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Inorganica Chimica Acta 315 (2001) 163– 171

Increase in coordination number of lanthanide complexes with

2,2%-bipyridine and 1,10-phenanthroline by using b-diketonates
with electron-withdrawing groups
Dave R. van Staveren a,1, Gerard A. van Albada a, Jaap G. Haasnoot a,
Huub Kooijman b, Anna Maria Manotti Lanfredi c, Peter J. Nieuwenhuizen a,2,
Anthony L. Spek b, Franco Ugozzoli c, Thomas Weyhermüller d, Jan Reedijk a,*
a
Leiden Institute of Chemistry, Gorlaeus Laboratories, Leiden Uni6ersity, P.O. Box 9502, 2300 RA Leiden, The Netherlands
b
Bij6oet Center for Biomolecular Research, Department of Crystal and Structural Chemistry, Utrecht Uni6ersity, Padualaan 8,
3584 CH Utrecht, The Netherlands
c
Dipartimento di Chimica Generale ed Inorganica Chimica Analitica Chimica Fisica, Uni6ersità di Parma,
Centro di Studio per la Strutturistica Diffractometrica del C.N.R., Parco area delle Scienze 17 /a, 43100 Parma, Italy
d
Max-Planck-Institut für Strahlenchemie, Stiftstrasse 34 -36, D-45470 Mülheim an der Ruhr, Germany
Received 3 November 2000; accepted 16 January 2001

Abstract

The coordination chemistry of Ln(hfpd)3 (hfpd=1,1,1,5,5,5-hexafluoropentane-2,4-dionate) with phen and bpy depends on the
size of the Ln3 + ion and on the used solvent. The complexes [Er(hfpd)3(phen)] (7) and [Er(hfpd)3(bpy)] (14) were obtained from
the synthesis of Er(CF3SO3)3 with Hhfpd, CsOH and either 1,10-phenanthroline or 2,2%-bipyridine in acetonitrile. The structure
of 7 was determined by X-ray crystallography. Similar reactions, but performed in methanol, with various other lanthanide
elements resulted in isolation of five different types of complexes, according to stoichiometry and spectral properties.
With elements later in the lanthanide series eight-coordinated complexes of the types [Ln(hfpd)3(bpy)] (for Ln = Dy, Ho and
Yb) and [Ln(hfpd)3(phen)] (for Ln = Tb, Ho and Yb), like 7, were obtained, whereas with the early lanthanide elements
ten-coordinated complexes of the types [Ln(hfpd)3(bpy)2] (for Ln = La and Sm) and [Ln(hfpd)3(phen)2] (for Ln = La, Ce, Pr and
Nd) were isolated. The X-ray crystal structure of [La(hfpd)3(bpy)2] (9) was determined, which provided proof for ten-coordination
around the La ion. In addition to [Sm(hfpd)3(bpy)2], the synthesis with Sm and bpy and a trace of water yielded a second
compound: the nine-coordinated complex [Sm(hfpd)3(H2O)(bpy)]·(bpy) (11), which was structurally characterised by X-ray
crystallography. The LnN distances vary largely, depending on the used N-donor and the Ln3 + ion, and do not run parallel with
the Ln3 + ionic radius. © 2001 Elsevier Science B.V. All rights reserved.

Keywords: Crystal structures; Lanthanide complexes; Bidentate ligand complexes

1. Introduction of their luminescent properties [1], their use as NMR

Lanthanide b-diketonato complexes have been the
subject of extensive research in the last decades because
* Corresponding author. Tel.: + 31-71-527 4459; fax: + 31-71-527
4671.
E-mail address: reedijk@chem.leidenuniv.nl (J. Reedijk).
1
Present address: Max-Planck-Institut für Strahlenchemie, Stift-
strasse 34-36, D-45470 Mülheim an der Ruhr, Germany.
2
Present address: Akzo Nobel Chemicals Research, P.O. Box 9300,
6800 SB Arnhem, The Netherlands.
shift reagents and their application in the synthesis of
electroceramics, e.g. superconductors such as
LnBa2Cu3O7 − l [2,3] and La2 − x Srx CuO4 [3,4].
Ln(dpm)3 (dpm =dipivaloylmethanato) and tris-com-
plexes with fluorinated b-diketonates, such as Ln(fod)3
(fod= 2,2-dimethyl-6,6,7,7,8,8-heptafluoro-octane-3,5-
dionato), are amongst the most frequently used NMR
shift reagents. For this application, also Ln(hfpd)3 com-
pounds have attracted some attention [5,6]. Apart from
increased solubility in common organic solvents, the

