Complexation of cobalt(II) at the upper rim of two new calix[4]arene/bipyridine-based podands

Article abstract of DOI:10.1002/(sici)1099-0682(200004)2000:4<683::aid-ejic683>3.0.co;2-n

Introduction of one or two 2,2'-bipyridine units at the upper rim of the calix[4]arene platform was performed by means of the Wittig reaction. The resulting alkenes were hydrogenated to give two new bipyridyl-based calixarene podands, which were studied a

Full text of DOI:10.1002/(sici)1099-0682(200004)2000:4<683::aid-ejic683>3.0.co;2-n

FULL PAPER
Complexation of Cobalt(II) at the Upper Rim of
Two New Calix[4]arene/Bipyridine-Based Podands
Jean-Olivier Dalbavie,[b] Jean-Bernard Regnouf-de-Vains,*[a] Roger Lamartine,[b]
Sylvain Lecocq,[c] and Monique Perrin[c]
Keywords: Calix[4]arenes / Bipyridines / Podands / Cobalt complexes
Introduction of one or two 2,2’-bipyridine units at the upper
rim of the calix[4]arene platform was performed by means of
pyridyldichlorocobalt complex was notably fully charac-
terised by 1H-NMR and X-ray crystal structure analyses,
the Wittig reaction. The resulting alkenes were hydrogen- which confirmed the tetrahedral coordination mode invol-
ated to give two new bipyridyl-based calixarene podands,
which were studied as ligands for CoII cation. The mono-bi-
ving the bipyridyl subunit and the two chlorine atoms around
the cobalt centre.
Introduction
are bound by an ethylenic linkage to the upper rim of the
calixarene platform.
As recently reviewed by Matt et al.,[1] the calixarenes dis-
play interesting properties for transition metal chemistry,
via their own binding sites (oxygens, aryl rings), or by their
ability to act as carriers and spatial organisers of various
types of chelating agents, such as esters, phosphanes, or het-
erocycles. In this domain, our contribution resulted in the
synthesis and study of the complexation properties of vari-
ous podands incorporating 2,2’-bipyridine and 2,2’-bithia-
zole chelating units at the lower rim of the tetra-p-tert-bu-
tylcalix[4]arene platform.
In order to develop a similar approach at the upper rim,
but in a different way than through the potentially coordin-
ating amide links developed by Beer and coll.,[3] we found
that the Wittig reaction could be an interesting synthetic
tool for building a new family of lipophilic ligands in which
the chelating units would be attached by a stable and non-
coordinating ethylenic linkage to the calixarene platform.
As a first step, this reaction was applied on the mono[p-
(formyl)]tris[p-(tert-butyl)]calix[4]arene model, leading to
the conjugated phenol-bipyridyl system 1.[4] The relative in-
stability of this ligand and its copper(I) complex ([1/Cu/
1]PF6),[5] especially on chromatographic supports, limited
the interest of this family of unsaturated ligand in our field
of investigations, and led us to develop the complexation
studies of the corresponding saturated podands.
Results and Discussion
Syntheses of ligands (Scheme 1 and Scheme 2). Ligand 2
was obtained quantitatively by catalytic hydrogenation of 1,
but we found it better to reduce the raw Wittig material
directly, in order to eliminate the loss of 1 during chromato-
graphy. In this way, 2 was obtained in a yield of 40% vs the
formylcalixarene platform, instead of 27% with isolation
of 1.
The synthetic strategy developed for the disubstituted po-
dand 3 was similar to 1 and 2, and involved a selective
double deterbutylation of the tetra-p-tert-butylcalix[4]arene
4, followed by a double Gross formylation[6] applied on the
unprotected calixarene platform. The resulting aldehyde
was then treated in alcoholic basic conditions with the mon-
ophosphonium salt of bipyridine 5 to give the correspond-
ing diene which was directly catalytically hydrogenated into
the desired armed calixarene.
The selective introduction of two chelates at the 5th and
17th positions of the calix[4]arene platform 4 involved a
preliminary retro-Friedel and Crafts di-deterbutylation step
developed by Gutsche and coll.[7] via a selective protective
dinitrobenzoylation of two hydroxyl groups in diametrical
positions. The resulting diester was obtained in three differ-
ent acylation media, namely dichlorophenylphosphate/di-
nitrobenzoic acid/DMF/ pyridine, AlCl3/dinitrobenzoyl
chloride/DMF, or dinitrobenzoyl chloride/pyridine systems,
with yields of 75, 67, and 95%, respectively. More recently,
Huang and coll.[8] described the formation of the dibenzoyl
analogue 6 in a benzoyl chloride/CHCl3/NEt3 medium with
a yield of 68%. We found that 6 could easily be synthesised
from 4 and benzoyl chloride using MeCN as solvent and
K2CO3 as base, with a good yield of 91%.
We thus present here the syntheses and some com-
plexation properties towards Cobalt(II) of two new calixar-
ene-based bipyridine ligands, in which the chelating units
[a]
´
Laboratoire de Chimie Therapeutique,
´
UMR 7565 CNRS-UHP, Faculte de Pharmacie,
5, rue Albert Lebrun, F-54001 Nancy Cedex, France
Fax: (internat.) ϩ 333/83178863
E-mail: jean-bernard.regnouf@pharma.u-nancy.fr
Laboratoire de Chimie Industrielle
[b]
[c]
Laboratoire de Cristallographie, ESA 5078 du CNRS,
´
Universite Claude Bernard Lyon I,
The subsequent retro-Friedel and Crafts deterbutylation
step was carried out in toluene using only five equivalents
43 Bd du 11 Novembre 1918, F-69622,
Villeurbanne Cedex, France
Eur. J. Inorg. Chem. 2000, 683Ϫ691
WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2000
1434Ϫ1948/00/0404Ϫ0683 $ 17.50ϩ.50/0
683

J.-O. Dalbavie, J.-B. Regnouf-de-Vains, R. Lamartine, S. Lecocq, M. Perrin
FULL PAPER
Scheme 1
Scheme 2
of AlCl3 relative to 6. The reaction was initiated by a should not be in a pure cone conformation. The reson-
gentle warming and was completed in ca. 1–2 hours, ance signals of the Ar–CH2-Ar groups appear at δ ϭ
giving 7 with a yield of 80%. Based on the recent work 33.39 and 33.84, respectively, between the standard δ ϭ
of Magrans and coll., dedicated to the conformational 31 and 37 values observed for the pure syn and anti
study of 1,3-di-O-benzoylated calix[4]arenes,[9] the 13C- conformations. This suggests that a rapid exchange be-
NMR analyses of compounds 6 and 7 show that they tween the conic and the 1,3-alternate conformations takes
684
Eur. J. Inorg. Chem. 2000, 683Ϫ691

Two New Calix[4]arene/Bipyridine-Based Podands
FULL PAPER
place in solution. Nevertheless, for legibility, 6 and 7 are
Thus, reacting 2 with one equivalent of anhydrous CoCl2
drawn in the conic conformation in Scheme 2.
