Synthesis and Characterization of the Cerium(III) UV-Emitting 2D-Coordination Polymer 2 ∞[Ce2Cl6(4, 4′-bipyridine)4]·py

Article abstract of DOI:10.1002/zaac.201400375

The 2D-coordination polymer ² _∞[Ce₂Cl₆(bipy)₄]·py (bipy = 4, 4′-bipyridine) shows a 5d-4f centered emission in the soft UV-B region. It was synthesized via the reaction of anhydrous CeCl₃ and 4, 4′-bipyridine in pyridine under solvothermal conditions. The two-dimensional sheet structure consisting of 4, 4′-bipyridine coordinated Ce₂Cl₆ dimers closes the gap between the known lanthanum ³ _∞[La₂Cl₆(bipy)₅]·4bipy framework and the 2D networks of the formula ² _∞[Ln ₂Cl₆(bipy)₃]·2bipy from praseodymium on. They differ in the number of coordinating bipy linkers, which decreases along La > Ce > Pr, with the remarkable observation that lanthanum, cerium, and praseodymium exhibit different network constitutions. The structure of ² _∞[Ce₂Cl₆(bipy)₄]·py exhibits a cem topology constituted of double strands, which are diagonally linked by 4, 4′-bipyridine forming trapezoid cavities in-between the strands. The cavities contain intercalated pyridine molecules.

Full text of DOI:10.1002/zaac.201400375

ARTICLE
DOI: 10.1002/zaac.201400375
Synthesis and Characterization of the Cerium(III) UV-Emitting 2D-
2
Coordination Polymer [Ce Cl (4,4Ј-bipyridine) ]·py
ϱ
2
6
4
[a]
[a]
Philipp R. Matthes and Klaus Müller-Buschbaum*
Dedicated to Professor Martin Jansen on the Occasion of His 70th Birthday
Keywords: Coordination polymers; Cerium; MOFs; Luminescence; 4,4Ј-Bipyridine
Abstract. The 2D-coordination polymer 2
[Ce
Cl
(bipy)
]·py (bipy =
the number of coordinating bipy linkers, which decreases along
ϱ
2
6
4
4,4Ј-bipyridine) shows a 5d-4f centered emission in the soft UV-B La Ͼ Ce Ͼ Pr, with the remarkable observation that lanthanum,
region. It was synthesized via the reaction of anhydrous CeCl
,4Ј-bipyridine in pyridine under solvothermal conditions. The
two-dimensional sheet structure consisting of 4,4Ј-bipyridine coordi-
nated Ce Cl dimers closes the gap between the known lanthanum
(bipy) ]·4bipy framework and the 2D networks of the for-
[Ln Cl (bipy)
3
and cerium, and praseodymium exhibit different network constitutions. The
2
4
structure of
ϱ
[Ce
2
Cl
6
(bipy)
4
]·py exhibits a cem topology constituted
of double strands, which are diagonally linked by 4,4Ј-bipyridine
forming trapezoid cavities in-between the strands. The cavities contain
intercalated pyridine molecules.
2
6
3
ϱ
[La
mula 2
2
Cl
6
5
ϱ
2
6
3
]·2bipy from praseodymium on. They differ in
Introduction
Metal-organic frameworks and coordination polymers[
stitution, whilst the intermediate with cerium was missing prior
to this work.
1]
[2]
show a wide diversity of physical properties like porosity,
magnetism,[ and luminescence, which can be used for a
3]
[4]
Results and Discussion
[
5]
variety of potential applications like gas-storage, sensor-de-
velopment,[ and as light-converter materials. In recent
years, the investigation and determination of the luminescent
properties of these materials progressively moves into the fo-
6]
[7]
In order to close this gap, the solvent free approach was
modified by assisting solvents. Hereby, pyridine can be benefi-
cial for crystallization due to the partial dissolution of LnCl3
III
forming a small amount of reactive LnCl -pyridine complexes,
cus of scientific interest. Ce -centred luminescence can be ob-
3
initially.[ Under solvothermal reaction conditions the coordi-
nated pyridine can be replaced by bridging bipyridine mol-
ecules leading to an exclusively bipy-connected network based
13]
served in purely lanthanide containing coordination polymers
[8]
and MOFs as well as doped into lanthanide free host lat-
tices.[ Cerium containing frameworks are still rare and are
commonly accessed via solvothermal reactions of hydrated ce-
rium salts with carboxylic acids. We were able to utilize a
solvent free melt synthesis strategy to obtain coordination
polymers and networks based on anhydrous lanthanide chlor-
9]
on CeCl -SBUs (secondary building units). Accordingly, the
3
reaction product marks the missing link between lanthanum
and praseodymium, which can be achieved by the formation
2
of the 2D coordination polymer [Ce Cl (4,4Ј-bipy) ]·py, pre-
ϱ
2
6
4
ides and dinitriles[ or 4,4Ј-bipyridine (bipy),
10]
[11]
bypassing
sented herein.
