Synthesis and characterization of new lanthanide complexes with hexadentate hydrazonic ligands

Article abstract of DOI:10.1016/j.ica.2004.10.003

In this paper, we report the synthesis and the characterization of a novel series of lanthanide (III) complexes with two potentially hexadentate ligands.The ligands contain a rigid phenanthroline moiety and two flexible hydrazonic arms with different donor atom sets (NNN′N′OO and NNN′N′N″N″, respectively for H₂L¹ (2,9-diformylphenanthroline)bis(benzoyl)hydrazone and H₂L² (2,9-diformylphenanthroline)bis(2-pyridyl)hydrazone).Both nitrate and acetate complexes of H₂L¹ with La, Eu, Gd, and Tb were prepared and fully characterized, and the X-ray crystal structure of the complex [Eu(HL¹)(CH₃ COO)₂] ? 5H₂O is presented.The stability constants of the equilibria Ln³⁺ + H ₂L¹ = [Ln(H₂L¹)]³⁺ and Ln³⁺ + (L¹)^2- = [Ln(L₁)]⁺ (Ln = La(III), Eu(III), Gd(III), and Tb(III)) are determined by UV spectrophotometric titrations in DMSO at t = 25°C. The nitrate complexes of H₂L² with La, Eu, Gd and Tb were also synthesized, and the X-ray crystal structures of [La(H₂L²)(NO ₃)₂(H₂O)](NO₃), [Eu(H ₂L²)(NO₃)₂](NO₃) and [Tb(H₂ L²)(NO₃)₂](NO₃) are discussed.

Full text of DOI:10.1016/j.ica.2004.10.003

Inorganica Chimica Acta 358 (2005) 903–911
www.elsevier.com/locate/ica
Synthesis and characterization of new lanthanide complexes with
hexadentate hydrazonic ligands
a
M. Carcelli , S. Ianelli , P. Pelagatti , G. Pelizzi , D. Rogolino
a
a
a
a,
*
,
b
C. Solinas , M. Tegoni
a
a
`
Dipartimento di Chimica Generale ed Inorganica, Chimica Analitica, Chimica Fisica, Universita degli Studi di Parma, Parco Area delle Scienze,
17/A-43100 Parma, Italy
b
`
Dipartimento di Scienze del Farmaco, Universita di Sassari, Via Muroni 23/A-07100 Sassari, Italy
Received 6 April 2004; accepted 4 October 2004
Available online 28 October 2004
Abstract
In this paper, we report the synthesis and the characterization of a novel series of lanthanide (III) complexes with two potentially
hexadentate ligands. The ligands contain a rigid phenanthroline moiety and two flexible hydrazonic arms with different donor atom
sets (NNN0N0OO and NNN0N0N00N00, respectively for H2L1 (2,9-diformylphenanthroline)bis(benzoyl)hydrazone and H2L2 (2,9-dif-
ormylphenanthroline)bis(2-pyridyl)hydrazone). Both nitrate and acetate complexes of H2L1 with La, Eu, Gd, and Tb were prepared
and fully characterized, and the X-ray crystal structure of the complex [Eu(HL1)(CH3 COO)2] Æ 5H2O is presented. The stability con-
stants of the equilibria Ln3+ + H2L1 = [Ln(H2L1)]3+ and Ln3+ + (L1)2ꢀ = [Ln(L1)]+ (Ln = La(III), Eu(III), Gd(III), and Tb(III)) are
determined by UV spectrophotometric titrations in DMSO at t = 25 ꢀC. The nitrate complexes of H2L2 with La, Eu, Gd and Tb
were also synthesized, and the X-ray crystal structures of [La(H2L2)(NO3)2(H2O)](NO3), [Eu(H2L2)(NO3)2](NO3) and [Tb(H2
L2)(NO3)2](NO3) are discussed.
ꢁ 2004 Elsevier B.V. All rights reserved.
Keywords: Lanthanide ions; Hydrazones; Hexadentate ligands, crystal structure; Phenantroline derivatives
1. Introduction
of nucleic acids is another active field of research, mainly
because it is essential for further developments in bio-
technology, molecular biology, therapy and related
fields [6–9]. The numerous applications of lanthanide
complexes motivate the significant efforts that have been
made in recent years to design polydentate ligands for
their complexation [10,11]. In particular, many studies
have been done on lanthanide complexes with Schiff
base macrocycles, due to their high stability [12–14].
Acyclic Schiff bases have not been extensively studied,
but they offer the advantage of a flexible cavity size, as
some studies regarding pentadentate bis acylhydrazones
of 2,6-diacetylpyridine suggest [15–17]. As a part of our
ongoing research on the coordination properties of
hydrazonic ligands, we recently reported about
the chelating abilities of the potentially hexadentate
Lanthanide complexes have an increasingly impor-
tant role in medicine, where they are employed as diag-
nostic as well as therapeutic agents [1]. The peculiar
electronic properties of lanthanide ions, in fact, are
exploited for the development of powerful NMR probes
for medical application [2]; gadolinium(III) complexes
are in current clinical use for magnetic resonance imag-
ing [3,4] and lutetium compounds have shown a great
potential as radio sensitizer for the treatment of certain
types of cancers [5]. The study of the remarkable cata-
lytic activity of the rare earth metals for the hydrolysis
*
Corresponding author. Tel.: +39 521 905422; fax: +39 521 905557.