0020-1693/01/$ - see front matter © 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 0 - 1 6 9 3 ( 0 1 ) 0 0 3 3 4 - 6
164 D.R. 6an Sta6eren et al. / Inorganica Chimica Acta 315 (2001) 163–171
advantage of fluorinated b-diketonato complexes over
Ln(dpm)3 is primarily enhancement of the Lewis acidity
of the lanthanide ion and subsequent increase of the
shifting power, due to the inductive effect of the
fluorine atoms [7,8].
Tris-b-diketonato lanthanide complexes with the
chelating ligands 2,2%-bipyridine and 1,10-phenanthro-
line were first reported more than two decades ago
[9,10]. Since then a substantial number of these com-
plexes with various b-diketonates have been structurally
characterised by X-ray crystallography [11 – 18]. X-ray
crystal structures of eight-coordinated adducts of Ln-
(hfpd)3 elucidated so far include Cs[Eu(hfpd)4] [19],
[Tb(hfpd)3(H2O)2] [20] and [Gd(hfpd)3(H2O)(Me2CO)]
[21]. Furthermore, several tris-hfpd lanthanide com-
plexes with various substituted nitronyl nitroxide radi-
cals have been structurally characterised by X-ray
crystallography [22 – 28].
Our interest concerned the structure of tris-hfpd lan-
thanide complexes with bpy and phen. The objective
was to determine whether the inductive effect of the
ligand’s fluorine atoms would be reflected in the struc-
ture of these complexes compared to analogous com-
plexes containing b-diketonates without electron-
withdrawing substituents. In a previous paper [29] it
was reported that the reaction of Er(CF3SO3)3 with
Hhfpd, CsOH and either phen or bpy in methanol
yields the dinuclear complexes [Er(hfpd)2-
(m-OCH3)(phen)]2 and [Er(hfpd)2(m-OCH3)(bpy)]2, re-
spectively. By performing an analogous reaction in
acetonitrile, now the complexes [Er(hfpd)3(phen)] (7)
and [Er(hfpd)3(bpy)] were obtained and the structure of
7 was determined by X-ray crystallography. Subse-
quently, it was investigated whether the previously re-
ported [29] remarkable reactivity of Er in methanol,
yielding methoxo-bridged dimers, would extend to the
other lanthanide elements as well. Similar syntheses
with various lanthanide elements have now yielded five
different types of mononuclear complexes, i.e. two in
which the lanthanide ion is ten-coordinated, two with
eight-coordination around the lanthanide ion and one
type in which a Sm ion is nine-coordinated.3 Which
type is formed for a specific lanthanide element appears
to be ion-size dependent. The elements later in the
series form complexes of the types [Ln(hfpd)3(phen)]
and [Ln(hfpd)3(bpy)], whereas the early lanthanide ele-
ments, which have larger ionic radii, yield complexes of
the types [Ln(hfpd)3(phen)2] and [Ln(hfpd)3(bpy)2].
Ten-coordination around the La-ion in [La(hfpd)3-
(bpy)2] (9) was confirmed by X-ray crystallography. In
the case of Sm and bpy, two types of complexes were
isolated: [Sm(hfpd)3(H2O)(bpy)]·(bpy) (11) and [Sm-
3
Although officially being a Group 3 member, lanthanum is also
called a lanthanide element in this work for reasons of convenience.
(hfpd)3(bpy)2] and the former was structurally charac-
terised by X-ray crystallography. These five types of
complexes mentioned above are discussed in the present
paper in relation to Ln3 + -ion size and solvent used.
2. Experimental
2.1. Materials
2,2%-Bipyridine (99+ %) was obtained from Lan-
caster Synthesis. Cesium hydroxide monohydrate
(99.5%), CDCl3 (99.9% D) as well as 1,10-phenanthro-
line monohydrate (99+%) were purchased from Acros.
1,1,1,5,5,5-Hexafluoro-2,4-pentanedione (98%) and
Er(CF3SO3)3 (98%) were received from Aldrich.
Methanol and acetonitrile, both hplc grade, were pur-
chased from Biosolve Ltd. Methanol was dried over
activated 3 A, molecular sieves for the synthesis of
[Sm(hfpd)3(bpy)2].
2.2. Spectroscopy and analysis
Infrared spectra were recorded on a Perkin –Elmer
Paragon 1000 FTIR spectrophotometer as KBr disks
(4000 –300 cm − 1, with a resolution of 4 cm − 1). Ele-
mental analyses were performed using a Perkin –Elmer
Series II CHNSIO elemental analyser. 1H NMR spectra
were recorded on a Bruker WM-300 spectrometer
(300.13 MHz for 1H) in CDCl3. Chemical shifts are
given in parts per million (ppm) relative to TMS. X-ray
powder diffraction patterns were recorded on a Philips
PW 1050 diffractometer using Cu Ka: (u= 1.54184 A, )
with 2q in the range 10–45° or 10–70° and a scan rate
of 0.03° s − 1.
2.3. Synthesis of [Er(hfpd)3(bpy)] (14) and
[Er(hfpd)3(phen)] (7)
A solution of 0.32 g (1.5 mmol) Hhfpd, 0.25 (1.5
mmol) CsOH·H2O and either 0.08 g (0.5 mmol) bpy or
0.10 g (0.5 mmol) phen·H2O in 5 ml of acetonitrile was
mixed with a hot solution of 0.30 g (0.5 mmol)
Er(CF3SO3)3 in 15 ml of acetonitrile. After cooling to
room temperature, the mixture was filtered to remove
any undissolved material. Slow evaporation of the sol-
vent at room temperature yielded a microcrystalline
precipitate in the case of bpy and needle-shaped crystals
suitable for X-ray analysis in the case of phen after 2–3
weeks. The yield and colour of the isolated precipitates,
as well as the results from elemental analyses, are
presented in Table 1.
 D.R. 6an Sta6eren et al. / Inorganica Chimica Acta 315 (2001) 163–171 165

