Tetra-μ-acetato-κ⁴ O:O′;κ³ O,O′:O′;κ³ O:O,O′-bis­[(acetato-κ² O,O′)(1,10-phenanthroline-κ² N,N′)europium(III)]

Abstract

In the title centrosymmetric dinuclear Eu^III complex, [Eu₂(CH₃COO)₆(C₁₂H₈N₂)₂], each Eu^III cation is coordinated by seven O atoms from five acetate anions and two N atoms from one phenanthroline ligand in a distorted tricapped trigonal-prismatic geometry. Four acetate anions bridge two Eu^III cations to form the dinuclear complex, with an Eu⋯Eu distance of 3.9409 (8) Å. Weak inter­molecular C—H⋯O hydrogen bonding is present in the crystal structure.

Related literature

For related lanthanide complexes with 1,10-phenanthroline and acetate ligands, see: Hu et al. (2006 ▶); Panagiotopoulos et al. (1995 ▶).

Experimental

Crystal data

• [Eu₂(C₂H₃O₂)₆(C₁₂H₈N₂)₂]

• M _r = 1018.61

• Triclinic,

• a = 8.7671 (19) Å

• b = 8.9265 (19) Å

• c = 12.992 (3) Å

• α = 103.631 (2)°

• β = 109.254 (2)°

• γ = 98.300 (3)°

• V = 905.1 (3) ų

• Z = 1

• Mo Kα radiation

• μ = 3.50 mm⁻¹

• T = 298 K

• 0.20 × 0.19 × 0.18 mm

Data collection

• Bruker SMART CCD diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T _min = 0.541, T _max = 0.571

• 5010 measured reflections

• 3474 independent reflections

• 3062 reflections with I > 2σ(I)

• R _int = 0.021

Refinement

• R[F ² > 2σ(F ²)] = 0.030

• wR(F ²) = 0.062

• S = 1.05

• 3474 reflections

• 247 parameters

• H-atom parameters constrained

• Δρ_max = 0.80 e Å⁻³

• Δρ_min = −0.64 e Å⁻³

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O2i	0.93	2.57	3.287 (6)	135
C12—H8⋯O6ii	0.93	2.44	3.078 (6)	126
C16—H10C⋯O1iii	0.96	2.45	3.390 (6)	165

Symmetry codes: (i) ; (ii) ; (iii) .

supplementary crystallographic information

Comment

Dinuclear lanthanide complexes with 1,10-phenanthroline and acetate ligands had previously been reported (Panagiotopoulos et al., 1995; Hu et al., 2006). In this title complex, each Eu atom is coordinated by two N atoms from one chelating phenanthroline ligand and seven oxygen atoms from acetate ions, to form a distorted tricapped trigonal prism, giving a dimeric structure with an inversion center (Fig.1). The result of the dinuclear centrosymmetric molecule with the Eu···Eu distance of 3.9409 (8) Å was that acetate ions exhibit three different coordination modes: common bidentate chelating mode, bidentate bridging mode and tridentate bridging mode. The Eu1—O bond distances vary from 2.359 (3) Å to 2.586 (3) Å and the Eu1—N bond length are 2.594 (3) Å and 2.649 (4) Å. The C—O distances of CH₃COO^- are within the range of 1.257 (5)Å to 1.273 (5) Å. This complex exhibits a three-dimensional structure via C—H···O hydrogen-bonds (Table 1).

Experimental

A stoichiometric amount of acetic acid and a quantitative amount of 1,10-phenanthroline (0.5 mmol) were mixed and then dissolved in 95% ethanol solution (20 ml). The pH value of the solution was adjusted to 6.5 by adding 1.0 M NaOH solution, and then added dropwise to the ethanol solution (20 ml) of Eu(NO₃)₃.6H₂O (0.5 mmol). The solution mixture was stirred continuously for 2 h at room temperature and then filtered. Single crystals were obtained by evaporation after one week.

Refinement

H atoms were positioned in calculated positions, with C—H = 0.93 (aromatic) and 0.96 Å (methyl), and refined in riding mode with U_iso(H) = 1.5U_eq(C) for methyl and 1.2U_eq(C) for the others.

Figures

Fig. 1.

Displacement ellipsoid plot (40% probability level) of the title compound [symmetry code: (A) -x+1, -y+2, -z+1].