E-mail address: dominga.rogolino@unipr.it (D. Rogolino).
0020-1693/$ - see front matter ꢁ 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2004.10.003

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M. Carcelli et al. / Inorganica Chimica Acta 358 (2005) 903–911
(2,9-diformylphenanthroline)bis(benzoyl)hydrazone
(H2L1, Scheme 1) towards dibutyltin diacetate and
diphenyllead dichloride [18]. 2,9-Diformylphenanthro-
line has been widely employed as a metal-binding com-
ponent in all aspects of coordination chemistry, but
there are few reports about its derivatives, especially as
far as hexadentate ligands are concerned [19,20]. This
type of ligand mixes the rigidity imposed by the central
phenanthroline ring with the flexibility of the hydrazonic
arms and presents a cavity large enough to accommo-
date rare-earth metal ions. The variable and versatile
co-ordination behavior of these ions limits their selective
introduction into rigid preorganized molecular architec-
tures, and the development of flexible, predisposed
receptor with pendant arms that can adapt to the vary-
ing size of the lanthanide(III) ions is highly desirable
[21].
In this paper, we report the synthesis and characteri-
zation of both nitrate and acetate complexes of (2,9-dif-
ormylphenanthroline)bis(benzoyl)hydrazone with La,
Eu, Gd, and Tb and the crystal structure of the complex
[Eu(HL1)(CH3COO)2] Æ 5H2O is presented. The interac-
tions between trivalent lanthanide ions and polydentate
nitrogen ligands have attracted great interest in recent
years, mainly because of the task of actinide/lanthanide
separation in radioactive wastes coming from spent nu-
clear fuel processing [22]. Rare earth ions of the 4f series
are known to be hard acids in the Pearson classification
of acids and bases [23]. As a consequence, hard donor
ligands such as oxygen donors are expected to be pre-
ferred to soft S or N donor ligands. Nevertheless,
numerous studies have shown that lanthanide ions form
significantly stable complexes when a multidentate
nitrogen ligand is appropriately chosen [24–26]. There-
fore, the hexadentate N2N02N200 ligand (2,9-diformylphen-
anthroline)bis(2-pyridyl)hydrazone (H2L2, Scheme 1)
was also synthesized and characterized, together with
the nitrate series of its Ln(III) (Ln = La, Eu, Gd, Tb)
complexes; in particular, the X-ray structures of the
complexes [La(H2L2)(NO3)2(H2O)](NO3), [Eu(H2L2)-
(NO3)2](NO3) and [Tb(H2L2)(NO3)2](NO3) are also
discussed.
2. Experimental
2.1. General
All reagents of commercial quality were used without
1
further purification. H NMR spectra were recorded at
27 ꢀC on a Bruker 300 FT spectrophotometer by using
SiMe4 as internal standard, while IR spectra were ob-
tained with a Nicolet 5PCFT-IR spectrophotometer in
the 4000–400 cmꢀ1 range, using KBr disks. Elemental
analyses were performed by using a Carlo Erba Model
EA 1108 apparatus. 2,9-Diformyl-1,10-phenanthroline
(DFF) and H2L1 were made according to the literature
methods [18,27].
2.2. Synthesis
2.2.1. H2L2
A solution of 2-pyridylhydrazine (0.23 g, 2.1 mmol)
in methanol (20 ml) was added to a refluxing solution
of DFF (0.25 g, 1.05 mmol) in the same solvent (75
ml). After few minutes, a brown precipitate appeared.
The solution was refluxed for additional 2 h. After cool-
ing, the precipitate was filtered off and washed with
methanol. Yield: 64%; m.p. = 211–213 ꢀC. 1H NMR
(300 MHz, [D6] DMSO, 25 ꢀC): d = 6.86 (t, JH, H = 7
Hz; 2H, H7); 7.43 (d, JH, H = 8 Hz, 2H, H5); 7.72 (d,
JH, H
=
7 Hz; 2H, H6); 7.95 (s, 2H, H1); 8.19 (d,
1
1
2
2
3
3
N
N
H
N
H
N
H
H
4
4
N
N
N
N
NH
5
HN
NH
HN
N
7
N
O
O
5
7
8
6
6
H2L1
H2L2
Scheme 1. The potentially hexadentate ligands (2,9-diformylphenanthroline)bis(benzoyl)hydrazone (H2L1) and (2,9-diformylphenanthroline)bis(2-
pyridyl)hydrazone (H2L2).

M. Carcelli et al. / Inorganica Chimica Acta 358 (2005) 903–911
905
JH, H = 5 Hz, 2H, H8); 8.35 (d, JH, H = 8 Hz; 2H, H3);
8.45 (m, 4H, H2 + H4); 10.41 (s, 2H, N–H, exchange
with D2O). IR (cmꢀ1): mNH = 3268; mC@N = 1573. MS–
CI (pos. ions): m/z 420 [MH+, 100]. Anal. Calc. for
C28H20N6O2 Æ 3H2O: C, 63.90; H, 4.93; N, 15.95. Found:
C, 64.04; H, 4.69; N, 15.62%.
