C15—C16—O2—Cu2	−162.6 (2)	O9—Eu1—O10—N5	143.41 (18)
C11—C16—O2—Cu2	17.2 (3)	O12—Eu1—O10—N5	4.01 (15)
C15—C16—O2—Eu1	46.6 (3)	O11—N5—O12—Eu1	−173.7 (3)
C11—C16—O2—Eu1	−133.5 (2)	O10—N5—O12—Eu1	6.7 (2)
N2—Cu2—O2—C16	−12.5 (2)	O2—Eu1—O12—N5	−116.63 (16)
O1—Cu2—O2—C16	174.6 (2)	O1—Eu1—O12—N5	−153.03 (14)
N2—Cu2—O2—Eu1	146.33 (9)	O3—Eu1—O12—N5	164.50 (17)
O1—Cu2—O2—Eu1	−26.56 (7)	O4—Eu1—O12—N5	102.18 (16)
O1—Eu1—O2—C16	179.4 (2)	O7—Eu1—O12—N5	11.19 (18)
O3—Eu1—O2—C16	98.3 (2)	O6—Eu1—O12—N5	75.53 (16)
O4—Eu1—O2—C16	146.0 (2)	O10—Eu1—O12—N5	−3.94 (15)
O7—Eu1—O2—C16	−104.8 (2)	O9—Eu1—O12—N5	−45.68 (17)
O6—Eu1—O2—C16	48.2 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H18···O12^i	0.85	2.04	2.886 (3)	174

Symmetry code: (i) −x+1, −y+1, −z+1.