quenching effects caused by coordinated ligands containing –
OH or –NH functional groups.[
12]
However, the solvent
Crystal Structure
free approach is accompanied by a complex crystallization
process, so that not all products obtained can be identified
and characterized. The lanthanum containing3D frame-
2
The crystal structure of [Ce Cl (4,4Ј-bipy) ]·py was deter-
ϱ
2
6
4
mined on single crystals. It crystallizes in the monoclinic space
group C/2m. Crystallographic data is presented in Table 1, se-
lected interatomic distances can be found in Table 2. Trivalent
cerium is found on one crystallographic site and exhibits a
coordination number of eight, which is in-between lanthanum
3
[11a]
work
[La Cl (bipy) ]·4bipy
and the 2D network
(Ln = Pr, Nd, Sm, Eu, Gd, Tb),
mark examples with a significant structural difference and con-
ϱ
2
6
5
2
[11b,11c]
[
Ln Cl (bipy) ]·2bipy,
ϱ
2 6 3
*
Prof. Dr. K. Müller-Buschbaum
Fax: +49-931-3184785
E-Mail: k.mueller-buschbaum@uni-wuerzburg.de
3
[11a]
in [La Cl (bipy) ]·4bipy
with five bipy per dimeric unit
ϱ
2
6
5
2
(C.N.
=
[11b,11c]
8) and praseodymium in
with three bipy per dimeric unit (C.N. = 7). Ce-
[Ln
Cl (bipy) ]·
2 6 3
ϱ
[
a] Universität Würzburg
Institut für Anorganische Chemie
Am Hubland
2bipy
rium is coordinated by four nitrogen atoms of four 4,4Ј-bipyr-
idine molecules and four chloride ions, generating a dodecahe-
97074 Würzburg, Germany
Z. Anorg. Allg. Chem. 2014, 640, (14), 2847–2851
© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
2847

P. R. Matthes, K. Müller-Buschbaum
ARTICLE
dron as coordination sphere. Two cerium coordination spheres
form a Ce Cl dimer, which is edge connected by a bridge
2
6
consisting of two μ -chloride ions [Ce1–Cl3: 286.64(11) pm,
2
I
Ce1–Cl3 : 295.25(10) pm]. The other chloride ions are ter-
minally bound to cerium [Ce1–Cl1: 278.27(12) pm, Ce1–Cl2:
(274.16(13) pm].
Table 1. Crystallographic data for 2
[Ce
Cl
Cl (4,4Ј-bipyridine)
1196.91
ϱ
2
6 4
(4,4Ј-bipy) ]·py.
2
ϱ
[Ce
2
6
4
]·py
Formula weight /g·mol–1
Crystal system
Space group
a /pm
b /pm
c /pm
monoclinic
C2/m
1404.0(3)
1225.3(3)
1405.4(3)
92.27(3)
2415.8(8)
2
1.6355
β /°
3
6
Volume /pm ϫ10
Z
d
c
/g·cm–3
Figure 1. Extended dimeric unit of 2
ϱ
2 6 4
[Ce Cl (4,4Ј-bipy) ]·py The ther-
Diffractometer
X-ray radiation
Temperature /K
Bruker SMART Apex I
mal ellipsoids depict 30% of the probability level of the atoms. Sym-
Mo-K
α
(graphite monochromator)
I
II
III
IV
metry operations: 3/2 –x, ½–y, –z; x, –y, z; 3/2 –x,y–1/2,–z; x, 1 –
168(3)
60.3
2.233
1164
V
VI
VII
VIII
y, z; 1–x, y, 1 –z; 1–x, 1 –y, 1 –z; 1–x,y,1–z;
x–1/2, y–1/2, 1+z;
2
θ max /°
IX
–x, –y, 1 –z; Xx–1/2, y–1/2. 1+z; 1–x, –y, 1 –z; 1–x, y–1, 1 –z.