2.2.7. [Eu(H2L1)(NO3)2](NO3) Æ 2H2O
1
Yield: 65%; m.p. >300 ꢀC. H NMR (300 MHz, [D6]
DMSO, 25 ꢀC): d = 7.56–7.65 (m, 6H, H6 + H7); 7.97 (d,
JH, H = 7 Hz, 4H, H5); 8.08 (s, 2H, H1); 8.39 (d, br; 2H,
H3); 8.58 (d, JH, H = 8 Hz; 2H, H2); 8.84 (s, 2H, H4); 9.71
(s, 2H, N–H, exchange with D2O). IR (cmꢀ1):
m
OH = 3419; mNH = 3162; mC@O = 1623; mNO2(sym) = 1497;
2.2.2. [La(HL1)(CH3COO)2] Æ 2H2O
mNO3(ionic) = 1377; mNO2(asym) = 1301. Anal. Calc. for
C28H20EuN9O11 Æ 2H2O: C, 39.74; H, 2.83; N, 14.88.
Found: C, 39.50; H, 2.55; N, 14.45%.
The ligand (0.08 g, 0.16 mmol) was dissolved in
warm ethanol (50 ml). After addition of the metal salt
(0.053 g, 0.16 mmol), the solution turned from brown
to intense yellow. After refluxing for 4 h, the solution
was concentrated and diethyl ether added: a yellow
powder precipitated, which was filtered off and washed
2.2.8. [Gd(H2L1)(NO3)2](NO3) Æ 2H2O
Yield: 71%; m.p. >300 ꢀC. IR (cmꢀ1):mOH = 3417;
mNH = 3134; mC=O = 1615; NO2(sym) = 1498; mNO3(ionic) =
1
with ether. Yield: 61%; m.p. >300 ꢀC. H NMR (300
1384;
m
NO2(asym) = 1302.
Anal.
Calc.
for
MHz, [D6] DMSO, 25 ꢀC): d = 1.56 (s, 6H, CH3COO);
7.49 (m, 6H, H6 + H7); 8.03 (s, 2H, H1); 8.08 (d,
JH, H = 8 Hz; 2H, H3); 8.30 (m, 4H, H5); 8.65 (s,
2H, H4); 8.70 (d, JH, H = 8 Hz; 2H, H2). IR (cmꢀ1):
C28H20GdN9O11 Æ 2H2O: C, 39.49; H, 2.81; N, 14.79.
Found: C, 39.50; H, 2.46; N, 14.29%.
2.2.9. [Tb(H2L1)(NO3)2](NO3) Æ H2O
1
m
OH = 3414; mNH ꢁ 3200 br; mC–O = 1545; mC@O(acet)
=
Yield: 63%; m.p. >300 ꢀC. H NMR (300 MHz, [D6]
1437, 1355. Anal. Calc. for C32H25LaN6O6 Æ 2H2O: C,
50.26; H, 3.92; N, 10.99. Found: C, 50.39; H, 3.66;
N, 10.73%.
DMSO, 25 ꢀC): d = 7.57–7.66 (m, 6H, H6 + H7); 7.98 (d,
JH, H = 6 Hz, 4H, H5); 8.09 (s, 2H, H1); 8.38 (d,
JH, H = 8 Hz; 2H, H3); 8.60 (d, JH, H = 8 Hz; 2H, H2);
8.84 (s, 2H, H4); 12.28 (s, 2 H, N–H, exchange with
The other complexes are synthesized by using the
same procedure, with the appropriate metal salt.
D2O). IR (cmꢀ1): mOH = 3419; mNH = 3175; mC@O
1614; mNO2(sym) = 1493; mNO3(ionic) = 1384; mNO2(asym)
=
=
2.2.3. [Eu(HL1)(CH3COO)2] Æ 3H2O
1302. Anal. Calc. for C28 H20N9O11Tb Æ H2O: C, 40.28;
H, 2.65; N, 15.09. Found: C, 40.43; H, 2.40; N, 15.11%.
1
Yield: 52%; m.p. >300 ꢀC. H NMR (300 MHz, [D6]
DMSO, 25 ꢀC): d = 2.69 (s, br); 5.46–5.55 (m, br); 5.80
(s, br); 6.19 (s, br). IR (cmꢀ1): mOH = 3425; mNH ꢁ 3200,
br; mC–O = 1548; mC@O(acet) = 1438, 1360. Anal. Calc. for
C32H25EuN6O6 Æ 3H2O: C, 48.31; H, 3.72; N, 10.55.
Found: C, 48.14; H, 3.46; N 10.30%.
2.2.10. [La(H2L2)(NO3)2](NO3)
The ligand (0.08 g, 0.19 mmol) was dissolved in warm
THF (50 ml). After addition of the metal salt (La(-
NO3)3 Æ 6H2O, 0.060 g, 0.19 mmol), the solution turned
from brown to intense yellow and a precipitate occurred
within few minutes. The reaction mixture was stirred at
reflux for additional 2 h, the yellow-brown powder was
filtered off and washed with ether. Yield: 67%; m.p.
>300 ꢀC. 1H NMR (300 MHz, [D6]DMSO, 25 ꢀC):
d = 6.88 (t, JH, H = 6 Hz, 2H, H7); 7.43 (d, JH, H = 8
Hz, 2H, H5); 7.75 (t, JH, H = 8 Hz, 2H, H6); 7.97 (s,
2H, H1); 8.20 (d, JH, H = 6 Hz, 2H, H8); 8.38 (d, 2H,
JH, H = 8 Hz, H3); 8.44–8.49 (s + d, 4H, H4 + H2);
10.38 (s, 2H, N–H, exchange with D2O). IR (cmꢀ1):
2.2.4. [Gd(HL1)(CH3COO)2] Æ 2H2O
Yield: 54%; m.p. >300 ꢀC. IR (cmꢀ1): mOH = 3380;
mNH ꢁ 3200, br; mC–O = 1550; mC–O(acet) = 1437, 1380.