2.4. General synthesis of other lanthanide 2.6. X-ray crystallography

hexafluoropentane-2,4 -dionato complexes with bpy
Reactions were performed with La, Sm, Dy, Ho and
Yb. A solution of 0.32 g (1.5 mmol) Hhfpd, 0.25 g (1.5
mmol) CsOH·H2O and 0.08 g (0.5 mmol) bpy in 10 ml
of methanol was added to a hot solution of 0.5 mmol
Ln(CF3SO3)3 in 10 ml of methanol. For the synthesis of
[Sm(hfpd)3(bpy)2] dry methanol was used. After cooling
to room temperature, the mixture was filtered to re-
move any undissolved material. Slow evaporation of
the solvent at room temperature yielded precipitates
after 2–3 weeks. Experimental details, such as the yield,
form and colour of the isolated precipitates, as well as
the composition and results from elemental analyses,
are tabulated in Table 1.
2.5. General synthesis of other lanthanide
hexafluoropentane-2,4 -dionato complexes with phen
Reactions were performed with La – Nd, Tb, Ho and
Yb in an analogous manner as for the bpy complexes,
but by using 1,10-phenanthroline monohydrate (0.10 g;
0.5 mmol) instead of 2,2%-bipyridine. The yield, form,
colour and composition of the isolated precipitates are
presented in Table 1, together with the results from
elemental analyses.
The crystal data and the most relevant experimental
parameters used in the X-ray measurements and in the
crystal structure analyses are reported in Table 2.
A pink crystal of 7 was mounted on a Lindemann-
glass capillary and transferred into the cold nitrogen
stream of a Nonius KappaCCD diffractometer on ro-
tating anode (graphite monochromated Mo Ka radia-
tion, u= 0.71073 A, , € and (… scans). Data were
corrected for absorption effects using a multi-scan
method (transmission range 0.730 –0.754). Pertinent
data for the structure determinations are given in Table
3. The structure was solved with automated Patterson
and subsequent difference Fourier methods using
SHELXS-86 [30]. Full matrix refinement on F 2 was per-
formed with SHELXL-97 [31], no observance criterion
was applied during refinement. Hydrogen atoms were
included in the refinement on calculated positions rid-
ing on their carrier atoms. The non-hydrogen atoms
were refined with anisotropic displacement parameters.
The hydrogen atoms were refined with a fixed isotropic
displacement parameter related to the value of the
equivalent isotropic displacement parameter of their
carrier atoms. All CF3 moieties were refined with a
disorder model involving two sites: an occupation fac-
tor was refined for each CF3 group. Mild distance

Table 1
Composition, experimental details and results from elemental analysis for the obtained complexes

Complex Assigned type Colour Form a Yield (%) Anal. Calc. Anal. Found

IR X-ray C H N C H N

1 [La(hfpd)3(phen)2] b A "a colourless c 10 c 41.8 1.7 5.0 41.5 1.7 4.8

2 [Ce(hfpd)3(phen)2] A a yellow c 14 c 41.7 1.7 5.0 41.0 1.8 4.8
3 [Pr(hfpd)3(phen)2] A a green c 43 c 41.7 1.7 5.0 40.9 1.8 4.7
4 [Nd(hfpd)3(phen)2] A "a blue c 15 c 41.6 1.7 5.0 40.6 1.8 5.1
5 [Tb(hfpd)3(phen)] D "d light-yellow c 45 d 33.8 1.2 2.9 33.2 1.1 2.9
6 [Ho(hfpd)3(phen)] D d light-orange p 6d 33.5 1.1 2.9 32.4 1.3 2.9
7 [Er(hfpd)3(phen)] e,f D d pink c 10 d 33.5 1.1 2.9 33.0 1.1 3.0
8 [Yb(hfpd)3(phen)] D d colourless p 17 d 33.3 1.1 2.9 31.8 1.2 2.8
9 [La(hfpd)3(bpy)2] f,g B " colourless c 65 h 39.2 1.8 5.2 38.7 1.8 5.0
10 [Sm(hfpd)3(bpy)2] B " yellow m 40 h 38.8 1.8 5.2 37.3 1.9 4.8
11 [Sm(hfpd)3(bpy)(H2O)](bpy) f C yellow c 5h 38.1 1.9 5.1 37.6 1.9 5.1
12 [Dy(hfpd)3(bpy)] E "e colourless m 16 d 31.9 1.2 3.0 30.6 1.3 3.4
13 [Ho(hfpd)3(bpy)] E e light-orange p 18 d 31.9 1.2 3.0 30.9 1.2 2.8
14 [Er(hfpd)3(bpy)] c,e E e pink m 30 d 31.8 1.2 3.0 30.2 1.1 2.8
15 [Yb(hfpd)3(bpy)] E e colourless p 20 d 31.6 1.2 3.0 31.1 1.2 2.8

a
c= crystalline; m = micro-crystalline; p = powder.
b1
H NMR: l= 9.13 (d, 4H, 3J= 6 Hz), 7.95 (d, 4H, 3J= 8 Hz), 7.85 (t, 4H, 3J =8 Hz), 7.38 (t, 4H, 3J =6 Hz), 5.65 (s, 3H).
c
Yield is calculated with respect to phen.
d
Yield is calculated with respect to Ln3+.
e
Isolated from acetonitrile.
f
X-ray crystal structure solved.
g1
H NMR: l = 9.57 (d, 4H, 3J= 6 Hz), 8.32 (d, 4H, 3J= 7Hz), 7.82 (s, 4H), 7.70 (dd, 4H, 3J =7 Hz), 5.48 (s, 3H).
h
Yield calculated with respect to bpy.
166 D.R. 6an Sta6eren et al. / Inorganica Chimica Acta 315 (2001) 163–171