Crystal data

[Eu2(C2H3O2)6(C12H8N2)2]	Z = 1
Mr = 1018.61	F(000) = 500
Triclinic, P1	Dx = 1.869 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.7671 (19) Å	Cell parameters from 2079 reflections
b = 8.9265 (19) Å	θ = 0.7–25.2°
c = 12.992 (3) Å	µ = 3.50 mm−1
α = 103.631 (2)°	T = 298 K
β = 109.254 (2)°	Block, colorless
γ = 98.300 (3)°	0.20 × 0.19 × 0.18 mm
V = 905.1 (3) Å3

Data collection

Bruker SMART CCD diffractometer	3474 independent reflections
Radiation source: fine-focus sealed tube	3062 reflections with I > 2σ(I)
graphite	Rint = 0.021
ω scans	θmax = 26.0°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −10→10
Tmin = 0.541, Tmax = 0.571	k = −8→10
5010 measured reflections	l = −14→15

Refinement

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.062	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.025P)2] where P = (Fo2 + 2Fc2)/3
3474 reflections	(Δ/σ)max < 0.001
247 parameters	Δρmax = 0.80 e Å−3
0 restraints	Δρmin = −0.64 e Å−3

Special details

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

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	0.47430 (3)	0.84412 (3)	0.356229 (17)	0.02341 (8)
O3	0.5788 (4)	1.1409 (4)	0.4756 (2)	0.0312 (7)
O4	0.6208 (4)	1.0735 (4)	0.3157 (2)	0.0336 (7)
O2	0.2565 (4)	0.5955 (4)	0.2687 (3)	0.0419 (8)
O1	0.5000 (4)	0.5829 (4)	0.3834 (3)	0.0373 (8)
O5	0.7449 (4)	0.8969 (4)	0.4988 (2)	0.0310 (7)
N1	0.6375 (4)	0.7194 (4)	0.2384 (3)	0.0277 (8)
C1	0.7671 (6)	0.6658 (5)	0.2863 (4)	0.0362 (11)
H1	0.7915	0.6637	0.3612	0.043*
C2	0.8702 (6)	0.6116 (6)	0.2307 (4)	0.0423 (12)
H2	0.9609	0.5753	0.2678	0.051*
C3	0.8341 (6)	0.6134 (6)	0.1215 (4)	0.0450 (13)
H3	0.9007	0.5782	0.0829	0.054*
C4	0.6972 (6)	0.6680 (6)	0.0664 (4)	0.0368 (11)
C7	0.4176 (6)	0.7809 (6)	−0.0387 (4)	0.0421 (13)
C6	0.4559 (6)	0.7750 (5)	0.0747 (3)	0.0294 (10)
N2	0.3612 (5)	0.8179 (4)	0.1353 (3)	0.0323 (9)
C12	0.2280 (6)	0.8637 (6)	0.0849 (4)	0.0437 (13)
H8	0.1601	0.8895	0.1249	0.052*
C11	0.1825 (7)	0.8757 (7)	−0.0271 (4)	0.0565 (16)
H7	0.0883	0.9110	−0.0592	0.068*
C10	0.2789 (7)	0.8348 (7)	−0.0871 (4)	0.0524 (15)
H6	0.2516	0.8431	−0.1607	0.063*
C5	0.6006 (6)	0.7203 (5)	0.1290 (4)	0.0299 (10)
C15	0.6463 (5)	1.1743 (5)	0.4079 (4)	0.0284 (10)
C13	0.3479 (6)	0.5207 (5)	0.3230 (4)	0.0327 (11)
C8	0.5223 (7)	0.7281 (7)	−0.0976 (4)	0.0534 (15)
H5	0.4986	0.7328	−0.1718	0.064*
O6	0.7627 (4)	1.0478 (4)	0.6690 (2)	0.0336 (7)
C14	0.2753 (7)	0.3534 (6)	0.3168 (5)	0.0506 (14)