Anal. Calc. for C32H25GdN6O6 Æ 2H2O: C, 49.09; H,
3.73; N, 10.74. Found: C, 49.23; H, 3.47; N 10.80%.
2.2.5. [Tb(HL1)(CH3COO)2] Æ 5H2O
Yield: 66%; m.p. >300 ꢀC. IR (cmꢀ1): mOH = 3401;
NH = 3218, br; mC–O = 1552; mC@O(acet) = 1455, 1369.
m
Anal. Calc. for C32H25N6O6Tb Æ 5H2O: C, 45.94; H,
3.97; N, 10.04. Found: C, 46.07; H, 3.71; N, 10.13%.
mOH = 3456; mNH = 3233; mNO2(sym) = 1485; mNO3(ionic) =
1384; mNO2(asym) = 1292. Anal. Calc. for C24H18La-
N11O9: C, 38.78; H, 2.44; N, 20.71. Found: C, 38.65;
H, 2.35; N, 20.46%.
2.2.6. [La(H2L1)(NO3)2](NO3)(C2H6O)
1
Yield: 47%; m.p. >300 ꢀC. H NMR (300 MHz, [D6]
DMSO, 25 ꢀC): d = 7.56–7.65 (m, 6H, H6 + H7); 7.97 (d,
JH, H = 8 Hz, 4H, H5); 8.28 (m, 4H, H1 + H3); 8.58 (d,
JH, H = 8 Hz; 2H, H2); 9.01 (s, 2H, H4); 9.70 (s, 2 H,
N–H, exchange with D2O). IR (cmꢀ1): mOH = 3420;
2.2.11. [Eu(H2L2)(NO3)2](NO3)
1
Yield: 72%; m.p. >300 ꢀC. H NMR (300 MHz, [D6]
DMSO, 25 ꢀC): d = 6.90 (t, JH, H = 6 Hz, 2H, H7); 7.44
(d, JH, H = 8 Hz, 2H, H5); 7.77 (t, JH, H = 8 Hz, 2H,
H6); 7.98 (s, 2H, H1); 8.20 (d, JH, H = 6 Hz, 2H, H8);
8.39 (d, 2H, JH, H = 8 Hz, H3); 8.46–8.50 (s + d, 4H,
H4 + H2); 10.32 (s, 2H, N–H, exchange with D2O). IR
m
NH = 3201; mC@O = 1639; mNO2(sym) = 1465; mNO3(ionic) =
1383; mNO2(asym) = 1297. Anal. Calc. for C28H20La-
N9O11 Æ C2H6O: C, 42.72; H, 3.10; N, 14.93. Found: C,
42.78; H, 2.65; N, 15.24%.
(cmꢀ1):
m
OH = 3410;
m
NH = 3265;
mNO2(sym) = 1486;

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M. Carcelli et al. / Inorganica Chimica Acta 358 (2005) 903–911
m
C24H18EuN11O9: C, 38.11; H, 2.39; N, 20.36. Found:
C, 37.95; H, 2.63;, N, 20.15%.
NO3(ionic) = 1383; mNO2(asym) = 1292. Anal. Calc. for
cally. Hydrogen atoms were partly located from
difference Fourier maps and refined isotropically and
were partly introduced in idealized positions. Details
of data collection and structure refinement are summa-
rized in Table 1.
2.2.12. [Gd(H2L2)(NO3)2](NO3)
Yield: 76%; m.p. >300 ꢀC. IR (cmꢀ1): mOH = 3404;
NH = 3274; mNO2(sym) = 1486; mNO3(ionic) = 1383; mNO2(asym)
m
2.4. UV–Vis measurements and calculations
= 1291. Anal. Calc. for C24H18GdN11O9: C, 37.84; H,
2.38; N, 20.21. Found: C, 37.86; H, 2.22; N, 20.67%.
UV–Vis spectra were recorded on a Perkin–Elmer
Lambda 25 spectrophotometer by using match cells
of 1 cm pathlength. Stock solution of H2L1 and
Na2L1 (ca. 2.5 · 10ꢀ3 M) and of the metal nitrates
(ca. 1.0 · 10ꢀ2 M) in DMSO was prepared and used
within 2 days. Absorption spectra of H2L1 and
Na2L1 were registered using a ca. 1.5 · 10ꢀ5 M solu-
tion that is prepared by dilution of the stock solution;
the same solution was employed for the complexation
studies. Each metal/ligand system was studied by
titrating a 10 ml sample of the ligand solution with
the metal stock solution; 8–12 spectra of samples with
M:L molar ratio ranging from 0 to 1.5 are measured.
The stability constants were calculated by means of
the PSEQUAD program [32]. All titrations were per-
formed twice in order to ensure the reproducibility
of the data.
2.2.13. [Tb(H2L2)(NO3)2](NO3) Æ 3/2H2O
Yield: 68%. 1H NMR (300 MHz, [D6] DMSO,
25 ꢀC): d = 6.86 (t, br, 2H, H7); 7.44 (d, br, 2H, H5);
7.73 (t, br, 2H, H6); 7.97 (s, 2H, H1); 8.18 (d, br, 2H,
H8); 8.38 (d, 2H, JH, H = 8 Hz, H3); 8.46 (m, 4H,
H4 + H2); 10.44 (s, 2H, N–H, exchange with D2O). IR
(cmꢀ1):
m
OH = 3426;
m
NH = 3274;
mNO2(sym) = 1486;
m
NO3(ionic) = 1384; mNO2(asym) = 1286. Anal. Calc. for
C24H18N11O9Tb Æ 1.5H2O: C, 36.47; H, 2.67; N, 19.48.