in a MeOH/CH2Cl2 mixture at room temperature gave the
The benzoate groups were then removed in alcoholic light-blue complex 13 (Scheme 3), which was purified by
NaOH at reflux. The 11,23-di-p-tert-butylcalix[4]arene 8 chromatography on Sephadex LH20, and then crystallised
was thus obtained in an almost quantitative yield.
as fine needles from a hexane/CH2Cl2 mixture. Unfortu-
Introduction of the two formyl groups at the upper rim nately these were unsuitable for X-ray analysis. Elemental
of 8 failed when the previously described conditions were analysis was consistent with the presence of 0.2 equivalent
employed. The use of TiCl4 instead of SnCl4 was successful, of CH2Cl2.
affording the bis-aldehyde 9 and some mono-aldehyde 10,
The latter was found in the standard 1H-NMR spectrum
in yields of 65 and 19%, respectively. It is interesting to
of 13, which also did not display the resonance pattern of
note that, as previously mentioned,[4] a treatment of the raw
the bipyridyl group, thereby confirming the paramagnetic
electrophilic substitution material over Al2O3 was mandat-
nature of the complex subunit. The remaining part of the
ory to liberate the formylated species.
molecule, out of the sphere of direct influence of CoII, dis-
Reaction of 9 with two equivalents of 5[4] in the presence
played resonance signals in the expected regions. In CDCl3,
of an excess of NaOMe in MeOH afforded a mixture of
at 300 MHz, two singlets assigned to tert-butyl groups were
compounds from which only low amounts of pure bis(alk-
found at δ ϭ 1.24 (9 H) and δ ϭ 2.15 (18 H); four broad
ene) 11 were isolated. For this reason, we preferred to hy-
singlets located at δ ϭ 2.50, 2.95, 3.34, and 3.94 (2 H each)
drogenate the raw Wittig material directly. From the re-
were assigned to the Ar–CH2-Ar groups, considering that
sulting mixture, the bisalkane 3 was isolated after chroma-
the ethylenic bridge, which supports the effect of the cobalt
tography in a yield of 22%.
cation, did not give resonance signals. Changing CDCl3 for
CD2Cl2 resulted in the transformation of these four singlets
into two well-separated broad AB systems, confirming our
previous assignment and suggesting a probable rigid-
Complexation Studies
ification due to a specific interaction between this solvent
and the macrocycle.
Cobalt(II) Complex of 2
The reactivity of 6,6’-dimethyl-2,2’-bipyridine (dmbpy)
towards CoII cation has notably been studied by Newkome
and coll., who prepared, based on UV/Vis spectroscopy and
elemental analysis, the neutral tetrahedral Co(dmbpy)Cl2
complex 12.[10] The same approach applied to an octobipyr-
idylcalix[4]resorcinarene ligand allowed us to prepare, based
on UV/Vis spectroscopy, elemental and ES-MS analyses,
In the aromatic part, two sharp singlets at δ ϭ 6.92 and
7.06, and a broad one at δ ϭ 7.82, each integrating 2H,
were assigned to the aromatic protons of the unsubstituted
phenol rings. Finally, a broad singlet located at δ ϭ 9.32
was assigned to the four hydroxyl groups.
The fact that the resonance signals of protons close to
the corresponding octodichlorocobalt species,[2b] which the metallic centre, with regards to the supposed structure
demonstrated that the presence of a bulky substituent close of complex 13, are absent in these classical analytical condi-
to the chelating site was not limiting the complexation pro- tions led us to seek them in a larger frequency domain.
cess.
Recording data over 65000 Hz (216 ppm at 300 MHz) al-
In 2 or 3, the presence of the ethylenic linkage should lowed the exhibition of ten new signals: six relatively sharp
give a more pronounced (dimethyl)bipyridine character to singlets (∆ν1/2 ϭ 30–38 Hz) integrating for 1 H each, at δ ϭ
the chelating site than in the above-mentioned example, and 70.71, 69.92, 49.10, 46.67, –14.77, and –15.72 that we sus-
therefore facilitate the coordination process of CoII.
pect correspond to the bipyridine protons; a larger singlet
Scheme 3
Eur. J. Inorg. Chem. 2000, 683Ϫ691
685

J.-O. Dalbavie, J.-B. Regnouf-de-Vains, R. Lamartine, S. Lecocq, M. Perrin
FULL PAPER
Figure 1. COSY correlations between protons of complex 13 (CDCl3, 500 MHz, 293 K) (main spectrum: bipyridine resonance pattern;
offset: aryl resonance pattern)
at δ ϭ –2.63 (∆ν1/2 ϭ 48 Hz) integrating for 2 H, which was centred transition at 655.5 nm with a molar extinction coef-
assigned to the substituted phenol ring protons, and three ficient of ca. 530 dm3.mol–1.cm–1, identical to the values
large singlets, one integrating for 2 H (∆ν1/2 ϭ 92 Hz) at reported for 12 and corresponding to a tetrahedral coor-
δ ϭ –17.21, another one integrating for 3 H (∆ν1/2
ϭ
dination mode.[10]
169 Hz) at δ ϭ –21.68, and the last singlet integrating for 2
ES-MS analysis confirmed the formation of 13. The pre-
H (∆ν1/2 ϭ 300 Hz) at δ ϭ –37.73, which were assigned to liminary measurements were performed in CH2Cl2 con-
the CH2-phenol, the CH3-bpy and the CH2-bpy groups, re- taining some MeOH as proton source. In the positive mode,
spectively.
three peaks corresponding to species containing the native
Working at 500 MHz resulted in slight changes in chem- ligand 13 were observed at 846.5, 811.6 and 789.7 a.m.u.
ical shifts (see Experimental Section). 500-MHz COSY ex- and were attributed to the mono-charged cations [13 –
periment (58000 Hz, 116 ppm) (Figure 1) confirmed the at- 2Cl– – Hϩ]ϩ, [13 – CoCl2 ϩ Naϩ]ϩ, and [13 – CoCl2 ϩ
tribution of the bipyridine protons, with two groups of sig- Hϩ]ϩ, respectively. They were accompanied by compounds
nals at δ ϭ 66.06, 43.87, –14.30, and δ ϭ 65.35, 46.17, – of higher molecular weights which were analysed as com-
13.52, the negative signals corresponding to the H(4) and plex 13 in which one or two phenol groups were O-methyl-
H(4’) spin systems. Another scalar correlation was found in ated and one chlorine was exchanged with a methoxy an-
the calixarene aromatic region between the singlets at δ ϭ ion: 906.6 a.m.u. [(CH3O)2 13–2Cl– ϩ CH3O–]ϩ and 892.6
7.75 and δ ϭ 7.07, which were thus assigned to the two a.m.u. [(CH3O) 13–2Cl– ϩ CH3O–]ϩ (Scheme 4).
lateral phenol rings.
