New conjugates of calix[4]arenes bearing dipyridine and indolizine heterocycles

Article abstract of DOI:10.1080/10610278.2012.688122

A simple route to introduce various heterocycles, derivatives of dipyridyls and indolizines on the lower rim of the para-tert-butylcalix[4]arene via ester bond formation to afford 1,3-disubstituted conjugates is described. The conformation of the new compounds and some intermolecular interactions are discussed on the basis of X-ray and NMR analyses. Preliminary complexation properties of some of the new tert-butylcalix[4]arene heterocyclic conjugates with Cu (II), Co (II) and Ni (II) were studied by means of UV-Vis titration.

Full text of DOI:10.1080/10610278.2012.688122

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New conjugates of calix[4]arenes bearing dipyridine
and indolizine heterocycles
Ramona Danac a , Raluca Rusu a , Alexandru Rotaru b , Aurel Pui a & Sergiu Shova b
a Department of Chemistry, Alexandru Ioan Cuza University of Iasi, 14 Carol I, Iasi, 700506,
Romania
b Petru Poni Institute of Macromolecular Chemistry, 41A Grigore Ghica Voda Alley, Iasi,
700487, Romania
Available online: 24 May 2012
To cite this article: Ramona Danac, Raluca Rusu, Alexandru Rotaru, Aurel Pui & Sergiu Shova (2012): New conjugates of
calix[4]arenes bearing dipyridine and indolizine heterocycles, Supramolecular Chemistry, DOI:10.1080/10610278.2012.688122
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Supramolecular Chemistry
iFirst article, 2012, 1–13
New conjugates of calix[4]arenes bearing dipyridine and indolizine heterocycles
Ramona Danaca*, Raluca Rusua, Alexandru Rotarub, Aurel Puia and Sergiu Shovab
b
aDepartment of Chemistry, Alexandru Ioan Cuza University of Iasi, 14 Carol I, Iasi 700506, Romania; Petru Poni Institute of
Macromolecular Chemistry, 41A Grigore Ghica Voda Alley, Iasi 700487, Romania
(Received 15 February 2012; final version received 4 April 2012)
A simple route to introduce various heterocycles, derivatives of dipyridyls and indolizines on the lower rim of the para-tert-
butylcalix[4]arene via ester bond formation to afford 1,3-disubstituted conjugates is described. The conformation of the new
compounds and some intermolecular interactions are discussed on the basis of X-ray and NMR analyses. Preliminary
complexation properties of some of the new tert-butylcalix[4]arene heterocyclic conjugates with Cu (II), Co (II) and Ni (II)
were studied by means of UV–Vis titration.
Keywords: calixarenes; heterocycles; metal complexes
Introduction
cations. Furthermore, incorporation of these moieties into
calixarenes allows the combination of the peculiar features
of the macrocycle with the photochemical and electro-
chemical properties displayed by the metal complexes of
these heterocyclic units (7, 8). Dipyridyl podants were
introduced in several synthetic steps via either ether
calixarene bonds (6c–l), CZC bonds (6a) or amide bonds
(6b) on both the lower rim (6c–l) and the upper rim (6a,b) of
the calixarene scaffold.
Calixarenes are versatile molecular scaffolds for the
design of wide variety of structural entities. Through the
pioneering studies of Gutsche in the late 1970s,
calixarenes have rapidly become the most employed
macrocyclic compounds in supramolecular chemistry (1).
By tethering various functional groups, calixarenes have
also become an important class of macrocyclic receptors
able to complex various metal ions (2).
In this study we report a simple way of selective
introduction of nitrogen-containing heterocycles on the
lower rim of the tert-butylcalix[4]arene by esterification
reaction. Despite the labile properties of the phenol ester
bond, we succeeded both the synthesis and some
preliminary studies of binding properties for new
conjugates towards transition metal cations (Cu2þ, Co2þ
and Ni2þ).
Heterocycles, as molecules of life, are ubiquitous in
biological systems and are involved in many biological
functions because of their ability to undergo various non-
covalent interactions with ions as well as neutral species.
Thus, by equipping the upper or the lower rim of
calixarenes with heterocycles, new compounds as func-
tional materials or multifunctional enzyme models were
elaborated (3). Particularly, nitrogen-containing functional
groups suitable for transition metal binding are of great
interest due to the combination of the complexation
features of nitrogen ligands with the hydrophobic cavity of
calixarenes within the same molecule (3, 4). Calixarenes
with covalently attached fluorophores and coordinating
properties, bear a great potential in terms of an easy
monitoring of the complexation processes (5).
From the previous reports on the narrow rim
esterification (9), using acid halides and sodium hydride,
acid anhydrides and sulphuric acid, the acylation or
aroylation generally involves all of the OH groups if the
derivatising agent is used in excess. By using acid halides
in the presence of bases weaker than NaH and limiting
amounts of the esterifying reagent, it is possible to obtain
partially substituted calixarenes in a selective fashion (10).
Although many methods that allow their straightforward
functionalisation are now available, the selective introduc-
tion of functional groups into the calixarenes on both narrow
or wide rim is still an interesting and challenging subject to
study. Earlier, different groups reported the synthesis and
metal complexation features of dipyridyl-based calix[4]
arenes (5a, 6), emphasising their affinity for transition metal
Results and discussions
One of the first goals of our research aiming to obtain new
calixarenes bearing heterocycles on the lower rim of their
scaffold was to investigate the reaction conditions for the
introduction of reactive halogen groups able to get easily
*Corresponding author. Email: rdanac@uaic.ro
ISSN 1061-0278 print/ISSN 1029-0478 online
q 2012 Taylor & Francis
http://dx.doi.org/10.1080/10610278.2012.688122
http://www.tandfonline.com