Found: C, 36.51; H, 2.33; N 19.32%.
2.3. X-ray Crystallography
Single crystals of [La(H2L2)(NO3)2(H2O)](NO3),
[Ln(H2L2)(NO3)2](NO3) (Ln = Eu, Tb) and [Eu(HL1)
(CH COO)2] Æ 5H2O suitable for X-ray structure anal-
3
ysis were obtained by slow evaporation of the mother
liqueur. For [Ln(H2L2)(NO3)2](NO3) (Ln = Eu, Tb),
cell dimensions and diffraction intensities were meas-
ured at room temperature on a Philips PW 1100 dif-
fractometer, using graphite monochromated Mo Ka
3. Results and discussion
3.1. Synthesis and characterization of the complexes
The hydrazonic ligand H2L1 (Scheme 1) was synthe-
sized, following a strategy previously described [18].
H2L2 was analogously prepared by condensation of
2,9-diformylphenanthroline and 2-pyridylhydrazine. In
both cases, the spectroscopic characterization does not
show any remarkable aspects: in solution, the ligands
show C2v symmetry and, accordingly, only one set of
˚
radiation (k = 0.71073 A). Both the crystal structures
are described by the triclinic system and the systematic
absences allowed to identify the correct space group as
ꢀ
P1. The unit-cell dimensions were obtained from the
setting angles of 24 reflections with h > 8ꢀ for Tb and
h > 10ꢀ for Eu complex. Crystal decay resulted negligi-
ble in both cases. The intensity data were corrected for
Lorentz, polarization and absorption effects using psi-
scan technique. X-ray diffraction data for [La(H2L2)-
(NO3)2(H2O)](NO3) and [Eu(HL1)(CH3COO)2] Æ 5H2O
were collected at room temperature on a Bruker-Sie-
mens SMART AXS 1000 equipped with CCD detector,
using graphite monochromated Mo Ka radiation. Data
were corrected for absorption effects by the SADABS
[28] procedure. The phase problem was solved by direct
methods [29] and refined by full matrix least squares on
all F2 [30] by using the WinGX package [31]. Aniso-
tropic displacement parameters were refined for all
non hydrogen atoms, except for O4w and O5w in the
Eu acetate complex and for the uncoordinated nitrate
ions in all the nitrate complexes, since they show very
high thermal motions and were therefore refined iso-
tropically. In [La(H2L2)(NO3)2(H2O)](NO3), only the
metal, the nitrogens, the oxygens and the carbons in-
volved in the chelation rings were refined anisotropi-
1
signals is present in their H NMR spectrum.
The acetate complexes of H2L1 were obtained by add-
ing the metal salts (Ln(III) = La, Eu, Gd, Tb) to a
refluxing solution of the ligand in methanol: the com-
plexes were isolated as air stable solids after partial re-
moval of the solvent. In all cases, the IR spectrum
shows a weak absorption around 3200 cmꢀ1, attributa-
ble to the presence of the NH group, suggesting that
the ligand is not completely deprotonated. A partial
deprotonation of the ligand is supported by a peak
around 1550 cmꢀ1, which is characteristic of the phe-
nolic C–O stretching mode [33], while a shoulder at
1635 cmꢀ1 is assignable to the coordinated C@O of
the still protonated hydrazonic arm (1682, 1653 cmꢀ1
in the free ligand). The coordinated acetate groups are
confirmed by two bands at around 1435 and 1360
cmꢀ1 (D @ 75 cmꢀ1), which are diagnostic for a bidentate
chelating acetate [34,25]. Eu and Tb complexes show

M. Carcelli et al. / Inorganica Chimica Acta 358 (2005) 903–911
907
Table 1
Crystal data and structure refinement for [Ln(H2L2)(NO3)2](NO3) (Ln = Eu, Tb), [La(H2L2)(NO3)2(H2O)](NO3), and [Eu(HL1)(CH3 COO)2] Æ 5H2O
Identification code
[Tb(H2L2)(NO3)2](NO3)
[Eu(H2L2)(NO3)2](NO3)
[La(H2L2)(H2O)(NO3)2](NO3) [Eu(HL1)(CH3COO)2] Æ
5H2O
Empirical formula
Formula weight
Crystal system
C24H18N11O9Tb
762.41
triclinic
C24H18EuN11O9
756.45
triclinic
C24H20LaN11O10
761.31
C32H25EuN6O11
821.54
monoclinic
C2/c
monoclinic
P21/c
ꢀ
ꢀ
Space group
Unit cell dimensions
P1
P1
˚
a (A)
11.317(5)
13.000(7)
9.796(3)
100.98(3)
100.88(4)
93.57(3)
1382(1)
2
11.310(3)
12.994(10)
9.802(5)
101.01(5)