XI
XII
1
–
1
μ /mm
F(000)
All reflections collected
Independent reflections
Data / restraints / parameters
S
18425
3713
3713/0/221
1.121
1
R for n reflections [IϾ =
0
.0288
a)
2
R
σ (I)]
1
[all data] a)
0.0310
0.0700
b)
2
wR [all data]
Largest diff. peak/hole
1
.30/–0.78
= Σw(|F 2| – |F 2|)2/Σw|F
| ] .
o c o
–3
–6
/
(e pm )·10
2 2 1/2
a) R = ∑[|F
1
o
| – |F
c
|]/∑|F
o
|. b) wR
2
Table 2. Selected interatomic distances /pm for 2
[Ce Cl (4,4Ј-bipy) ]·
ϱ 2 6 4
py.
Ce1
Ce1
Ce1
Ce1
Ce1
Ce1
Ce1
Ce1
Cl1
Cl2I
Cl3
Cl3
278.27(12) N2
274.16(13) N2
295.25(10) N2
286.64(11) C8
C10A
C6B
138.1(6)
146.1(17)
112.0(15)
148.6(6)
149.2(6)
C10B
III
C8
II
II
N1
262.8(2)
262.8(2)
283.7(2)
283.7(2)
C3
C3
N1
N2
range (C–N, C–C) 110(7)–145.1(19)
II
N2
Symmetry operations: 1–x, y, 1–z; IIx, –y, z; III3/2 –x, 1/2 –y, –z.
I
Figure 2. Crystal structure of 2
[Ce Cl (4,4Ј-bipy) ]·py, showing a
ϱ 2 6 4
The dimeric unit is depicted in Figure 1. The Ce–Cl dis- two-dimensional sheet structure. The thermal ellipsoids depict 30% of
tances are in good agreement with the dimeric complex the probability level of the atoms, intercalated pyridine molecules are
[14]
at disordered positions within cavities.
[
CeCl (μ-Cl)(py-(R,R)-chxn)]
(terminal Ce–Cl 274.3–
2
2
278.3 pm, bridging Ce–Cl 284.0–290.8 pm). All six chloride
ions and both cerium atoms of the dimer are positioned on the nitrogen atoms of the 4,4Ј-bipyridyl ligands that bind to cerium
1
2
bc plane. This structural motif has not yet been reported for [Ce1–N1,N 262.8(2) pm, Ce1–N2,N2 283.7(2) pm] are also
other compounds based on lanthanide halides coordinated by positioned on a plane perpendicular to the Ce Cl plane. Each
2
6
pyridyl ligands.
nitrogen atom belongs to a μ -bridging 4,4Ј-bipyridine mol-
2
Dinuclear species with double halide bridged lanthanides ecule, which interconnects the dimeric Ce Cl units to a two-
2
6
and a coordination number of eight can show out-of-plane co- dimensional network (Figure 2). Two distinct 4,4Ј-bipyridine
ordination of the chloride anions, as found for Nd Cl (1,10- molecules connect the Ce Cl dimers along the a axis perpen-
2
6
2
6
phenanthroline)4,[ La Cl (pyridine) ,
15]
[13b]
and [La Cl (4,4Ј- dicular to the lanthanide–chloride plane. The distance between
ϱ 2 6
. In [Ce Cl (4,4Ј-bipy) ]·py, the four the longitudinal axes of both 4,4Ј-bipyridine molecules is
3
2
6
8
[11a]
2
bipy) ]·4(4,4Ј-bipy)
5
ϱ
2
6
4
2
848
www.zaac.wiley-vch.de
© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2014, 2847–2851

Cerium(III) UV-Emitting 2D-Coordination Polymer
3
78.9(3) pm, revealing parallel-displaced π–π repulsion of the sheets are filled with pyridine molecules, which have two dif-
aromatic pyridyl pairs. These ladder-like strands are diagonally ferent preferred orientations. Platon[ calculations reveal a
20]
3
6
connected via two 4,4Ј-bipyridine molecules per SBU forming theoretically accessible void volume of 2415 pm ϫ10 corre-
trigonal cavities within the sheet network. The topology was lating to 19.1% unit cell volume.