In the negative mode, which usually gives, in the calixar-
UV/Vis spectroscopy of 13 in CH2Cl2 showed a complex ene family, the mono- or polyphenate anions, the same phe-
ligand-centred absorption pattern associated with a metal- nomenon was observed at –50 V, but with a much lower
686
Eur. J. Inorg. Chem. 2000, 683Ϫ691

Two New Calix[4]arene/Bipyridine-Based Podands
FULL PAPER
Scheme 4
intensity, the base peak at 787.6 a.m.u. corresponding to the leaning of the supporting phenol ring A, while C, in the
deprotonated ligand 2. The molecular peak was observed at alternate position, is strongly inclined. The tert-butyl group
916.6 a.m.u. [13 – Hϩ]–, accompanied by the mono- and of the latter occupies two positions, differing by a rotation
the bis-dehalogenated species at 880.5 a.m.u. [13 – Cl– – of about 60°, with occupancies of 51% and 49%.
2Hϩ]– and 844.5 a.m.u. [13 –2Cl– – 3Hϩ]–, respectively.
Each complex unit is associated with a molecule of Et2O
Three peaks at 950.6, 940.6, and 926.6 a.m.u. were attrib- and one of CH2Cl2. The former, which is not shown in Fig-
uted to complexes containing one tris-, one bis-, and one ure 2, is located between the macrocycles, while the latter is
monomethylated ligand with a double or single anion meta- trapped into the calixarene cavity, on the level of the tert-
thesis, i.e. [(CH3O)313 –2Cl– ϩ 2CH3O– – Hϩ]– (Scheme 4), butyl groups (Figure 3).[11] This molecule of CH2Cl2 is
[(CH3O)213 – Cl– ϩ CH3O– – Hϩ]–, and [(CH3O) 13 – Cl– found in disordered positions called Cl20–C100–Cl10 (73%)
ϩ CH3O– – Hϩ]–. We found in fact, that these methylation (Figure 2), and Cl30–C200–Cl40 (27%); Cl20 and C200 on
reactions and anion metatheses occurred during the ana- one part, Cl40 and C100 on the other part, are positioned
lysis: changing the solvent for alcohol-free CH2Cl2 (sta- on the same sites. The interactions between dichlorome-
bilised with 2-methyl-2-butene), gave, in the positive mode thane and calixarene are found between C100 and ring C
˚
˚
(ϩ 80 V), peaks at 882.5, 846.6, and 789.9 5 a.m.u. which (3.46 A) and C200 and ring A (3.34 A).
were attributed to [13 – Cl–]ϩ, [13 –2Cl– – Hϩ]ϩ, and [13 –
This specific complexation found in the solid state can be
CoCl2 ϩ Hϩ]ϩ, respectively.
correlated with the modifications of the 1H-NMR spectrum
Blue single crystals of complex 13, suitable for X-ray dif- of complex 13, which were previously observed between its
fraction analysis, were obtained in a closed tube by liquid CDCl3 and CD2Cl2 solutions.
diffusion of Et2O into a solution of 13 in CH2Cl2. This
According to the proposal for classification and nomen-
study confirmed the presence of the expected dichlorocob- clature of host-guest type compounds given by Weber and
alt-bipyridine complex subunit attached by an ethylene link Josel,[12] compound 13 can be defined as a cryptato-tubul-
to the upper rim of the tri-tert-butylcalix[4]arene platform ato clathrate.
(Figure 2). The cobalt cation is coordinated in a distorted
tetrahedral mode to the two bipyridyl nitrogen atoms and
Cobalt(II) Complex of 3
to the two chlorine anions (Table 1), confirming the hypo-
In a similar way, ligand 3 was reacted with two equiv.
thesis of Newkome et al.[10] The bipyridyl group is parallel of CoCl2 to give the dinuclear grey-blue complex 14. The
to the supporting phenol ring A, making with it an angle expected M2L stoichiometry was verified by UV/Vis spec-
of only 4.25°.
troscopy in CH2Cl2, with an ε value of 1030 dm3 mol–1 cm–1
The cyclic tetramer is in a boat-shaped cone conforma- at 656.5 nm, twice the value of 13, and by C, H, and N
tion, with the expected usual hydrogen bonds between the elemental analyses. Positive- or negative mode ES-MS ana-
hydroxyl groups (2.608–2.731 Ä). The angles between the lysis of 14 showed methylation reactions and anion meta-
phenol rings A, B, C, and D, and the mean plane defined theses similar to those observed with 13 when methanolic
by the methylene bridges amount to 122.7(2), 118.0(2), CH2Cl2 was used as the solvent (see Experimental Section).
132.7(1), and 117.1(2)°, respectively. Surprisingly, the pres- In the negative mode (–50 V), in alcohol-free CH2Cl2, the
ence of the bulky complex substituent do not result in the complex exhibited a single mass of peaks at 1185.5–1189.3
Eur. J. Inorg. Chem. 2000, 683Ϫ691
687

J.-O. Dalbavie, J.-B. Regnouf-de-Vains, R. Lamartine, S. Lecocq, M. Perrin
FULL PAPER
Figure 2. Numbering scheme and ORTEP underside-view of complex 13
Table 1. Selected geometric parameters around the cobalt centre
Unfortunately, the lack of solubility of 14 did not allow
us to verify the H-NMR results obtained with 13.
1
˚
Bond lengths [A]
Co–N52
Co–Cl2
2.021(5)
2.213(2)
Co–N61
Co–Cl3
2.027(6)
2.222(2)
Conclusion
Bond angles [°]
Cl2–Co–Cl3
Cl2–Co–N52
N52–Co–Cl3
118.4(9)°
119.6(2)°
108.7(2)°
N52–Co–N61
Cl3–Co–N61
N61–Co–Cl2
82.3(2)
By a Wittig reaction plus hydrogenation process, we have
110.1(2)
112.0(2) selectively incorporated one and two bipyridine units at the
upper rim of p-(tert-butyl)calix[4]arene platforms. The two
new ligands thus obtained displayed coordinating behavi-
our towards cobalt(II), and the resulting mono- and dinuc-
lear complexes were fully characterised. With the monomet-
1
allic species, H-NMR COSY experiment performed on a
large frequency domain allowed us to recover and to assign
the bipyridine resonance signals, and X-ray analysis con-
firmed the tetrahedral coordination of the bipyridine and
the two chlorine atoms around the cobalt centre. The com-
plexation studies of other transition metal cations and the
building of the tris- and tetra-substituted analogues are now
under investigation.