H9A	0.1575	0.3255	0.2737	0.076*
H9B	0.2959	0.3470	0.3927	0.076*
H9C	0.3264	0.2814	0.2800	0.076*
C16	0.7559 (6)	1.3374 (6)	0.4417 (4)	0.0422 (12)
H10A	0.8097	1.3412	0.3886	0.063*
H10B	0.8385	1.3612	0.5172	0.063*
H10C	0.6894	1.4140	0.4409	0.063*
C9	0.6513 (7)	0.6730 (7)	−0.0494 (4)	0.0539 (15)
H4	0.7136	0.6367	−0.0914	0.065*
C18	0.9975 (5)	0.9554 (6)	0.6560 (4)	0.0395 (12)
H11A	1.0003	0.8457	0.6445	0.059*
H11B	1.0414	1.0106	0.7365	0.059*
H11C	1.0636	1.0025	0.6206	0.059*
C17	0.8220 (5)	0.9669 (5)	0.6038 (4)	0.0277 (10)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Eu1	0.02392 (12)	0.02795 (13)	0.02150 (12)	0.00926 (9)	0.01093 (9)	0.00800 (9)
O3	0.0368 (18)	0.0376 (18)	0.0297 (16)	0.0146 (15)	0.0192 (14)	0.0159 (15)
O4	0.0410 (19)	0.0386 (19)	0.0242 (16)	0.0079 (15)	0.0181 (14)	0.0077 (15)
O2	0.039 (2)	0.038 (2)	0.045 (2)	0.0085 (16)	0.0110 (16)	0.0142 (17)
O1	0.038 (2)	0.0360 (19)	0.0442 (19)	0.0151 (15)	0.0170 (16)	0.0167 (16)
O5	0.0288 (17)	0.0393 (19)	0.0243 (16)	0.0108 (14)	0.0111 (13)	0.0056 (14)
N1	0.030 (2)	0.028 (2)	0.0260 (19)	0.0091 (16)	0.0132 (16)	0.0064 (16)
C1	0.044 (3)	0.038 (3)	0.032 (3)	0.017 (2)	0.019 (2)	0.011 (2)
C2	0.034 (3)	0.047 (3)	0.050 (3)	0.018 (2)	0.018 (2)	0.013 (3)
C3	0.046 (3)	0.047 (3)	0.048 (3)	0.016 (3)	0.031 (3)	0.004 (3)
C4	0.043 (3)	0.037 (3)	0.032 (3)	0.011 (2)	0.021 (2)	0.003 (2)
C7	0.050 (3)	0.048 (3)	0.025 (2)	0.007 (3)	0.014 (2)	0.010 (2)
C6	0.036 (3)	0.027 (2)	0.022 (2)	0.004 (2)	0.011 (2)	0.0032 (19)
N2	0.034 (2)	0.035 (2)	0.027 (2)	0.0104 (18)	0.0096 (17)	0.0088 (18)
C12	0.039 (3)	0.061 (4)	0.031 (3)	0.024 (3)	0.011 (2)	0.012 (3)
C11	0.064 (4)	0.074 (4)	0.033 (3)	0.033 (3)	0.009 (3)	0.021 (3)
C10	0.069 (4)	0.060 (4)	0.027 (3)	0.018 (3)	0.013 (3)	0.016 (3)
C5	0.037 (3)	0.025 (2)	0.028 (2)	0.005 (2)	0.015 (2)	0.005 (2)
C15	0.027 (2)	0.034 (3)	0.031 (2)	0.012 (2)	0.014 (2)	0.015 (2)
C13	0.043 (3)	0.033 (3)	0.029 (2)	0.012 (2)	0.024 (2)	0.006 (2)
C8	0.067 (4)	0.071 (4)	0.029 (3)	0.018 (3)	0.027 (3)	0.015 (3)
O6	0.0333 (18)	0.0416 (19)	0.0257 (16)	0.0171 (15)	0.0109 (14)	0.0052 (15)
C14	0.064 (4)	0.033 (3)	0.057 (3)	0.004 (3)	0.027 (3)	0.016 (3)
C16	0.049 (3)	0.036 (3)	0.046 (3)	0.007 (2)	0.027 (3)	0.009 (2)
C9	0.063 (4)	0.066 (4)	0.037 (3)	0.017 (3)	0.030 (3)	0.008 (3)
C18	0.030 (3)	0.044 (3)	0.041 (3)	0.013 (2)	0.009 (2)	0.009 (2)
C17	0.027 (2)	0.028 (2)	0.034 (3)	0.0086 (19)	0.014 (2)	0.014 (2)

Geometric parameters (Å, °)