Table 2
Summary of the crystallographic parameters for 7, 9 and 11

Crystal data 7 11 9

Empirical formula C27H11ErF18N2O6 C35H21F18N4O7Sm C35H19F18LaN4O6

Formula weight 968.63 1101.94 1072.45
Crystal size (mm) 0.40×0.15×0.15 0.2×0.3×0.5 0.54×0.50×0.40
Crystal system monoclinic triclinic monoclinic
Space group C2/c (no. 15) Pbarl (no. 2) C2/c (no. 15)
Unit cell dimensions
a (A, ) 23.4477(5) 12.087(5) 21.928(2)
b (A, ) 17.6282(4) 15.262(5) 11.9096(12)
c (A, ) 17.1720(4) 11.988(5) 18.183(2)
h (°) 90 91.680(5) 90
i (°) 113.4140(10) 100.500(5) 118.99(2)
k (°) 90 82.650(5) 90
V (A, 3) 6513.4(3) 2156(1) 4153.6(7)
Z 8 2 4
z (calc.) (g cm−3) 1.9756(1) 1.697 1.715
F (000) 3720 1078 2096
Data collection
T (K) 150 295 213(2)
q Range for data collection (°) 1.6–27.50 3.00–30.00 2.01–30.00
Index ranges −305h527, 05k522, −155h517, −215k513, −225h533, −185k59, −275l528
05l522 −165l516
Reflections collected 48 255 13 161 19 698
Independent refections 6864 [Rint = 0.1068] 12 515 6016 [Rint =0.0231]
Observed reflections 6864 (no criterion applied) 7319 (I]2|(I)) 5246 [I]2|(I)]
Data/restraints/parameters 6864/72/446 12515/0/512 6003/60/346
Weighting scheme a w= [| 2(Fo 2)+(0.0851P)2]−1 w= [| 2(Fo 2)+(0.1452P)2]−1 w= [| 2(Fo 2)+(0.0923P)2+4.66P]−1
Goodness-of-fit on F 2 b 0.942 0.972 1.040
Final wR2 (all. data) c 0.173 0.199 0.137
Final R1 (I\2|) d 0.0554 0.0691 0.0479
Largest difference peak and hole 2.81, −1.52 (near Er) 1.46 and −0.92 1.422 and −0.583
(e A, 3)

a
P = (Fo 2+2Fc 2)/3.
b
GooF= [w(Fo 2-Fc 2)2/(n-p)]1/2, where n is the number of reflections and p the number of parameters.
c
wR2 =[w (Fo 2-Fc 2)2/wFo 4]1/2.
d
R1 =  Fo−Fc 2 /Fo.

Table 3
Selected bond lengths (A, ) for 7, 9 and 11

[Er(hfpd)3(phen)] (7) [La(hfpd)3(bpy)2] (9) [Sm(hfpd)3(H2O)(bpy)]·(bpy) (11)

ErO(32) 2.305(6) ErO(34) 2.326(7) LaO(18) 2.524(3) SmO(lW) 2.422(5) SmO(l) 2.491(5)
ErO(42) 2.309(7) ErO(44) 2.291(7) LaO(19) 2.541(2) SmO(2) 2.434(5) SmO(3) 2.394(5)
ErO(52) 2.311(7) ErO(54) 2.266(7) LaO(29) 2.557(2) SmO(4) 2.414(5) SmO(5) 2.387(6)
ErN(ll) 2.482(8) LaN(1) 2.773(3) SmO(6) 2.522(5) SmN(1) 2.611(5)
ErN(21) 2.468(7) LaN(8) 2.771(3) SmN(2) 2.650(5)