Experimental Section
Figure 3. ORTEP side-view of complex 13
General: Melting points (°C, uncorrected) were determined on an
Electrothermal 9100 in Capillary apparatus. – 1H and 13C NMR
spectra were recorded on a Bruker AM 300 or DRX 300 and DRX
500 (CDCl3, TMS as internal standard, chemical shifts in ppm). –
Mass spectra (electrospray, ES) were recorded on a Platform Mic-
a.m.u. which was attributed to the monophenate species
[14 – Hϩ]–, confirming the results of UV/Vis and ele-
mental analyses.
688
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Two New Calix[4]arene/Bipyridine-Based Podands
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romass apparatus at the Service Central d’Analyse du CNRS, Sola-
ize. – Infrared spectroscopy was performed on a Mattson 5000 FT
apparatus (KBr, ν˜ in cm–1). – UV spectra were recorded on a Shim-
adzu UV 2401 PC or a SAFAS UV mc2 apparatus, λmax in nm, ε
in dm3 mol–1 cm–1. – Elemental analyses were performed at the
Ar and C6H5); 150.43, 148.87, 143.34, 142.61, 131.92, 127.78,
129.38 (Co, Cp, Cipso of Ar; Cipso C6H5); 165.01 (CϭO). – ES-MS
(neg. mode); m/z: 855.7 [6 – H]–; (pos. mode): 857.6 [6 ϩ H]ϩ. –
C58H64O6 (857.15): calcd. C 81.27, H 7.53, O 11.20; found C 81.08,
H 7.90, O 11.16.
´
Service Central de Microanalyse, Ecole Superieure de Chimie,
Calix[4]arene-26,28-diol 7: A mixture of 6 (6 g, 7 10–3 mol) and
AlCl3 (4.7 g, 35 10–3 mol) in 300 mL of toluene was heated until a
red colouration persisted, and then stirred at room temp. for 2 h.
H2O (100 mL) was added, and the resulting emulsion was stirred
for 30 min. The toluene phase was washed with water
(3 ϫ 100 mL), the latter extracted with CH2Cl2, and the combined
organic phases evaporated to dryness. The yellow residue was dis-
Montpellier. – Macherey–Nagel TLC plates were used for chroma-
tography analysis (SiO2, Polygram SIL G/UV254, ref.805021). All
commercially available products were used without further puri-
fication unless otherwise specified.
Calix[4]arene-25,26,27,28-tetrol 2. – Indirect Method: To a solution
of 0.05 g of 1[3] (0.063 10–3 mol) in 5 mL of EtOH/CH2Cl2, was
added 0.01 g of 5% Pd/C, and H2 was bubbled through the solution solved in a mixture of CH2Cl2 (50 mL) and MeOH (250 mL) and
for 1 min. The mixture was stirred at room temp. overnight under
H2 and then filtered over Celite. Evaporation of the filtrate to dry-
ness afforded 0.045 g of pure 2 (90%).
then concentrated in vacuo to ca. 100 mL to give 4.2 g of 7 (80%)
as a white precipitate; m.p. 320 °C(dec). – UV/Vis (CH2Cl2): λ
(ε) ϭ 275.0 (9480), 282.0 (sh, 8330). – IR: ν˜ ϭ 1735 (CϭO). – H
1
NMR (CDCl3): δ ϭ 1.08 (s, 18 H, Me3C); 3.87, 3.57 ("q", AB,
JAB ϭ 14.1 Hz, 8 H, Ar–CH2-Ar); 6.59 (t, J ϭ 7.4 Hz, 2 H, Ar);
6.93 (d, J ϭ 7.4 Hz, 4 H, Ar); 7.00 (s, 4 H, Ar); 7.52 (t, J ϭ 7.7
Hz, 4 H, C6H5); 7.72 (t, J ϭ 7.4 Hz, 2 H, C6H5); 8.22 (d, J ϭ 7.0
Hz, 4 H, C6H5). – 13C NMR (CDCl3): δ ϭ 31.19 (Me3C); 33.84
(Ar–CH2-Ar); 34.15 (Me3C); 119.62, 130.70, 129.27, 128.68,
126.31, 133.75 (CH of Ar and C6H5); 128.05, 131.95, 144.05,
149.04, 152.91 (Co, Cp, Cipso of Ar, Cipso of C6H5); 164.76 (CϭO). –
ES-MS (neg. mode); m/z: 535.5 [7– H]–. – C50H48O6 (744.94): calcd.
C 80.62, H 6.50, O 12.88; found C 80.57, H 6.73, O 12.81.