determined via TOPOS[
16]
counting 4,4Ј-bipyridine and the
X-ray powder diffraction investigations reveal good accord-
III
double chloride bridge as normal bridges and the Ce ions ance of the observed powder diffractogram with the simulated
as network nodes (Figure 3 top). Determination revealed an diffractogram based on single-crystal data (Figure 4). Further-
Archimedean cem topology type.
more, about one percent of unreacted CeCl can be observed
3
in the diffractogram and was determined by the Rietveld-re-
finement using TOPAS.[
21]
Figure 4. Rietveld-plot of the observed X-ray powder diffractogram
2
of
ϱ
[Ce
2
Cl
6
4
(bipy) ]·py with a combined fit of the Ce network (bottom)
and CeCl
3
(above).
Photoluminescence and IR Spectroscopy
The two-dimensional network 2 [Ce Cl (bipy) ]·py shows
ϱ
2
6
4
3+
interesting photoluminescence properties with Ce -centred
light-emission in the UV-blue range below the visible border.
Determinations via photoluminescence spectroscopy (Figure 5)
reveal a broad band emission in the range of λ = 330–380 nm,
which can be correlated to the fluorescent Ce3+ 5d Ǟ4f tran-
sition. Furthermore, the split emission profile with two max-
ima at λmax = 336 nm and 360 nm can be correlated to the
1
1
Figure 3. Depiction of the Archimedean cem topology type of the
2
ϱ
[Ce
2
Cl
6
(4,4Ј-bipy)
4
] network (top). View along a axis revealing the
2
2
splitting of the ground level into F and F levels due to
7
/2
5/2
channel like structures (black circles) through overlaying network
[Ce Cl (4,4’-bipy) ] (bottom).
1
1
sheets of 2
spin-orbit coupling. The 5d Ǟ4f transition is strongly influ-
ϱ
2
6
4
enced by the crystal and ligand field as well as the nephelaux-
The point symbol for the uninodale 5-c network etic effect caused by the coordinated chloride anions. The in-
2
3+
[
Ce Cl (4,4Ј-bipy) ] and the corresponding Ce ions is fluence of the chloride ions in the coordination sphere of the
ϱ
2
4
6
3 [17]
4
3
{
3 .4 .5 } with a Vertex symbol of [3.3.3.4.4.*] and the ring cerium ion leads to a shift in the energetic position of the low-
1
–1
types are [3a.3a.3a.4a.4a.*] (the asterisk marks calculated ring est 5d excited state to ca. 32.000 cm . Related energies and
circulations above 20 that were omitted). Analogous networks similar splitting of the emission could be observed for CeCl3
with cem topology can be found in transition metal MOFs doped in NaCl, exhibiting the same two maxima in emission
2
[18]
based on carboxy ligands like [Cd(Hpptpz)(bpba)]·2H O
at wavelengths with slightly lower energy (λ
= 346 nm and
max
ϱ
2
2
[19]
[22]
and [Co(1,2-phda)(4-bpmp) (H O)]. The sheets are alter- 373 nm).
nately stacked along [101] perpendicular to their proliferation rium content of the network 2 [Ce Cl (bipy) ]·py. An energy
The emission can clearly be addressed to the ce-
ϱ
1.5
2
ϱ
2
6
4
plane along (201). The alternating stacking between two sheets diagram as well as a structure-property graphic is also shown
can be best described with half an elemental cell displacement in Figure 5. The excitation spectrum exhibits a maximum at
1
1
along the b axis for the Ce Cl dimeric units. This alignment λmax = 284 nm, which can be correlated to the 4f Ǟ5d transi-
2
6
leads to a formation of a channel like structure along the a tion and a shoulder at λ Ͻ 250 nm. The excitation maxima at λ
axis formed by trapezoid like cavities of the sheets. Pyridine Ͻ 250 nm may be correlated to the coordinated 4,4Ј-bipyridine
molecules are intercalated in every second cavity between the molecules as the free ligand shows a similar excitation spec-
sheets (Figure 3, bottom). The cavities in between the layer trum in this wavelength range. An actual formation of a pos-
Z. Anorg. Allg. Chem. 2014, 2847–2851
© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
2849

P. R. Matthes, K. Müller-Buschbaum
ARTICLE
sible antenna effect[23] between 4,4Ј-bipyridine and Ce3+ can- the 2D network shows intense UV emission of allowed Ce
3+
1
1
2
2
not be proven as the referring excitation band in the range of transitions 5d Ǟ4f ( F , F5/2) at 336 nm and 360 nm repre-
7/2
300–350 nm correlating to 4,4Ј-bipyridine is within the senting a ligand and crystal field based splitting of the 5d-
shoulder of Ce transitions in the excitation spectrum of states, with the lowest energy levels being close to the visible
2
[
Ce Cl (4,4Ј-bipy) ]. Typically, these excitation bands can be range.