restraints were applied in order to ensure a tetrahedral
geometry on the CF3 moieties. Neutral atom scattering
factors and anomalous dispersion corrections were
taken from the International Tables for Crystallogra-
phy [32]. Geometrical calculations were performed with
PLATON [33].
A single crystal of 11 suitable for the X-ray analysis
was mounted on a glass rod and protected from the
atmosphere with perfluoric oil. The data were collected
on a Siemens AED diffractometer equipped with
graphite monochromated Mo Ka radiation (u=
0.71073 A, ). The intensities were corrected for Lorentz
and polarization effects but not for absorption effects.
The phase problem was solved by direct methods
using SIR-92 [34] and the structure was refined by
blocked full-matrix least-squares methods on F 2 using
the SHELXL-97 program [31]. The non-coordinated bpy
molecule was refined with some geometrical constraints
 D.R. 6an Sta6eren et al. / Inorganica Chimica Acta 315 (2001) 163–171
and with isotropic thermal parameters. The hydrogen
atoms were maintained at their calculated positions
with the geometrical constraint CH 0.96 A, and refined
‘‘riding’’ on their corresponding carbon atoms. The
final molecular geometry was analysed with the pro-
gram PARST-97 [35]. All the calculations were carried
out on the DEC Alpha 250 workstation at the Centro
di Studio per la Strutturistica Diffractometrica of
C.N.R., Parma.
A colourless single crystal of 9 sealed in a glass
capillary under an atmosphere of argon was mounted
on a Siemens Smart CCD diffractometer equipped with
a cryogenic nitrogen cold stream at 213(2) K. Graphite
monochromated Mo Ka radiation (u = 0.71073 A, ) was
used. Final cell constants were obtained from a least-
squares fit of a subset of 6379 strong reflections. Data
collection was performed by hemisphere runs taking
frames at 0.3° in …. A semi-empirical absorption cor-
rection using the program SADABS [36] was performed.
The Siemens SHELXTL [37] software package was used
for solution, refinement and artwork of the structure.
The structure was readily solved by direct methods and
refined by difference Fourier techniques. The CF3
groups of the hfpd-ligands were found to be heavily
disordered. A split atom model was used for
F(20)···F(25) with occupancies of about 2/3 and 1/3.
The CF and FF distances in these groups were
restrained to be equal within errors using the SADI
option (60 restraints). All non-hydrogen atoms were
refined anisotropically and hydrogen atoms were placed
at calculated positions and refined as riding atoms with
isotropic displacement parameters.
3. Results and discussion
3.1. Synthesis of the complexes and their composition
throughout the series
All compounds except the Er complexes are formed
by reaction of Ln(CF3SO3)3 with Hhfpd, CsOH and
either bpy or phen in a 1:3:3:1 ratio in MeOH. The Er
complexes are obtained from a similar reaction in
MeCN to prevent formation of methoxo-bridged
dimers [29]. No analogous dinuclear methoxo-bridged
compounds could as yet be obtained with the other
lanthanide elements. By slow evaporation of the solvent
at room temperature, the complexes precipitate after
2 – 3 weeks. An overview of the composition of the
isolated complexes for each lanthanide element used is
shown in Table 1, together with the assigned type based
on patterns in the IR spectra and X-ray powder diffrac-
tograms (XRD).
As shown in Table 1, the syntheses of the heavier
lanthanide elements Tb and Ho – Yb with phen all yield
eight-coordinated complexes of general composition
167
Fig. 1. Projection of the structure of [Er(hfpd)3(phen)] (7) and the
selected atom-labelling scheme. Fluorine atoms, which are all disor-
dered, and hydrogen atoms are omitted for clarity.
[Ln(hfpd)3(phen)]. Similarly, the synthesis of Dy and
Ho –Yb with bpy yield complexes of the type [Ln-
(hfpd)3(bpy)]. However, the elemental analyses on the
[Ln(hfpd)3(bpy)] and [Ln(hfpd)3(phen)] complexes
yielded consistent low-carbon values, but IR spectro-
scopic data and XRD establish the proposed constitu-
tion (see below). The elements with larger ionic radii do
yield ten-coordinated complexes of general composition
[Ln(hfpd)3(phen)2] (for Ln=La –Nd) and [Ln-
(hfpd)3(bpy)2] (for Ln= La and Sm).
With Sm and bpy two types of complexes were
isolated, depending on the trace water content of the
methanol. When dry methanol (dried over activated 3
A, molecular sieves) was used, [Sm(hfpd)3(bpy)2] was
easily obtained, whereas the use of regular methanol
( 1% H2O) invariably yielded [Sm(hfpd)3(bpy)-
(H2O)]·(bpy) (11).
These five different types of complexes can be clearly
distinguished by IR spectroscopy and their XRD. The
solid-state structures of the three compounds are de-
scribed and will be compared mutually, followed by
discussion of the IR spectra and XRD patterns.
3.2. X-ray crystal structure of [Er(hfpd)3(phen)] (7)
A drawing of complex 7 and the selected atom-la-
belling scheme are depicted in Fig. 1; the relevant bond
lengths are listed in Table 2. The structure consists of
Er(hfpd)3(phen) molecules, with the Er ion being octa-
coordinated, contributed by six oxygen atoms of three