Direct Method: The raw Wittig material obtained from 0.5 g
(0.8 mmol) of monoformylcalixarene was neutralised with 1  HCl
and evaporated to dryness. The resulting glassy material was dis-
solved in 50 mL of CH2Cl2, dried over Na2SO4 and concentrated
to ca. 20 mL. EtOH (30 mL) and 0.2 g of 5% Pd/C were added,
and the resulting mixture was stirred under H2 overnight. The sus-
pension was filtered over Celite and evaporated to dryness. The
residue was dissolved in CH2Cl2 and addition of MeOH resulted
in the precipitation of a raw material which was purified by chro-
matography (Al2O3, CH2Cl2/hexane, then CH2Cl2/MeOH 99:1) to
give 0.25 g of 2 (40%). –UV/Vis (CH2Cl2): λ (ε) ϭ 281.0 (23390),
Calix[4]arene-25,26,27,28-tetrol (8): A mixture of 7 (4.2 g, 5.6 10–3
1
289.0 (24180), 304.0 (10400). – H NMR (CDCl3): δ ϭ 1.198 (s, 9
mol) and NaOH (8 g, 200 10–3 mol) in a mixture of EtOH (120 mL)
H, Me3C); 1.205 (s, 18 H, Me3C); 2.62 (s, 3 H, Mebpy); 2.80–3.20 and H2O (40 mL) was heated under reflux for 12 h. After cooling,
(ABm, 4 H, CH2–CH2); 3.45, 4.22 (‘‘q’’, AB, JAB ϭ 13 Hz, 4 H, the solution was acidified to pH 5–6 with HCl to give a white
Ar–CH2-Ar); 3.45, 4.22 (‘‘q’’, AB, JAB ϭ 13 Hz, 4 H, Ar–CH2-
Ar); 6.93 (s, 2 H, Ar); 7.01–7.07 (m, 7H, 6 H of Ar, 1 H of bpy);
precipitate which was collected by filtration, and then dissolved in
CH2Cl2. Addition of MeOH resulted in the precipitation of 3 g of
7.02 (d, J ϭ 7.6 Hz, 1 H, bpy); 7.64 (t, J ϭ 7.6 Hz, 1 H, bpy); 8.19 8 (99%), m.p. 300 °C. – UV/Vis (CH2Cl2): λ (ε) ϭ 277.5 (10000),
1
(d, J ϭ 7.7 Hz, 1 H, bpy); 8.20 (d, J ϭ 7.7 Hz, 1 H, bpy); 10.28 (s, 282.5 (sh, 8600). – H NMR (CDCl3): δ ϭ 1.25 (s, 18 H, Me3C);
4H, OH). – 13C NMR (CDCl3): δ ϭ 24.67 (Mebpy); 31.40, 31.46 4.26, 3.56 ("q", 8 H, Ar–CH2-Ar); 6.73 (t, J ϭ 7.7 Hz, 2 H, Ar);
(Me3C); 32.34, 32.51 (Ar–CH2-Ar); 33.98, 34.03 (Me3C); 34.95, 7.08 (d, J ϭ 7.7 Hz, 4 H, Ar); 7.09 (s, 4 H, Ar); 10.29 (s, 4 H,
40.07 (CH2–CH2); 118.19, 118.53, 122.69, 123.05, 136.97 (C-3, C-
4, C-5, C-3’, C-4’, C-5’ of bpy); 125.71, 125.86, 126.03, 129.00 (CH
OH). – 13C NMR (CDCl3): δ ϭ 31.52 (Me3C); 32.22 (Ar–CH2-Ar);
34.12 (Me3C); 129.02, 125.91, 122.37 (CH of Ar); 148.72, 146.77,
of Ar); 127.41, 127.71, 127.90, 128.31, 135.36, 144.44, 146.37, 144.66, 128.5, 127.56 (Co, Cp, Cipso of Ar). – ES-MS (neg. mode);
146.70, 147.10 (Co, Cp, Cipso of Ar); 155.90, 155.98, 157.78, 160.67 m/z: 535.5 [8 – H]–. – C36H40O4 0.9 CH2Cl2 (613.15): calcd. C
(C-2, C-2’, C-6, C-6’, bpy). – ES-MS (neg. mode; –50V); m/z:
787.7–788.7 [2 – Hϩ]–. – C53H60N2O4 0.25 CH2Cl2 (810.31): calcd.
C 78.93, H 7.53, N 3.46, O 7.90; found C 79.09, H 7.58, N 3.31,
O 7.98.
72.28, H 6.87, O 10.44; found C 72.35, H 6.97, O 10.58.
Calix[4]arene-25,26,27,28-tetrol (9) and Calix[4]arene-25,26,27,28-
tetrol (10): TiCl4 (1.25 mL, 11.2 10–3 mol) was syringed into a soln.
of 8 (0.4 g, 0.65 10–3 mol) in 10 mL of CHCl3. The resulting red
solution was stirred under N2 during 30 min. Dichloromethylme-
Calix[4]arene-26,28-diol 6: A mixture of finely powdered K2CO3
(2.33 g, 17 10–3 mol) and 5 g of p-tert-butylcalix[4]arene 4 (7.7 10–3 thyl ether (1 mL, 11.2 10–3 mol) was then added dropwise. After
mol) in 250 mL of acetonitrile was stirred at 80 °C for 30 min.
Benzoyl chloride (1.8 mL, 15.4 10–3 mol) was then added by syring,
and heating was maintained for 4 h. After cooling, the solvent was
evaporated to dryness and the residue dissolved in 100 mL of
CH2Cl2. The resulting solution was washed with water
(3 ϫ 50 mL), dried over Na2SO4, then concentrated to 40 mL on a
Rotavapor. The residue was then mixed with 300 mL of EtOH and
the resulting cloudy solution was concentrated in vacuo to give 6 g
2 h, 25 mL of water was added and stirring was continued for 1 h.
After separation, the aqueous phase was washed with CH2Cl2
(3 ϫ 20 mL). The combined organic phases were dried over
Na2SO4, then concentrated to dryness. The residue was dissolved
in 1:1 MeOH/CH2Cl2 and 2 g of aluminium oxide were added to
give, after ca. 12 h, the raw aldehyde which was purified by chroma-