Eu1—O3i	2.358 (3)	C7—C10	1.384 (7)
Eu1—O6i	2.374 (3)	C7—C6	1.415 (6)
Eu1—O5	2.377 (3)	C7—C8	1.438 (7)
Eu1—O2	2.453 (3)	C6—N2	1.355 (5)
Eu1—O1	2.470 (3)	C6—C5	1.448 (6)
Eu1—O4	2.513 (3)	N2—C12	1.311 (6)
Eu1—O3	2.586 (3)	C12—C11	1.411 (7)
Eu1—N1	2.594 (3)	C12—H8	0.9300
Eu1—N2	2.649 (4)	C11—C10	1.358 (7)
Eu1—C13	2.815 (5)	C11—H7	0.9300
Eu1—C15	2.920 (4)	C10—H6	0.9300
Eu1—Eu1i	3.9409 (8)	C15—C16	1.500 (6)
O3—C15	1.276 (5)	C13—C14	1.508 (6)
O3—Eu1i	2.358 (3)	C8—C9	1.324 (8)
O4—C15	1.245 (5)	C8—H5	0.9300
O2—C13	1.262 (6)	O6—C17	1.273 (5)
O1—C13	1.262 (5)	O6—Eu1i	2.374 (3)
O5—C17	1.256 (5)	C14—H9A	0.9600
N1—C1	1.319 (6)	C14—H9B	0.9600
N1—C5	1.351 (5)	C14—H9C	0.9600
C1—C2	1.402 (6)	C16—H10A	0.9600
C1—H1	0.9300	C16—H10B	0.9600
C2—C3	1.352 (7)	C16—H10C	0.9600
C2—H2	0.9300	C9—H4	0.9300
C3—C4	1.399 (7)	C18—C17	1.492 (6)
C3—H3	0.9300	C18—H11A	0.9600
C4—C5	1.410 (6)	C18—H11B	0.9600
C4—C9	1.437 (7)	C18—H11C	0.9600
O3i—Eu1—O6i	75.03 (10)	C5—N1—Eu1	120.7 (3)
O3i—Eu1—O5	76.96 (10)	N1—C1—C2	123.7 (4)
O6i—Eu1—O5	137.07 (10)	N1—C1—H1	118.2
O3i—Eu1—O2	86.29 (10)	C2—C1—H1	118.2
O6i—Eu1—O2	81.08 (11)	C3—C2—C1	118.2 (5)
O5—Eu1—O2	128.67 (11)	C3—C2—H2	120.9
O3i—Eu1—O1	77.36 (10)	C1—C2—H2	120.9
O6i—Eu1—O1	127.36 (11)	C2—C3—C4	120.5 (4)
O5—Eu1—O1	75.84 (10)	C2—C3—H3	119.8
O2—Eu1—O1	53.10 (11)	C4—C3—H3	119.8
O3i—Eu1—O4	125.07 (10)	C3—C4—C5	117.4 (4)
O6i—Eu1—O4	90.28 (11)	C3—C4—C9	123.4 (5)
O5—Eu1—O4	79.96 (10)	C5—C4—C9	119.2 (5)
O2—Eu1—O4	144.17 (10)	C10—C7—C6	117.6 (5)
O1—Eu1—O4	141.79 (10)	C10—C7—C8	123.9 (5)
O3i—Eu1—O3	74.40 (11)	C6—C7—C8	118.5 (5)
O6i—Eu1—O3	72.72 (10)	N2—C6—C7	122.5 (4)
O5—Eu1—O3	68.79 (10)	N2—C6—C5	118.0 (4)
O2—Eu1—O3	150.59 (10)	C7—C6—C5	119.5 (4)
O1—Eu1—O3	138.62 (10)	C12—N2—C6	117.9 (4)
O4—Eu1—O3	50.80 (9)	C12—N2—Eu1	122.8 (3)
O3i—Eu1—N1	143.33 (11)	C6—N2—Eu1	118.7 (3)
O6i—Eu1—N1	139.90 (10)	N2—C12—C11	123.2 (5)
O5—Eu1—N1	77.84 (10)	N2—C12—H8	118.4
O2—Eu1—N1	89.07 (11)	C11—C12—H8	118.4
O1—Eu1—N1	70.92 (11)	C10—C11—C12	118.8 (5)
O4—Eu1—N1	75.40 (10)	C10—C11—H7	120.6
O3—Eu1—N1	119.64 (10)	C12—C11—H7	120.6
O3i—Eu1—N2	149.00 (11)	C11—C10—C7	120.0 (5)
O6i—Eu1—N2	77.11 (11)	C11—C10—H6	120.0