didentate hfpd ligands and two nitrogen atoms of a
didentate phen. The symmetry around the Er ion is
square-antiprismatic.
The ErO distances vary between 2.266(7) A,
(ErO(54)) and 2.326(7) A, (ErO(34)), whereas the
ErN distances are 2.468(7) A, (ErN(21)) and 2.482(8)
A, (ErN(11)).
Complex 7 can be compared to [Yb(acac)3(bpy)] [16],
although it must be noted that phen is sterically more
168 D.R. 6an Sta6eren et al. / Inorganica Chimica Acta 315 (2001) 163–171
Fig. 2. Projection of the structure of [Sm(hfpd)3(H2O)(bpy)]·(bpy)
(11) and the selected atom-labelling scheme. Fluorine atoms, which
are all disordered, hydrogen atoms and the disordered uncoordinated
2,2%-bipyridine molecule are omitted for clarity.
Fig. 3. Projection of the structure of [La(hfpd)3(bpy)2] (9) and the
used atom-labelling scheme. Fluorine atoms, which are all disordered,
and hydrogen atoms are omitted for clarity.
demanding and much more rigid than bpy. The average
YbO and YbN distances in [Yb(acac)3(bpy)] are 2.27
and 2.52 A, , respectively. When compensated for the
approximate 0.01 –0.02 A, smaller ionic radius of Yb3 +
for eight-coordination compared to Er3 + [38], the
LnO distances are roughly similar (average ErO =
2.30 A, ), whereas the ErN bond lengths (average 2.47
A, ) are significantly shorter compared to the YbN
bond lengths. Transfer of electron density to the CF3
groups results in a relatively more positively charged Er
ion and, apparently, the ErN bonds become stronger
and shorter, although shortening of the ErO bonds is
not observed.
3.3. X-ray crystal structure of
[Sm(hfpd)3(bpy)(H2O)] ·(bpy) (11)
A plot of 11 together with the atom-labelling scheme
is shown in Fig. 2, the relevant bond lengths are listed
in Table 2. The asymmetric unit of 11 consists of the
complex [Sm(hfpd)3(bpy)(H2O)] and a non-coordinated
2,2%-bipyridine, which is not depicted because it is disor-
dered. The coordination sphere around the Sm ion
consists of seven oxygen atoms, from three didentate
hfpd ligands and a water molecule, and two nitrogen
atoms of a didentate bpy. The SmO(hfpd) bond
lengths are between 2.387(6) A, (SmO(5)) and 2.522(5)
A, (SmO(6)) and an average 2.44 A, , whereas the
distance of the Sm ion to the aqua oxygen atom is
2.422(5) A, . Significantly longer are the SmN(bpy)
bond lengths, which are 2.611(5) A, (SmN(1)) and
2.650(5) A, (SmN(2)). The unit cell of 11 contains two
[Sm(hfpd)3(bpy)(H2O)] complexes and two non-coordi-
nated 2,2%-bipyridine molecules lying around the crys-
tallographic centre of symmetry at (0,0,0). The bpy
molecules are involved in a stacking interaction, with
an interplanar distance of 3.71(1) A, . The level of refine-
ment does not allow the detection of the hydrogen
atoms of the aqua ligand. But the two short interac-
tions between the aqua ligand and the two nitrogen
atoms of the non-coordinated bpy (not depicted)
[O(1W)···N(2G) 2.948(14) A, and O(1W)···N(12G)
3.142(7) A, ] seem to suggest that only one hydrogen
atom of the aqua ligand interacts via a bifurcated
hydrogen bond with the two nitrogen atoms of the
non-coordinated bpy. This is in agreement with the IR
spectroscopic data of 11 (see below).
Nine-coordinated tris-b-diketonato lanthanide com-
plexes with a didentate nitrogen donor ligand and a
monodentate ligand occupying the remaining three co-
ordination sites have not been reported thus far. Com-
plex 11 can be compared to the nine-coordinated
compounds [Eu(dpm)3(terpy)] [39] and [Eu-
(terpy)3](ClO4)3 [40] (terpy= 2,2%:6%2¦-terpyridine), both
in which the lanthanide ion is nine-coordinated. The
average SmN bond lengths in 11 (2.63 A, ) are slightly
shorter than the EuN bond lengths in the compound
[Eu(dpm)3(terpy)] (average 2.65 A, ) but longer than the
EuN bond lengths in the complex [Eu(terpy)3](ClO4)3,
which lie in the range of 2.57 –2.62 A, . The average
SmO(hfpd) bond length (2.44 A, ) in 11, however, is
longer than the average EuO(dpm) bond length (2.38
A, ) in [Eu(dpm)3(terpy)].
3.4. X-ray crystal structure of [La(hfpd)3(bpy)2] (9)
A plot of 9 and the atom-labelling scheme are shown
in Fig. 3; the relevant bond lengths are listed in Table
2. Contrary to 11, both bpy ligands are coordinated to
the La ion. Furthermore, three hfpd ligands are present
 D.R. 6an Sta6eren et al. / Inorganica Chimica Acta 315 (2001) 163–171
in the first coordination sphere, resulting in a [O6N4]
coordination environment around the La ion. The
structure possesses a C2 rotation axis through the La
ion and C(20), which implies symmetry-equivalence of
the two remaining hfpd ligands and also of the bpy
ligands. Furthermore, the atoms C(26), C(27) and the
three fluorine atoms, which are not depicted, of the
third hfpd ligand present are equivalent on basis of
symmetry to the other half of this hfpd ligand. The
LaO distances vary between 2.524(3) A, (LaO(18) and
LaO(18)%) and 2.557(2) A, (LaO(29) and LaO(29)%),
whereas the complex shows two similar LaN distances
of 2.771(3) A, (LaN(8) and LaN(8)%) and 2.773(3) A
(LaN(1) and LaN(1)%). This crystal structure is the
first example of a structurally characterised ten-coordi-