2
R. Danac et al.
Br
But
Cl
Cl
O
O
O
O
O
Br
;
Cl
Cl
O
Cl
OH
But
OH
OH
But
HO
O
OH
But
OH
O
OH
But
O
O
OH
But
O
O
O
O
XCH2COX, a
X=Cl, Br
;
OH
tBu
But
tBu
tBu
But
tBu
But
But
But
But
1
4
2
3
5, b
O
Me
Me
4"
5"
N
N
Py or
,b
Me
6"
3"
O
O
5
2"
2'
1"
3'
O
EtOOC
Cl
Cl
O
O
OH HO
O
1'
4'
N
N
N
COOEt
EtOOC
5'
9'
8'
6'
7'
4
But
But
But
tBu
5
6
3
6
2
N
Br
1
Br
O
O
O
OH
O
OH
But
But
But
tBu
7
Scheme 1. Reaction of tert-butylcalix[4]arene with halogenoacyl halides at the lower rim. (a) Et3N, MeCN, rt; (b) MeCN, reflux.
functionalised. Thus, treating tert-butylcalix[4]arene 1
with chloroacetyl chloride or bromoacetyl bromide in
acetonitrile in the presence of triethylamine (TEA), we
afforded different compounds depending on the number of
equivalents of acyl halide used. Reacting 1 with 5
equivalents of chloroacetyl chloride in dry acetonitrile in
the presence of TEA resulted in the corresponding 1,3-
diester 2 isolated in good yield (Scheme 1). The 1H NMR
spectra showed a cone conformation of this compound
with the characteristic AB pattern for bridging CH2 groups
whereas the IR spectra showed strong absorption band for
CvO ester bond at 1763 cm21 and for the free OH groups
flattened partial cone conformation with the phenol OH
group laying on the opposite side of the ester groups
(Figure 1).
The perspective view of the molecular structure of 3,
investigated by single-crystal X-ray diffraction analysis,
along with the atomic labelling scheme, is shown in
Figure 1. Crystal 3 has a molecular structure, in which the
calix[4]arene core adopts a partial cone conformation.
This conformation seems to be facilitated by two
CZH· · ·O hydrogen bonds between methylene group,
denoted by C37 carbon atom, and two ester oxygen atoms
O2 and O6 (Figure 1), whereas the free OH group does not
exhibit any hydrogen bonding. An examination of the
torsion angles (Table 1) shows the sequence of signs for f
and x to be þ 2 , þ 2 , þþ, 22 as expected for partial
cone conformation (11).
at 3512 cm21
.
When the ratio of number of equivalents was increased
(1/chloroacetyl chloride/TEA: 1/8/9), the triester deriva-
tive 3 was obtained. The 1H NMR spectra showed spectral
patterns (three singlets from tert-Bu hydrogen atoms and
four doublets from the bridging methylene groups)
compatible with either a cone or a partial cone
conformation of this triester derivative in solution, while
the solid-state structure was assigned on the basis of X-ray
diffraction which showed whereas triester 3 in a uudu
The same triester 3 was isolated when we continued to
increase the number of equivalents of chloroacetyl
chloride, being unable to obtain the corresponding
tetraester under these conditions (Scheme 1).
In order to obtain pyridinium quaternary salt
derivatives, the next step in our research plan was to