100.63(8)
93.89(8)
1382(2)
2
20.133(2)
27.187(3)
12.010(1)
8.574(1)
27.362(4)
17.204(2)
˚
b (A)
˚
c (A)
a (ꢀ)
b (ꢀ)
c (ꢀ)
121.72(1)
93.66(1)
3
˚
Volume (A )
5592(1)
8
1.804
4028(1)
4
1.335
Z
Density (calculated)
(Mg/m3)
Absolute coefficient
(mmꢀ1
1.835
1.818
2.634
0.710
1.606
1.615
)
F(000)
h Range (ꢀ)
Index ranges
752
532
3008
1640
1.90–26.59
3.11–28.10
ꢀ14 6 h 6 14,
ꢀ16 6 k 6 16,
ꢀ12 6 l 6 12
3.11–30.02
ꢀ15 6 h 6 15,
ꢀ17 6 k 6 11,
ꢀ13 6 l 6 13
8042/5158
8042/0/464
0.867
1.86–30.63
ꢀ26 6 h 6 26,
ꢀ37 6 k 6 37,
ꢀ17 6 l 6 17
21,368/7769
7769/6/282
0.742
0 6 h 6 10,
0 6 k 6 34,
ꢀ21 6 l6 21
Reflection collected/unique 6652/6652
Data/restraints/parameters 6652/0/464
Goodness-of-fit on F2
Final R indices [I > 2r(I)]
R indices (all data)
4814/4727
4727/0/442
1.295
1051
R1 = 0.0697, wR2 = 0.1157 R1 = 0.0441, wR2 = 0.0934 R1 = 0.0675, wR2 = 0.1410
R1 = 0.1348, wR2 = 0.1370 R1 = 0.0811, wR2 = 0.1042 R1 = 0.2502, wR2 = 0.1912
R1 = 0.0686, wR2 = 0.1692
R1 = 0.0686, wR2 = 0.1692
1.874; 1.072
Largest difference peak and 0.968; ꢀ0.967
1.826; ꢀ2.215
1.645; 0.757
ꢀ3
˚
hole (e A
)
1
very broad H NMR signals and a significant shift to
higher fields of the aromatic protons with respect to
the diamagnetic La complex. The spectrum of the La
compound shows that the symmetry of the ligand is
maintained in the complex. As a consequence of the
coordination, the protons in position (5) (Scheme 1)
are deshielded versus the free ligand and an analogous
shift to lower fields can be observed for the phenanthr-
oline protons in position (2). From the spectroscopic
data, it is possible to conclude that H2L1 is monodeprot-
onated and N2N02O2 hexadentate; the coordination
sphere of the metal ions is completed by two bidentate
acetate anions. The stoichiometries of the complexes
are confirmed by the elemental analysis. Finally, crystals
of [Eu(HL1)(CH3COO)2] Æ 5H2O suitable for X-ray
analysis were obtained by slow evaporation of the
mother liqueur (see Section 3.2).
are near 1384 cmꢀ1. Upon coordination, the carbonyl
group absorption shifts to 1615–1630 cmꢀ1 (1682–
1653 cmꢀ1 in the free ligand). In conclusion, also
H2L1 still behaves as hexadentate, the coordination
of the metal being completed by two bidentate nitrate
groups; an ionic nitrate assures the neutrality of the
system.
In order to investigate the coordination properties
of a similar hexadentate ligand, the nitrate complexes
of La, Eu, Gd and Tb with the ligand H2L2 were pre-
pared. Attempts to isolate the acetate analogs were
unsuccessful, probably because of the presence of side
reactions and the formation of different chemical spe-
cies. On the contrary, the reaction between the metal
nitrate and a refluxing solution of H2L2 in THF leads
to the corresponding compounds with general formula
[Ln(H2L2)(NO3)](NO3). Elemental analysis and spect-
roscopic data (see Section 2) led us to conclude that
the ligand is neutral and coordinates the metal by
means of the phenanthroline, imine and pyridine nitro-
gen atoms; as in the H2L1 nitrate complexes, the coor-
dination sphere of the metal ion is completed by two
bidentate nitrates, while an ionic nitrate assures the
neutrality of the system. Crystals of [La(H2L2)(NO3)2-
(H2O)](NO3), [Eu(H2L2)(NO3)2](NO3) and [Tb(H2L2)-
The corresponding nitrate complexes were obtained
by an analogous procedure. In this case, the deproto-
nation of H2L1 does not occur (in the IR spectra,
m(N–H) 3200 cmꢀ1; in the 1H NMR spectra, d(N–
H) in the 10–12 ppm range); the absorptions of the
asymmetric and symmetric stretching modes of the
bidentate covalent nitrates are visible around 1490
and 1300 cmꢀ1, respectively, while the anionic nitrates

908
M. Carcelli et al. / Inorganica Chimica Acta 358 (2005) 903–911
0.150
(NO3)2](NO3) suitable for X-ray analysis were obtained
by slow evaporation of the mother liqueur and their
crystal structure is discussed below (see Section 3.2).