tography (SiO2, CH2Cl2) to give 0.08 g of the mono aldehyde 10
(19%) and 0.25 g of 9 (64%). – Compound 9: m.p. Ͼ350 °C. – UV/
1
of 6 (91%), white precipitate, m.p. 320–330 °C (dec.). – UV/Vis Vis (CH2Cl2): λ (ε) ϭ 281.0 (18300). – IR: ν˜ ϭ 1680 (CϭO). – H
(CH2Cl2): λ (ε) ϭ 278.5 (6100). – IR: ν˜ ϭ 1735 (CϭO). – 1H NMR
(CDCl3): δ ϭ 1.01 (s, 18 H, Me3C); 1.15 (s, 18 H, Me3C); 3.49, Ar–CH2-Ar); 7.15 (s, 4 H, Ar); 7.61 (s, 4 H, Ar); 9.74 (s, 2 H,
3.97 ("q", AB, JAB ϭ 14.1 Hz, 8 H, Ar–CH2-Ar); 6.91 (s, 4 H, Ar);
CHO); 10.30 (s, 4 H, OH). – 13C NMR (CDCl3): δ ϭ 31.50 (Me3C),
NMR (CDCl3): δ ϭ 1.24 (s, 18 H, Me3C); 4.27,3.69 (br. AB, 8 H,
7.02 (s, 4 H, Ar); 7.52 (t, J ϭ 7.4 Hz, 4 H of C6H5); 7.70 (t, J ϭ 31.99 (Ar–CH2-Ar); 34.28 (Me3C); 126.41, 131.16 (CH of Ar),
7.4 Hz, 2 H of C6H5); 8.33 (d, J ϭ 7.1 Hz, 4 H of C6H5). – 13C 126.83, 129.15, 131.30, 145.87, 146.14, 154.70 (Co, Cp, Cipso of Ar);
NMR (CDCl3): δ ϭ 31.53, 31.09 (Me3C); 33.39 (Ar–CH2-Ar);
33.86, 34.06 (Me3C); 133.71, 130.50, 128.99, 126.12, 125.64 (CH of C38H40O6 0.1 CH2Cl2 (601.23): calcd. C 76.11, H 6.74, O 15.97;
190.56 (CHO). – ES-MS (pos. mode); m/z: 615.4 [9 ϩ Na]ϩ. –
Eur. J. Inorg. Chem. 2000, 683Ϫ691
689

J.-O. Dalbavie, J.-B. Regnouf-de-Vains, R. Lamartine, S. Lecocq, M. Perrin
found C 76.20, H 7.18, O 15.58. – Compound 10: m.p. Ͼ 350 °C. –
and Ar(D)]; 7.75 [s, ∆ν1/2 ϭ 26.24 Hz, 2 H, H(5) or H(3) of Ar(B)
FULL PAPER
UV/Vis (CH2Cl2): λ (ε) ϭ 280.0 (13500). – IR: ν˜ ϭ 1685 (CϭO). – and Ar(D)]; 9.33 (s, ∆ν1/2 ϭ 39.60 Hz, 4H, OH); 43.87 [s, ∆ν1/2
1H NMR (CDCl3): δ ϭ 1.27 (s, 18 H, Me3C); 3.60, 4.29 (br. AB, 36.50 Hz, 1 H, H(5 or 5’) or H(3 or 3’) of bpy]; 46.17 [s, ∆ν1/2
8 H, Ar–CH2-Ar); 6.74 (t, J ϭ 7.5 Hz, 1 H, Ar); 7.06 (d, J ϭ 7.5 35.20 Hz, 1 H, H(5’ or 5) or H(3’ or 3) of bpy]; 65.35 [s, ∆ν1/2
Hz, 2 H, Ar); 7.13 (s, 4 H, Ar); 7.64 (s, 2 H, of Ar); 9.77 (s, 1 H, 36.80 Hz, 1 H, H(3 or 3’) or H(5 or 5’) of bpy]; 66.06 [s, ∆ν1/2
ϭ
ϭ
ϭ
ϭ
ArCHO); 10.30 (br. s, 4 H, OH). – 13C NMR (CDCl3): δ ϭ 31.47 38.62 Hz, 1 H, H(3’ or 3) or H(5’ or 5) of bpy]. – ES-MS, for
(Me3C), 32.06 (Ar–CH2-Ar); 34.16 (Me3C); 122.55, 125.93, 126.29, C53H60CoCl2N2O4 (918.91; 918): CH2Cl2 ϩ amylene, positive mode:
129.00, 131.15 (CH of Ar), 125.81, 126.53, 127.82, 128.17, 129.35, 882.6, 883.6, 884.6, 885.6 [2 ϩ CoCl2 – Cl–]ϩ; 846.6, 847.7 [2 ϩ
131.12, 145.21, 146.41, 148.53, 154.92 (Co, Cp, Cipso of Ar); 190.67 CoCl2 – 2 Cl– – Hϩ]ϩ; 789.7, 790.7, 791.8 [2 ϩ Hϩ]ϩ. CH2Cl2 ϩ
(CϭO).
–
ES-MS (pos. mode); m/z: 587.5 [10
ϩ
Na]ϩ.
–
amylene ϩ MeOH as ionising agent, positive mode: 906.6, 907.7,
C37H40O5 0.8 CH2Cl2 (632.67): calcd. C 71.76, H 6.63, O 12.64; 908.8, 909.9 [2 (OCH3)2 ϩ CoCl2 – 2 Cl– ϩ CH3O–]ϩ; 892.6, 893.6,
found C 71.82, H 6.89, O 12.51.
894.6, 895.5 [2 (OCH3) ϩ CoCl2 – 2 Cl– ϩ CH3O–]ϩ; 846.5, 847.6,
848.6 [2 ϩ CoCl2 – 2 Cl– – Hϩ]ϩ; 811.6, 812.6, 813.6 [2 ϩ Naϩ]ϩ;
789.7, 790.7, 791.7 [2 ϩ Hϩ]ϩ; negative mode: major peaks 787.6,
788.6, 789.7 [2 – Hϩ]–; minor peaks 950.6, 951.6, 952.6 [2 (OCH3)3
ϩ CoCl2 – 2 Cl– ϩ 2 (CH3O–) – Hϩ]–; 940.6, 941.6, 942.6
[2 (OCH3)2 ϩ CoCl2 – Cl– ϩ CH3O– – Hϩ]–; 926.6, 927.6, 928.6,
929.5 [2(OCH3) ϩ CoCl2 – Cl– ϩ CH3O– – Hϩ]–; 916.6, 917.6,
918.6, 919.6 [2 ϩ CoCl2 – Hϩ]–; 880.5, 881.6, 882.6 [2 ϩ CoCl2 –
Cl– – 2 Hϩ]–; 844.5, 845.5, 846.6 [2 ϩ CoCl2 – 2 Cl– – 3 Hϩ]–. –
C53H60CoCl2N2O4 0.2 CH2Cl2 (935.90): calcd. C 68.27, H 6.50, N
2.99; found C 68.23, H 6.74, N 2.79.
Calix[4]arene-25,26,27,28-tetrol (3): The bipyridinephosphonium
salt 5 (0.585 g, 0.5 10–3 mol) was dissolved in a solution of NaOMe
in MeOH [10 ml; from 0.097 g of Na (4.05 10–3 mol)]. To the re-
sulting yellow solution was added 0.3 g of 9 (0.5 10–3 mol). The
solution was stirred at room temp. for 6 h and then evaporated to
dryness. The raw material was dissolved in CH2Cl2 and then
washed with 1  HCl and H2O. Evaporation of CH2Cl2 afforded
a glassy material which was dissolved in 10 mL of EtOH and
10 mL of CH2Cl2. 30 mg of 5% Pd/C was added and the solution
was stirred under a blanket of H2 overnight. Solid material was
filtered over Celite and rinsed with CH2Cl2 followed by acetone.