O5—Eu1—N2	133.80 (10)	C7—C10—H6	120.0
O2—Eu1—N2	76.19 (11)	N1—C5—C4	122.1 (4)
O1—Eu1—N2	110.07 (11)	N1—C5—C6	118.6 (4)
O4—Eu1—N2	67.99 (10)	C4—C5—C6	119.3 (4)
O3—Eu1—N2	109.76 (10)	O4—C15—O3	120.4 (4)
N1—Eu1—N2	62.79 (11)	O4—C15—C16	121.0 (4)
O3i—Eu1—C13	79.18 (11)	O3—C15—C16	118.5 (4)
O6i—Eu1—C13	103.79 (13)	O4—C15—Eu1	58.8 (2)
O5—Eu1—C13	102.11 (13)	O3—C15—Eu1	62.3 (2)
O2—Eu1—C13	26.59 (12)	C16—C15—Eu1	172.3 (3)
O1—Eu1—C13	26.61 (12)	O2—C13—O1	121.4 (4)
O4—Eu1—C13	154.90 (11)	O2—C13—C14	119.9 (4)
O3—Eu1—C13	153.35 (11)	O1—C13—C14	118.8 (5)
N1—Eu1—C13	80.57 (12)	O2—C13—Eu1	60.5 (2)
N2—Eu1—C13	94.65 (12)	O1—C13—Eu1	61.3 (2)
O3i—Eu1—C15	99.99 (11)	C14—C13—Eu1	173.6 (3)
O6i—Eu1—C15	82.87 (11)	C9—C8—C7	122.1 (5)
O5—Eu1—C15	70.72 (11)	C9—C8—H5	119.0
O2—Eu1—C15	160.62 (12)	C7—C8—H5	119.0
O1—Eu1—C15	146.09 (11)	C17—O6—Eu1i	136.1 (3)
O4—Eu1—C15	25.08 (10)	C13—C14—H9A	109.5
O3—Eu1—C15	25.89 (10)	C13—C14—H9B	109.5
N1—Eu1—C15	96.31 (11)	H9A—C14—H9B	109.5
N2—Eu1—C15	89.71 (11)	C13—C14—H9C	109.5
C13—Eu1—C15	172.71 (13)	H9A—C14—H9C	109.5
O3i—Eu1—Eu1i	39.20 (7)	H9B—C14—H9C	109.5
O6i—Eu1—Eu1i	69.54 (7)	C15—C16—H10A	109.5
O5—Eu1—Eu1i	68.14 (7)	C15—C16—H10B	109.5
O2—Eu1—Eu1i	122.20 (8)	H10A—C16—H10B	109.5
O1—Eu1—Eu1i	111.19 (7)	C15—C16—H10C	109.5
O4—Eu1—Eu1i	85.93 (7)	H10A—C16—H10C	109.5
O3—Eu1—Eu1i	35.19 (6)	H10B—C16—H10C	109.5
N1—Eu1—Eu1i	143.56 (8)	C8—C9—C4	121.4 (5)
N2—Eu1—Eu1i	137.30 (8)	C8—C9—H4	119.3
C13—Eu1—Eu1i	118.30 (9)	C4—C9—H4	119.3
C15—Eu1—Eu1i	60.89 (9)	C17—C18—H11A	109.5
C15—O3—Eu1i	160.5 (3)	C17—C18—H11B	109.5
C15—O3—Eu1	91.8 (3)	H11A—C18—H11B	109.5
Eu1i—O3—Eu1	105.60 (10)	C17—C18—H11C	109.5
C15—O4—Eu1	96.1 (2)	H11A—C18—H11C	109.5
C13—O2—Eu1	92.9 (3)	H11B—C18—H11C	109.5
C13—O1—Eu1	92.1 (3)	O5—C17—O6	125.1 (4)
C17—O5—Eu1	139.2 (3)	O5—C17—C18	117.4 (4)
C1—N1—C5	118.2 (4)	O6—C17—C18	117.5 (4)
C1—N1—Eu1	120.9 (3)

Symmetry codes: (i) −x+1, −y+2, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O2ii	0.93	2.57	3.287 (6)	135
C12—H8···O6i	0.93	2.44	3.078 (6)	126
C16—H10C···O1iii	0.96	2.45	3.390 (6)	165

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