The stability constants for the complexes
[Ln(H2L1)]3+ and [Ln(L1)]+ (Ln = La(III), Eu(III),
Gd(III), Tb(III)) are determined by UV spectrophoto-
metric titrations in DMSO and their values are reported
in Table 2. DMSO is required because of the poor solu-
bility of the ligands. The speciation model that gives the
best fitting of the experimental data involves only one
complex species with 1:1 metal:ligand molar ratio; this
is supported also by the presence of an isosbestic point
in each studied system. It is known [16] that the penta-
dentate ligand 2,6-diacetylpyridine bis(p-nitrobenzoyl-
hydrazone) gives with gadolinium(III) a 1:2 M:L
complex, so, alternative models with additional species
(i.e., [Ln2(L1)], [Ln(L1)2], etc.) were considered, but they
gave worse fitting of the experimental data. The exclu-
sive presence of species with a 1:1 metal:ligand molar ra-
tio can be correlated to the rigidity of the ligand, to the
dimensions of its cavity and to its capability of chelating
the metal ions with six donor atoms. In both series of
0.125
0.100
0.075
0.050
0.025
0.000
300
350
400
450
500
550
Wavelenght (nm)
Fig. 1. Experimental spectra of the titration of H2L1 (1.48 · 10ꢀ5
mol dmꢀ3) with a solution of Tb(NO3)3 Æ 5H2O (Tb3+: H2L1 ratio from
1:10 to 15:10).
0.8
0.6
0.4
0.2
0.0
spectra (Ln(III)/H2L1 and LnðIIIÞ=L 2ꢀ), the absorption
1
in the region 400–500 nm increases as the metal concen-
tration increases. The opposite trend is observed in the
range 300–370 nm, where an isosbestic point is present
close to 375 nm. The spectroscopic behavior is very sim-
ilar for all four lanthanide cations. In Figs. 1 and 2, the
experimental spectra for the titration of Tb(III)/H2L1
and Tb(III)/(L1)2ꢀ are reported. The values of the stabil-
ity constants show that all the complexes have almost
the same stability, starting from the neutral ligand; on
the contrary, with the deprotonated ligand (L1)2ꢀ, very
different values were obtained for the different cations.
The log b trend (Eu3+ < Gd3+ < Tb3+) could be ex-
plained in terms of an increased charge/radius ratio,
but the La3+ value is not easily interpreted just taking
into account this parameter.
250
300
350
400
450
500
Wavelenght (nm)
Fig. 2. Experimental spectra of the titration of L1
mol dmꢀ3) with a solution of Tb(NO3)3 Æ 5H2O (Tb3+: L1 ratio from
1:10 to 15:10).
(1.47 · 10ꢀ5
2ꢀ
2ꢀ
[Tb(H2 L2)(NO3)2](NO3) are isostructural; the crystal
structure of the former is presented in Fig. 5. The most
relevant bond distances and angles are shown in Table 3.
The crystal structure of the acetate complex [Eu-
(HL1)(CH3COO)2] Æ 5H2O (Fig. 3) confirms that only
one arm of the ligand is deprotonated, a situation al-
ready found in some bis-acylhydrazonic complexes of
2,6-diacetylpyridine [35]. The ligand acts as hexadentate
through the phenanthroline and imine nitrogen atoms
and the acylhydrazonic oxygens. The coordination of
the metal center is completed by two bidentate acetate
ions. The complex crystallizes with five water molecules
in the asymmetric unit and one of these forms an hydro-
3.2. X-ray Crystallography
The molecular structures of the complexes
[Eu(HL1)(CH3 COO)2] Æ 5H2O and [La(H2L2)(NO3)2-
(H2O)](NO3) are shown in Figs. 3 and 4, respectively.
The nitrate complexes [Eu(H2L2)(NO3)2](NO3) and
Table 2
Logarithm of the stability constants for the equilibria Ln3+ + H2L1 =
[Ln(H2L1)]3+ and Ln3+ + (L1)2ꢀ = [Ln(L1)]+ (Ln = La(III), Eu(III),
Gd(III), Tb(III)), in DMSO at t = 25 ꢀC
[Ln(H2L1)]3+
[Ln(L1)]+
˚
gen bond with N1 (N1. . .O2w 2.832(16) A; H1. . .O2w
La3+
Eu3+
Gd3+
Tb3+
5.85(11)
6.03(12)
6.48(9)
6.00(6)
6.56(4)
4.53(4)
5.08(9)
7.24(11)
. . .
˚
2.014(13) A; and N1–H1 O2w 158.7(7)ꢀ). As it will
be found also in the complexes of H2L2, the two flexible
arms of H2L1 are folded in order to embrace the cation.
The hydrazonic chains form with the planar phenanthr-
Standard deviations are given in parentheses.

M. Carcelli et al. / Inorganica Chimica Acta 358 (2005) 903–911
909
Fig. 5. ORTEP drawing of the complex [Eu(H2L2)(NO3)2](NO3).
Hydrogens, with the exception of the hydrazone ones, are omitted for
clarity.
Fig. 3. ORTEP drawing of the complex [Eu(HL1)(CH3COO)2] Æ 5H2O
with the atom-labeling scheme. Hydrogens, with the exception of the
hydrazone one, and water molecules are omitted for clarity.
respectively), while in [Eu(HL1)(CH3COO)2] Æ 5H2
O
the four metal-nitrogen distances are similar.