The filtrate was evaporated to dryness and the residue was dis-
solved in 1 mL of CH2Cl2. Addition of 10 mL of MeOH resulted
in the formation of a white precipitate which was recovered and
purified by chromatography (Al2O3, CH2Cl2/MeOH 97/3) to give
Calix[4]arene-25,26,27,28-tetrol Cobalt(II) (14): A solution of an-
hydrous CoCl2 (0.018 g, 0.072 10–3 mol) in MeOH (6 mL) and
CH2Cl2 (6 mL) was added to a solution 3 (0.06 g, 0.065 10–3 mol)
in 30 mL of CH2Cl2. The resulting light blue solution was evapor-
ated to dryness; the residue was dissolved in CH2Cl2 and then puri-
fied by chromatography over Sephadex LH20 (CH2Cl2) to give
0.105 g of 3 (22%); m.p: 274 °C. – UV/Vis (CH2Cl2): λ (ε) ϭ 289.5
1
(43200). – H NMR (CDCl3): δ ϭ 1.21 (s, 18 H, Me3C); 2.62 (s, 6 0.072 g of 14 (92%). Blue-grey powder. – UV/Vis (CH2Cl2): λ (ε) ϭ
H, Me-bpy); 3.06, 2.90 (ABm, 8 H, CH2CH2); 4.24, 3.46 ("q", AB, 280.0 (20300); 287.0 (19700), 306.0 (16600); 316.5 (17200); 572.0
JAB ϭ 13.0 Hz, 8 H, Ar–CH2-Ar); 6.91 (s, 4 H, Ar); 7.04 (s, 4 H, (700); 656.5 (1030). – ES-MS: 1) negative mode, alcohol-free
Ar); 7.05 (d, J ϭ 7.0 Hz, 2 H, bpy); 7.13 (d, J ϭ 7.4 Hz, 2 H, bpy);
7.65 (t, J ϭ 7.0 Hz, 4 H, bpy); 8.19 (t, J ϭ 5.7 Hz, 4 H, bpy); 10.3
(br. s, 4 H, OH). – 13C NMR (CDCl3): δ ϭ 24.68 (Me–bpy); 31.47
CH2Cl2, –50V: 1185.5, 1187.6, 1188.4, 1189.3 [3 ϩ 2 CoCl2 – H];
2) positive mode, alcohol-free CH2Cl2, ϩ120V: 851.7, 853.6, 854.7
[3 ϩ CoCl2 – (C11H9N2) – Cl]ϩ; 989.5, 990.6, 991.6, 992.6, 994.7
(Me3C); 32.26 (Ar–CH2–Ar); 34.04 (Me3C); 34.95, 40.07 [3 ϩ CoCl2 –2Cl – H]ϩ; 3) positive mode, CH2Cl2 ϩ MeOH, ϩ50V:
(CH2CH2); 125.83, 128.98 (CH of Ar); 118.18, 118.49, 122.67, 929.7, 930.6 [3 ϩ H]ϩ; 951.7, 952.7, 953.7 [3 (OCH3) ϩ Na]ϩ;
123.06, 136.98 (CH of bpy); 127.56 128.24, 135.43, 144.48, 146.76
1032.7, 1033.6, 1034.6 [3 (OCH3) ϩ CoCl2 – 2Cl– ϩ CH3O–]ϩ;
(Co, Cp, Cipso of Ar); 155.90, 155.99, 157.80, 160.74 (C(2), C(2’), 1047.6 [3 (OCH3)2 ϩ CoCl2 – 2Cl– ϩ CH3O–]ϩ; 4) negative mode,
C(6), C(6’) of bpy). – ES-MS (pos. mode); m/z: 929.5 [3 ϩ H]ϩ. –
C62H64N4O4 0.1 CH2Cl2 (937.72): calcd. C 79.54, H 6.90, N 5.97,
O 6.82; found C 79.27, H 6.92, N 5.99, O 6.60.
CH2Cl2 ϩ MeOH, –50V: 731.6, 732.6, 733.5 [3 – CH2CH2bpy]–;
927.7, 928.8, 929.7 [3 – H]–; 1056.6, 1057.6, 1058.7, 1059.7 [3 ϩ
CoCl2 – H]–; 1065.5, 1067.5, 1068.5 [3 (OCH3) ϩ CoCl2 – H]–;
1187.4 [3 ϩ 2 CoCl2 – H]–. – C62H64Co2Cl4N4O4 H2O (1206.91):
calcd. C 61.70, H 5.51, N 4.64; found C 61.99, H 5.83, N 5.18.
Calix[4]arene-25,26,27,28-tetrol Cobalt(II) (13): A solution of an-
hydrous CoCl2 (0.0145 g, 0.111 ϫ 10–3 mol) in 3 mL of MeOH was
added to a solution of 2 (0.09 g, 0.111 ϫ 10–3 mol) in 15 mL of
CH2Cl2. The resulting blue solution was stirred at room temp. for
3 h and then evaporated to dryness. The blue residue was dissolved
in 3 mL of CH2Cl2 and purified by chromatography over Sephadex
LH20 (CH2Cl2). The middle fractions were collected and concen-
X-ray Crystallographic Study of Complex 13: C53H60Cl2Co1N2O4,
CH2Cl2, C4H10O, crystal system monoclinic, space group P2(1)/c
˚
˚
˚
with a ϭ 24.747(5) A, b ϭ 9.1648(18) A, c ϭ 24.231(5) A, β ϭ
93.12(3)°, V ϭ 5487.5(19) A , Dcalcd. ϭ 1.305 g/cm3 and Z ϭ 4. The
3
˚
data were collected at 173 K by X-ray diffraction on an Enraf–
trated; precipitation by hexane gave 0.096 g of 13 (92%), light-blue Nonius Kappa-CCD diffractometer. Full sphere of data was col-
solid. – UV/Vis (CH2Cl2): λ (ε) ϭ 254.5 (12300), 280.0 (16500),
lected by axis rotation with 1°.0 increments over 180°, with 30 s
exposures per frame. The crystal to detector distance was 30 mm.
Data were analyzed using Kappa-CCD Software.[13] Cell dimen-
sions were refined with HKL Scalepack.[14] The structure was
solved with direct methods using the SHELXS programme.[15] Re-
287.5 (14960), 308.0 (10420), 317.0 (11440), 341.0 (6208), 570.5
1
(284), 655.5 (530). – H NMR (500 MHz, CDCl3): δ ϭ –35.24 (br.
s, ∆ν1/2 ϭ 300 Hz, 2 H, CH2–CH2-bpy); –20.85 (br. s, ∆ν1/2
ϭ
169 Hz, 3 H, Me-bpy); –16.39 (br. s, ∆ν1/2 ϭ 92 Hz, 2 H, CH2–
CH2-bpy); –14.30 [s, ∆ν1/2 ϭ 30.50 Hz, 1 H, H(4) or H(4’) of bpy]; – finement by SHELXL [16] leads to an R factor of 0.077 for 3345 Fo
13.53 [s, ∆ν1/2 ϭ 30.12 Hz, 1 H, H(4) or H(4’) of bpy]; –2.08 [br. s, Ͼ 4 (Fo) and a goodness of fit of 0.947. All nonhydrogen atoms
∆ν1/2 ϭ 48 Hz, 2 H, Ar(A)]; 1.27 (s, ∆ν1/2 ϭ 21.14 Hz, 9 H, Me3C); were given anisotropic displacement parameters. All hydrogen
2.10 (s, ∆ν1/2 ϭ 21.93 Hz, 18 H, Me3C); 2.54 (br. s, ∆ν1/2 ϭ 109 Hz, atoms were located at their theoretical position and refined as a
2 H, Ar–CH2–Ar); 3.03 (br. s, ∆ν1/2 ϭ 104.50 Hz, 2H, Ar–CH2-
Ar); 3.34 (br. s, ∆ν1/2 ϭ 98.70 Hz, 2 H, Ar–CH2–Ar); 3.95 (br. s,
∆ν1/2 ϭ 85.25 Hz, 2 H, Ar–CH2-Ar); 6.94 [s, ∆ν1/2 ϭ 22.00 Hz, 2
riding model. EXYZ and EADP instructions were used for the
study of the CH2Cl2 disorder. The final electron density difference
–3
˚
map showed a maximum of 1.23 e.A and a minimum of –0.51
–3
[17]
˚
H, Ar(C)]; 7.07 [s, ∆ν1/2 ϭ 22.86 Hz, 2 H, H(3) or H(5) of Ar(B) eA . Molecular graphics were drawn with ORTEP.