ϱ
2 6 4
3+
observed for antenna triggered 4f-4f luminescence of Ln ions
in compounds based on LnCl -4,4Ј-bipy and py.
[11c,17]
Experimental Section
3
All manipulations were carried out in an inert atmosphere using glove
box, ampoule as well as Schlenk and Young vacuum line techniques.
The IR spectra were recorded with a THERMO NICOLET 380 spec-
trometer. IR investigations were done with KBr pellets under vacuum.
Thermal properties were determined by simultaneous DTA/TG
(
NETZSCH STA 409) in a constant argon and nitrogen flow of
–
1
2
0 ml·min . Micro analysis was carried out with an ELEMENTAR
was prepared by a modified am-
Hereby, high temperature calcined CeO
99.9%, Auer-Remy) was dissolved by boiling in concentrated acids
HCl (37%, fuming)/HNO (69%, fuming) and HCl (37%, fuming)/
(30%). Colorless, pure Ce(OH) was obtained by alkaline pre-
vario micro cube. Anhydrous CeCl
3
[
24]
monium halide route.
2
(
3
H
2
O
2
3
cipitation with concentrated aqueous NaOH solution (37%). Alterna-
tively, Cerium hydroxide was obtained by alkaline treatment of an
aqueous Ce(NO
sponding precipitates were dissolved in HCl acid (10 mol·L , reagent
grade) and NH Cl (99.9%, Fluka) was added. (NH CeCl was
3 3 2
) ·6(H O) (99%, Riedel-deHaën) solution. The corre-
–1
4
4
)
3
6
formed and decomposed at 500 °C under vacuum, followed by purifi-
cation by sublimation under vacuum at 850 °C yielding anhydrous
CeCl
3
. 4,4Ј-bipyridine (98%, Acros) was dried under vacuum prior to
reaction, and anhydrous pyridine (99%, Acros) was used as purchased.
Synthesis of 2
bipyridine (4,4Ј-bipy, C10
NH ; 491 mg, 6.2 mmol) were sealed in an evacuated (3ϫ
0–3 mbar) DURAN® glass ampoule. A heating program of six steps
[Ce
Cl
(bipy)
]·py: CeCl
2 8
N H ; 234 mg, 1.5 mmol), and pyridine (py,
ϱ
2
6
4
3
(148 mg, 0.6 mmol), 4,4Ј-
C
5
5
1
–
1
was applied starting with heating to 50 °C with a rate of 5 K·h , ad-
ditional heating to 100 °C with 1 °C·h , and then to 130 °C with
0.5 °C·h . The temperature was maintained for 168 h followed by
reducing to 100 °C with a rate of 0.5 °C·h and to room temperature
–
1
Figure 5. Excitation und emission spectra of 4,4Ј-bipyridine and
2
1
1
–1
ϱ
[Ce
2 6 4
Cl (4,4Ј-bipy) ] in the solid-state (top, left); the 5d –4f transi-
1
–1
tions from the excited state 5d to the split ground state are marked in
–
1
the graphics by the term symbols. Energy diagram of the cerium(III)- with 1 °C·h . The reaction yielded a yellowish crystalline powder
centred luminescence (top, right). Schematic diagram of the structure-
within the saturated solvent. Alternatively, the reaction can also be
luminescence coherence (bottom).