nated tris-b-diketonato lanthanide compound. With the
exception of 11, thus far only eight-coordinated tris-b-
diketonato complexes were found with bpy as the neu-
tral ligand. The structure of the nine-coordinated
polyether complex [La(hfpd)3(diglyme)] (diglyme=
bis(2-methoxyethyl) ether) is known and also formation
of [La(hfpd)3(triglyme)] (triglyme=2,5,8,11-tetraoxo-
dodecane) was reported [41]. However, the latter com-
pound was not structurally characterised and, thus, it
remains uncertain whether all four oxygen atoms of the
triglyme ligand are coordinated to the La ion. The
average LaO(hfpd) bond length in 3 (2.54 A, ) is
slightly shorter than the average LaO(hfpd) bond
length in [La(hfpd)3(diglyme)] (2.55 A, ), although the
coordination number of the La ion in 9 is ten compared
to nine for the diglyme compound.
Structurally characterised lanthanide complexes with
the Ln ion in a [LnO6N4] chromophore that resemble 9
constitute [La(NO3)3(bpy)2] and [La(NO3)3(phen)2]
[42,43]. Also in these cases a twofold crystallographic
axis is present through one of the anionic ligands
(nitrato ligands in these cases) and the La ion. The
average LaN bond length in 9 (2.77 A, ) is significantly
longer than the average LaN bond length in
[La(NO3)3(bpy)2] (2.66 A, ) and [La(NO3)3(phen)2] (2.67
A, ), whereas the average LaO(hfpd) bond length in 9
(2.54 A, ) is significantly shorter than the average LaO
distances in the nitrato compounds (in both cases 2.60
A, ). The hfpd ligands are sterically more demanding
than nitrates and contain, in contrast to the nitrates,
electron-withdrawing substituents. These differences be-
tween these two types of ligands result in elongation of
the LaN and compression of the LaO bonds in 9 in
comparison to [La(NO3)3(bpy)2] and [La(NO3)3(phen)2].
3.5. Infrared spectroscopy and X-ray powder
diffractograms
The vibrations observed in the IR spectra of the type
A, B, D and E complexes are all assigned as vibrations
originating from hfpd [44,45], bpy (for the types B and
169
E) and phen (for the types A and D) [46]. The differ-
ence between the eight-coordinated complexes (types D
and E) and the ten-coordinated complexes (types A and
B) is clearly reflected in the IR spectra. In particular, a
vibration originating from hfpd [44,45] clearly indicates
whether the coordination number of the complex is
eight or ten. The vibration at 802 cm − 1 in the types D
and E shifts to 794 cm − 1 in the types A and B. The
observed shift of this hfpd-vibration to lower wavenum-
bers upon increase of the coordination number from
eight to ten is consistent with elongation of the metal –
donor atom distance.
The IR spectrum of 11 is completely different from
those of the type A, B, D and E complexes due to the
presence of the coordinated water molecule. Additional
vibrations are present at 716, 1695, 3114 and 3610
cm − 1. The last vibration is at high frequency and
sharp, and is assigned as the wOH stretch vibration of
the non-hydrogen bonded OH group of the aqua lig-
and. The wOH stretch vibration of the OH group that
interacts with the uncoordinated bpy via a bifurcated
hydrogen bond is observed at 3114 cm − 1. This vibra-
tion is much broader than the vibration at 3610 cm − 1
and is of lower intensity. These IR spectroscopic data
are in agreement with the X-ray crystal structure of 11.
From IR spectroscopic data, it can clearly be deduced
which type of complex is formed. Since some of the
carbon percentages of the elemental analyses were too
low, X-ray powder diffraction patterns were recorded
to obtain further proof about isomorphism between
complexes that belong to the same type. Within the
[Ln(hfpd)3(phen)] complexes, the Ho, Er and Yb com-
pounds show isomorphic powder patterns. Therefore,
the Ho and Yb complexes possess a similar solid-state
structure as [Er(hfpd)3(phen)] (7), of which the X-ray
crystal structure is solved. The X-ray powder pattern of
the Tb complex, on the other hand, is completely
different. Within the [Ln(hfpd)3(bpy)] series, the Ho, Er
and Yb complexes show isomorphic powder patterns,
whereas the Dy compound displays a different type of
pattern. This trend is similar as observed for the com-
pounds [Ln(hfpd)3(phen)]. The elements with a slightly
larger ionic radius apparently favour a different orien-
tation of the ligands, leading to a different X-ray
powder pattern. The fact that these octa-coordinated
tris-b-diketonato complexes can exist in different iso-
mers has been previously demonstrated [15]. X-ray
crystallographic studies of [Ln(dpm)3(2,9-dimethyl-
phen)] (for Ln= La, Eu –Tb and Ho) revealed the
concomitant presence of two geometrical isomers in the
unit cell [15]. The [Ln(hfpd)3(phen)2] complexes show
three different types of X-ray powder diffraction pat-
terns: the Ce and Pr compounds are isomorphic,
whereas the La and Nd complexes each display a
unique pattern. Also both [Ln(hfpd)3(bpy)2] complexes
(La and Sm) each show a unique X-ray powder pattern.
170 D.R. 6an Sta6eren et al. / Inorganica Chimica Acta 315 (2001) 163–171
The coordination number of these compounds is ten,