Supramolecular Chemistry
3
Figure 1. X-ray molecular structure of compound 3. Thermal ellipsoids are drawn at 40% probability level. Non-relevant hydrogen
˚
atoms are omitted for clarity. H-bond parameters: C37ZH· · ·O6 [C37ZH 0.97 A, H· · ·O6 2.27 A, C37· · ·O6 3.115(4) A, C37ZH· · ·O6
˚
˚
˚
145.68]; C37ZH· · ·O2 [C37ZH 0.97 A, H· · ·O2 2.25 A, C37· · ·O2 3.038(4) A, C37ZH· · ·O6 137.78].
˚
˚
Table 1. Torsion angles to define the calixarene conformation in compound 3.
Torsion angle
f (8)
Torsion angle
x (8)
C20–C21–C25–C26
C33–C34–C38–C39
C46–C47–C1–C2
C9–C10–C12–C13
67.8 (4)
104.5 (4)
117.1 (4)
C21–C25–C26–C27
C34–C38–C39–C40
C47–C1–C2–C3
2110.0 (4)
258.6 (4)
129.4 (4)
2135.8 (3)
C10–C12–C13–C14
2110.2 (4)
carry out the reaction between the resulted calixarene-1,3-
diester 2 and the fluorescent pyridylindolizine derivative 5
which was recently synthesised in our group (12). First we
treated diester 2 with a simpler N-heterocycle as pyridine
in anhydrous acetonitrile, but instead of obtaining the
corresponding salt, a migration of one of the ester groups
occurred and 1,2 diester 6 was afforded in a cone
induced cleavage of one ester group occurred to obtain
compound 6 in the same conformation. No ester cleavage
was observed when triester 3 was treated in the same
conditions (no proximate OH to the ester groups), but only
traces of desired pyridinium salts were observed to be
formed in this reaction.
Interestingly, treating 1 with five or more equivalents
of bromoacetyl bromide, in order to synthesise esters
bearing a more reactive halogen, only the corresponding
1,3-diester 4 in cone conformation was obtained. The
treatment of 4 with monoindolizine 5 in refluxing
anhydrous acetonitrile gave indeed the corresponding
dipyridinium dibromide 7 in a cone conformation to the
detriment of the migration observed in case of compound
2. This salt becomes bright red coloured when treated with
1
conformation, the structure being confirmed by H NMR
(two singlets from tert-Bu groups and six doublets for
methylene bridging groups). This is in agreement with
literature reports, in which these migrations were observed
on different aroyl esters (10), the cleavage being facilitated
by a phenolic OH proximate to the ester carbonyl function.
The same migration was observed when diester 2 reacted
in the same conditions with indolizine 5, when an amine