–1
carried out at 220 °C (starting with heating to 120 °C at 10 °C·h and
further heating to 220 °C at 2 °C·h . The temperature was maintained
for 168 h then lowered down to 120 °C at 2 °C·h and to room tem-
perature at a rate of 1 °C·h ) leading to the same product, which was
–
1
Mid IR spectra of the product confirm the coordination of
–1
3
+
4
,4Ј-bipyridine to the Ce ion by a shift of the ν(C=N) ring
–1
–
1
vibration node from 1591 cm for the free molecule to confirmed by X-ray diffraction. The compound was washed two times
602 cm for the metal-bonded molecule in the network. with 1 mL anhydrous pyridine to remove excess 4,4Ј-bipyridine and
–
1
1
–
1
Furthermore, the IR band at 1483 cm confirms the presence dried in a vacuum. Yield: 179 mg (50%). The product is air and moist-
ure sensitive. Vibrational spectroscopy MIR (KBr): ν˜ = ν(C–H)
of pyridine intercalated into the cavities of the sheet structure.
3
1
1
050 w, 2921 w, 2852 w, ν(C–N ring, 4,4Ј-bipy) 1602 vs, ν(C–C ring)
532 w, 1413 m, 1139 w, 1073 w, δ(C–H, pyridine) 1438 w, δ(C–H)
488 w, 1322 vw, 1262 vw, 1224 m, ν(C–C, aromatic) 1002 w, γ(C–
Conclusions
H) 854 vw, 808 vs, 759 vw, δ(C=C, aromatic) 1042 w, 1110 w, 732 vw,
The 2D network 2ϱ [Ce Cl (bipy) ]·py was synthesized and 704 m, 618 s, 570 vw, 518 vw, 417 w, γ(C=C, aromatic) 465 vw,
2
6
4
–
1
2
–1
characterized as the missing link between the 2D MOFs 443 vw, 485 w cm .
ϱ
[Ce
2 6 4
Cl (bipy) ]·py (1196.91 g·mol ): C 44.96
2
(
calcd. 45.16); H 3.15 (3.16); N 10.48 (10.53)%.
[
Ln Cl (bipy) ]·2bipy (Ln = Pr – Tb) and the dense 3D
ϱ
2 6 3
3
framework [La Cl (bipy) ]·4bipy. As crystallization directly
ϱ
2
6
5
Crystal Structure Determination, Powder X-ray Diffraction,
from a melt of bipy failed, a solvent assisted solvothermal ap-
proach in pyridine was used to circumvent this problem. The
cerium containing network marks a real intermediate between
La and Pr regarding the coordination number and its crystal
and Photoluminescence Spectrometry: Suitable crystals of
2
ϱ
2 6 4
[Ce Cl (4,4Ј-bipy) ]·py for single-crystal X-ray analysis were se-
lected under viscous perfluorinated polyalkylether (ABCR). The data
collection was carried out with a BRUKER AXS SMART APEX dif-
structure that does not adopt one of the known phases, while fractometer equipped with graphite monochromator at 168 K and Mo-
the assisting solvent is not involved in coordination. Moreover, radiation (λ = 71.07 pm) using the BRUKER AXS SMART Soft-
K
α
2
850
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© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2014, 2847–2851

Cerium(III) UV-Emitting 2D-Coordination Polymer
ware package.[25] Multi-scan absorption via SADABS was applied.[26] [3] M. Kurmoo, Chem. Soc. Rev. 2009, 38, 13530.
[
4] a) M. D. Allendorf, C. A. Bauer, R. K. Bhakta, R. J. T. Houk,
Chem. Soc. Rev. 2009, 38, 1330; b) Y. Cui, Y. Yue, G. Qian,
B. Chen, Chem. Rev. 2012, 112, 1126; c) J. Heine, K. Müller-
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Further data processing was done with XPREP. Structure solution was
[
27]
achieved with the Patterson method
using SHELXS-97. The com-
pound crystallizes in the monoclinic space group C2/m. All non-
hydrogen atoms were refined anisotropically by least-squares tech-
niques (SHELXl-97).[ All hydrogen atoms were calculated into pre-
set positions with isotropic thermal parameters adjusted to 1.2 of the
corresponding carbon atom. The crystallographically independent pyr-
idyl rings of the coordinated 4,4Ј-bipyridine molecules show rotational
28]
[
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For further crystallographic information see
Crystallographic data (excluding structure factors) for the structure in
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Data Centre, CCDC, 12 Union Road, Cambridge CB21EZ, UK.
Copies of the data can be obtained free of charge on quoting the de-
pository number CCDC-988091 (Fax: +44-1223-336-033; E-Mail:
deposit@ccdc.cam.ac.uk, http://www.ccdc.cam.ac.uk).
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Acknowledgements
We gratefully acknowledge the Deutsche Forschungsgemeinschaft for
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