In [La(H2L2)(NO3)2(H2O)](NO3), [Eu(H2L2)(NO3)2]
(NO3) and [Tb(H2L2)(NO3)2](NO3), the ligand H2L2 is
neutral and hexadentate, through the phenanthroline,
imine and pyridine nitrogens. In the coordination sphere
of the Eu and Tb ions, there are two bidentate nitrate
groups (Fig. 5); in the case of the lanthanum ion, there
are one water molecule, one bidentate nitrate and one
nitrate that is intermediate between unidentate and
˚
bidentate (La–O4N = 2.833(7), La–O5N = 2.647(7) A)
(Fig. 4). The lengthening of the La–O4N distance can
be due to a significant steric crowding of the coordinated
water molecule that shows the shortest bond length
˚
(2.531(6) A) [36]. The coordination number is 10 for
europium and terbium and 11 for lanthanum. In all
cases, another nitrate, disordered on two positions, is
out of the coordination sphere of the metal. In [Eu-
(H2L2)(NO3)2](NO3) and [Tb(H2L2)(NO3)2](NO3), the
mean distance between the metal and the six nitrogen
Fig. 4. ORTEP drawing of the complex [La(H2L2)(NO3)2(H2O)](NO3)
with the atom-labeling scheme. Hydrogens, with the exception of the
hydrazone ones, are omitted for clarity.
˚
donors is 2.627(11) and 2.610(14) A, respectively, while
the mean distance between the metal and the four oxy-
gen atoms of the bidentate nitrate groups is 2.470(7)
oline moiety a dihedral angle of 12.3(3) and 9.0(3)ꢀ,
respectively; the deviations from the mean plane of the
˚
six donor atoms are maximum for O1 (0.591(9) A)
˚
and 2.450(10) A. These values are consistent with the
˚
and O2 (ꢀ0.445(8) A). Table 3 shows the most impor-
ones found in [Tb(tpen)(NO3)2](NO3) ꢂ 3H2O (tpen,
hexadentate ligand, tetrakis(2-pyridyl-methyl)-1,2-ethy-
lenediamine), where the Tb–N and Tb–O bond lengths
tant bond lengths and angles for the complex: the Eu–
˚
O distances (2.454(8) and 2.476(7) A) are shorter than
the Eu–N ones (ranging from 2.652(10) to 2.701(10)
˚
A), as can be expected for a hard oxygen donor bounded
to a f-lanthanide ion. In the previously reported [18] dib-
utyltin and diphenyllead complexes of H2L1, the metal–
N(imino) bond distances are remarkably shorter than
the metal–N(phenanthroline) ones (2.696(2) and
˚
are 2.624(29) and 2.492(33) A, respectively [37]. In [La
(tpen)(NO3)2](NO3) Æ 3H2O [37], the mean distance La–
˚
N (2.720(21) A) is similar to the one we found in
[La(H2L2)(NO3)2(H2O)](NO3) Æ (2.712(12) A), while
˚
the La–O mean distance is slightly shorter (2.587(13)
˚
versus 2.665(30) A). The bond distances between the me-
tal center and the nitrogen donors increase in the order
˚
2.678(4) versus 2.936(5) and 2.905(3) A for Pb and Sn,

910
M. Carcelli et al. / Inorganica Chimica Acta 358 (2005) 903–911
Table 3
2
2
2
˚
Most relevant bond distances (A) and angles (ꢀ) for the complexes [Tb(H2L )(NO3)2](NO3), [Eu(H2L )(NO3)2](NO3), [La(H2L )(NO3)2(H2O)](NO3),
and [Eu(HL1)(CH3COO)2] Æ 5H2O
[Tb(H2L2)(NO3)2](NO3)
[Eu(H2L2)(NO3)2](NO3)
[La(H2 L2)(NO3)2 (H2O)](NO3)
[Eu(HL1)(CH3COO)2] Æ 5H2O
Me–N1
Me–N3
Me–N4
Me–N5
Me–N6
Me–N8
Me–O1n
Me–O2n
Me–O4n
Me–O5n
Me–O1w
Me–O1
Me–O2
Me–O1a
Me–O2a
Me–O3a
Me–O4a
2.668(7)
2.632(7)
2.579(6)
2.580(7)
2.593(6)
2.625(7)
2.447(7)
2.431(6)
2.446(7)
2.475(6)
2.683(5)
2.636(4)
2.607(4)
2.599(4)
2.617(4)
2.651(5)
2.472(4)
2.455(4)
2.466(4)
2.488(4)
2.727(8)
2.697(8)
2.673(8)
2.714(8)
2.705(9)
2.767(9)
2.724(7)
2.625(7)
2.833(7)
2.647(7)
2.531(7)
2.619(9)
2.659(9)
2.697(9)
2.661(9)
2.454(8)
2.476(7)
2.505(8)
2.461(8)
2.486(8)
2.486(8)
N1–Me–N3
N3–Me–N4
N4–Me–N5
N5–Me–N6
N6–Me–N8
O1–Me–N3
O2–Me–N6
59.4(2)
61.1(2)
62.9(2)
61.5(2)
60.4(2)
59.5(1)
61.1(1)
62.2(1)
60.9(1)
60.3(1)
58.7(3)
60.2(3)
60.7(3)
59.0(3)
58.5(3)
60.3(3)
61.0(3)
59.5(3)
60.2(3)
60.0(3)
Tb <Eu <La and N(phenanthroline) < N(imine) < N
(pyridine). The two flexible arms of the ligand are not
coplanar and form an angle of 34.2(1)ꢀ for Tb and Eu
complexes and 23.4(2)ꢀ for La. In all the complexes,
the nitrogen atoms deviate from the planarity, with
N3, N4 and N8 above, and N1, N5, and N6 below the
mean plane. In all the complexes the nitrogen atoms
deviate from the planarity, with N3, N4, and N8 above,
and N1, N5, and N6 below the mean plane. In the Eu
and Tb complexes, the two bidentate nitrates are nearly
perpendicular to the ligand plane (177.9(2) av.).
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