for which it has been demonstrated that several differ-
ent geometries are possible [42,47 – 49] each of which is
expected to yield a unique XRD pattern.
3.6. 1H NMR spectra of the La-compounds
The 1H NMR spectrum of 9 is in accordance with a
hfpd/bpy ratio of 3:2. Only one set of signals is ob-
served for the protons of the bpy ligands between 7.37
and 9.13 ppm (two doublets and two triplets), as ex-
pected from the geometry in the X-ray crystal structure.
Observation of one signal for the three protons of the
three hfpd ligands (singlet at 5.65 ppm) indicates that
fluxional processes occur in solution because two sig-
nals are expected on the basis of symmetry from the
X-ray crystal structure.
Similarly, the 1H NMR spectrum of [La(hfpd)3-
(phen)2] (1) is consistent with a hfpd/phen ratio of 3:2.
Also in this case only one set of signals for the 1,10-
phenanthroline ligands between 7.69 and 9.58 ppm (one
singlet, two doublets and a triplet) is observed. Further-
more, the three protons of the three hfpd ligands show
one resonance at 5.48 ppm, which illustrates that 1 is,
like 9, fluxional in solution. Also, it can be observed
that the hfpd protons in 1 resonate 0.17 ppm upfield
compared to 9.
3.7. Results with other lanthanide elements
Results obtained from the syntheses of Sm – Gd with
phen as the neutral ligand were inconclusive. Although
the IR spectra are very similar to the type A and D
spectra, the elemental analyses are not consistent with
either type. The IR spectra of the precipitates obtained
with Ce –Nd and bpy are similar to the spectra of the
type B spectra, but the results obtained from elemental
analysis invariably displayed very low carbon values
(35.2 –37.2%; calculated values: 38.8 – 39.1%). The IR
spectra of the precipitates obtained with Eu – Tb and
bpy are dissimilar to the type B and E spectra and also
the results of elemental analysis are not consistent with
the formulations [Ln(hfpd)3(bpy)] or [Ln(hfpd)3(bpy)2].
Further research will be required to elucidate the exact
composition of these complexes, and to investigate
whether more types are possible.
4. Concluding remarks
All the characterised compounds and their variations
can be rationalised on the basis of the ionic radius of
the lanthanide ion. The elements with larger ionic radii,
i.e. the elements early in the series, can accommodate
two bpy or phen ligands in the first coordination
sphere, whereas the elements later in the series can
accommodate only one bpy or phen molecule. The bpy
complexes show a transition at Sm, because when a
small amount of water is present, formation of the
nine-coordinated complex 11 is preferred over forma-
tion of [Sm(hfpd)3(bpy)2].
The formation of ten-coordinated complexes with the
lanthanide elements early in the series can be attributed
to the strong electron-withdrawing effect of the ligand-
fluorine atoms. With other b-diketonates thus far in-
variably eight-coordinated compounds of general
composition [Ln(b-diketonate)3(bpy)] and [Ln(b-diketo-
nate)3(phen)] have been reported. Due to the inductive
effect of the CF3 groups, the lanthanide ion becomes
relatively more positively charged. In order to compen-
sate for that, the lanthanide ion apparently accommo-
dates a second bpy or phen ligand in the first
coordination sphere, in this way increasing the number
of electron density donating atoms. The electron-with-
drawing effect of the CF3 groups is also displayed in
the solid-state structure of [Er(hfpd)3(phen)] (7). Com-
pared to [Yb(acac)3(bpy)] [16], which contains a b-dike-
tonate without electron-withdrawing substituents, the
average ErN bond length in 7 is about 0.05 A, shorter,
whereas the average ErO distance is roughly similar to
the average YbO bond-distance. The behaviour of Er
is unique, because it is the only element for which
dinuclear methoxo-bridged complexes are isolated from
methanol [29]. Only, when the syntheses are performed
in dry in MeCN, the common mononuclear complexes
[Er(hfpd)3(bpy)] and [Er(hfpd)3(phen)] can be obtained.
5. Supplementary material
Crystallographic data (excluding structural factors)
for the structural analysis have been deposited with the
Cambridge Crystallographic Data Centre, CCDC nos.
150660 for compound 7, 150186 for compound 9 and
143569 compound 11. Copies of this information can
be obtained free of charge from The Director, CCDC,
12 Union Road, Cambridge, CB2 1EZ, UK (fax:
+ 44-1223-336-033; e-mail: deposit@ccdc.cam.ac.uk or
www: http://www.ccdc.cam.ac.uk).
Acknowledgements
This work was supported in part (A.L.S.) by the
Netherlands Foundation of Chemical Research (SON)
with financial aid from the Netherlands Organisation
for Scientific Research (NWO). Furthermore, we are
indebted to the Italian M.U.R.S.T. and C.N.R. for
providing financial support. The authors are grateful to
Akzo Nobel (Prof. Dr. J.W. Hofstraat, presently at
Philips) for the generous gift of lanthanide triflates.
Mrs. H. Schucht is kindly acknowledged for recording
the X-ray crystal data set of 9.
 D.R. 6an Sta6eren et al. / Inorganica Chimica Acta 315 (2001) 163–171
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