690 Eur. J. Inorg. Chem. 2000, 683Ϫ691

Two New Calix[4]arene/Bipyridine-Based Podands
FULL PAPER
Table 2. Crystal data and structure refinement of 13
[1]
C. Wieser, D. B. Dieleman, D. Matt, Coord. Chem. Rev. 1997,
165, 93.
Empirical formula
Mr
Crystal system, space group
C53H60Cl2Co1N2O4 CH2Cl2 C4H10
1078.23
Monoclinic, P2(1)/c
O
[2] [2a]
J.-B. Regnouf-de-Vains, R. Lamartine, Helv.Chim. Acta
[2b]
1994, 77, 181. –
R. Lamartine, Tetrahedron Lett. 1995, 36, 5745. –
gnouf-de-Vains, R. Lamartine, B. Fenet, C. Bavoux, A. Thozet,
J.-B. Regnouf-de-Vains, S. Pellet-Rostaing,
[2c]
J.-B. Re-
Cell dimensions
˚
a [A]
24.747(5)
9.1648(18)
24.231(5)
93.12(3)
5487.5(19)
4
1.305
not measured
173
[2d]
M. Perrin, Helv.Chim. Acta 1995, 78, 1607. –
S. Pellet-Ros-
˚
b [A]
taing, J.-B. Regnouf-de-Vains, R. Lamartine, Tetrahedron Lett.
˚
c [A]
1996, 37,5889. –[2e] S. Pellet-Rostaing, J.-B. Regnouf-de-Vains,
β [°]
V [A ]
R. Lamartine, P. Meallier, S. Guittonneau, B. Fenet, Helv.
3
˚
[2f]
Chim. Acta 1997, 80, 1229. –
J.-B. Regnouf-de-Vains, R.
Z
Lamartine, B. Fenet, Helv.Chim. Acta 1998, 81, 661–669.
Dx [Mg m–3
Dm
]
[3]
[3a] P. D. Beer, Z. Chen, A. J. Goulden, A. Grieve, D. Hesek, F.
Szemes, T. Wear, J. Chem. Soc., Chem. Commun. 1994, 1269. –
T [K]
[3b]
[3c]
P. D. Beer, Chem. Commun. 1996, 689. –
P. D. Beer, M.
Crystal size [mm]
Color
0.36 ϫ 0.18 ϫ 0.04
blue
G. B. Drew, D. Hezek, M. Shade, F. Szemes, Chem. Commun.
[3d]
1996, 2161. –
1998, 129.
P. D. Beer, J. B. Cooper, Chem. Commun.
Enraf–Nonius Kappa-CCD
diffractometer
Wavelength [A]
[4]
[5]
[6]
[7]
J.-B. Regnouf-de-Vains, R. Lamartine, Tetrahedron Lett. 1996,
37, 6311.
J.-B. Regnouf-de-Vains, R. Lamartine, poster 33-B, BOSS 6,
Gent, Belgium, July 8–12, 1996.
A. Arduini, G. Manfredi, A. Pochini, A. R. Sicuri, R. Ungaro,
J. Chem. Soc., Chem. Commun. 1991, 936.
K. A See, F. R Froncsek, W. H. Watson, R. P. Kashyap, C. D.
Gutsche, J. Org. Chem. 1991, 56, 7256.
˚
0.71073
none
Absorption correction
Rint
ϕ limits [°]
0
2.37 to 27.83
Limiting indices
Measured reflections
Independent reflections
Parameters
–28 Յ h Յ 28, –11 Յ k Յ 0, 0 Յ l Յ 31
11633
10917
637
H atoms riding
S
R
[8]
[9]
Z. T. Huang, G. –Q. Wang, Synthetic Commun. 1994, 24, 11.
J. O. Magrans, J. de Mendoza, M. Pons, P. Prados, J. Org.
Chem. 1997, 62, 4518.
0.947
R1 ϭ 0.0767, wR2 ϭ 0.1429
1.227 and –0.507
–3
˚
Densities (max),(min)[eA
]
[10]
[11]
G. R. Newkome, D. C. Pantaleo, W. E. Puckett, P. L. Ziefle,
W. A. Deutsch, J. Inorg. Nucl. Chem. 1981, 43, 1529.
for an other CH2Cl2 complex, see:[11a] J. L. Atwood, S. G. Bott,
C. Jones, C. L. Raston, J. Chem. Soc., Chem. Commun. 1992,
[11b]
1349. –
J. L. Atwood, P. C. Junk, S. M. Lawrence, C. L.
Crystallographic data (excluding structure factors) have been de-
posited with the Cambridge Crystallographic Data Centre as sup-
plementary publication n° 120557. Copies of the data can be ob-
tained free of charge on application to CCDC, 12 Union Road,
Cambridge CB2 1EZ, U.K. [Fax: (internat.) ϩ 44-1223/336033; E-
mail: deposit@ccdc.cam.ac.uk]. For other details see Table 2.
Raston, Supramol. Chem. 1996, 7, 15.
[12]
[13]
E. Weber, H. P. Josel, J. Incl. Phenom. 1983, 1, 79.
Enraf–Nonius, Kappa-CCD Software, 1997, Enraf–Nonius,
Delft, The Nederlands.
Z. Otwinowski, W. Minor, Methods Enzymol. 1996, 276, 307–
326.
G. M. Sheldrick, SHELXS-97 Program for Crystal Structure
Determination 1997, University of Gottingen, Germany.
[14]
[15]
[16]
[17]
Acknowledgments
Sheldrick, G.M., SHELXL-97. Program for the refinement of
Crystal Structures. 1997, University of Göttingen, Germany.
We are grateful to the  for financial support, especially J.-O.
D. for a PhD fellowship; to  (Monaco) and  S.A. for
UV spectroscopy and  facilities, respectively. We are in-
debted to Mrs Nicole Marshall for correcting the manuscript.
ORTEP-3 for Windows, L. J. Farrugia, J. Appl. Cryst. 1997,
565.
Received May 31, 1999
[I99192]
Eur. J. Inorg. Chem. 2000, 683Ϫ691
691