4
R. Danac et al.
5’
4’
3’
6’
6’
3’
1’
N
2’
N
N
1’N
5’
4’
N
2’
1
N
2
N
2
3
4
1N
6
COX
a
O
O
O
O
3
6
8. X=OH
9. X=Cl
5
4
5
, b
;
OH
N
N
OH
OH
O
OH
O
O
O
1
Bu
tBu
tBu
tBu
tBu tBu
tBu
tBu
tBu
10
11
Scheme 2. Reaction of tert-butylcalix[4]arene 1 with acyl chlorides of 2,20-dipyridine-4 carboxylic and 2,20-dipyridine-5 carboxylic
acids. (a) (COCl)2, DMF, C6H6; (b) Et3N, MeCN, rt.
bases (e.g TEA), the fact which probably indicates their
transformation to the corresponding ylides, which can be
interesting candidates for cycloaddition reactions.
In our further investigation using the previously
described conditions, we tethered the 2,20-dipyridine units
to the 1,3 positions of tert-butylcalix[4]arene via ester
bonds (Scheme 2) in order to obtain compounds
possessing heteroaromatic substituents which can provide
donor atoms for binding metal ions.
(obtained from the corresponding commercial available
carboxylic acids), we were able to isolate only the 1,3-
disubstituted products 10 or 11. Both compounds showed
1H NMR spectra with the same spectral patterns
corresponding to a cone conformation, their structures
being finally confirmed by X-ray diffraction (Figures 2
and 4).
The conformation of compound 10 can be described as
‘distorted cone’ facilitated by two OZH· · ·O intramole-
cular hydrogen bonds, formed between OH groups and
ester oxygen atoms. This conclusion is confirmed by the
values and the sequences of sign (þ 2 , þ 2 , þ 2 ,
þ 2 ) for torsion angles (11), given in Table 2.
Thus, treating 1 with 5 equivalents of 2,20-dipyridine-
4-carbonyl chloride or 2,20-dipyridine-5-carbonyl chloride
Two phenolic units B and D are almost perpendicular to
the mean plane through the C atoms of the methylene
bridges with the values of dihedral angles being equal to
84.89(9)8 and 84.9(1)8, respectively, which is in a good
correlation with the intramolecular distance between two
symmetrically related 2,2-dipyridine units. This is
evidenced by the centroid-to-centroid distances of
˚
3.585 A between adjacent overlapping aromatic rings.
Two aryl rings carrying the free OH groups are splayed
outward resulting in ‘flattened cone’ conformation. It is
important to note that the p–p stacking interaction is
extending in the crystal to the intermolecular system, which
determined the association of compound 10 molecules into
the infinite ribbon running 010 direction (Figure 3).
The crystal has a molecular structure constructed from
neutral molecules 11, depicted in Figure 4, and solvate
water molecules in 1:1.8 ratio.
Table 2. Torsion angles to define the calixarene conformation
in compound 10.
Torsion angle
f (8)
x (8)
Figure 2. X-ray molecular structure of compound 10. Thermal
ellipsoids are drawn at 40% probability level. Non-relevant
hydrogen atoms, as well as the tert- Bu atoms, are omitted for
clarity. Symmetry code for equivalent atoms: 1/2 2 x, 2 2 y, z.
A–B
B–C
C–D
D–A
106.4 (5)
64.2 (5)
106.4 (5)
64.2 (5)
264.3 (5)
2105.0 (5)
264.3 (5)
2105.0 (5)
˚
˚
H-bond parameters: O3ZH· · ·O1 [O3ZH 0.89 A, H· · ·O1 2.01 A,
0
˚
O3· · ·O1 (1/2 2 x, 2 2 y, z) 2.893(4) A, O3ZH· · ·O1 174.08].

Supramolecular Chemistry
5
Figure 3. p–p Stacking interaction in structure of 10.
This molecule is characterised by own symmetry,
determined by crystallographically imposed mirror plane
of C2/m space group. The molecule contains two free OH
groups in opposite orientation and exhibits partial cone
conformation even though the cone conformation is the
major species at equilibrium in solution. The character-
isation of partial cone conformation in terms of torsion
angles is presented in Table 3. The sequence of signs
(þ 2 , þ 2 , þþ, 22) for f and x dihedral angles,
confirms the partial cone conformation (11).
which was transformed in more reactive acyl chloride 13.
Keeping the equivalents of reactants ratio as previously
described for esterification reactions (1/13/TEA: 1/5/6),
we could isolate only the corresponding fluorescent 1,3-
diester in a cone conformation (13), even though the thin
layer chromatography (TLC) plate of the reaction mixture
showed few other fluorescent compounds as by-products
(Scheme 3).
A preliminary complexation study by UV–Vis
titrations in ethanol at 258C was carried out using the
ester derivative 10 with Ni2þ, Co2þ and Cu2þ inorganic
salts. Typically, a solution of M2þ (2 £ 1023 mol l21) with
a total volume of 10 ml was added stepwise in portions of
1 ml to a solution of 2 ml of 10 (1 £ 1025 mol l21), and the
absorption spectra were measured using a Cintra 101
spectrophotometer in the range of 200–400 nm (Figure 6).
The free ligand 10 (L) shows two absorption maxima
at 232 and 260 nm (Figure 3), the latter one being
characteristic to the absorption of the bipyridyl moiety of
compound 10. The addition of M(II) solution causes a
bathochromic shift of the absorption maximum from 260
It is important to note that the crystal structure motif of
11 is characterised by the formation of the channel which
contains statistically distributed solvate water molecules.
The projection of the crystal structure packing is shown in
Figure 5.
The next goal of our investigation was to synthesise,
using the same method, fluorescent calixarenes which can
be used as potential ligands in metals complexation. Thus,
the hydrolysis of the ethyl ester group of our fluorescent
pyridylindolizine derivative 5 was carried out in basic
conditions giving the corresponding carboxylic acid 12,

6
R. Danac et al.
stoichiometry of metal/ligand (M/L) main species was
determined by mole ratio (14) and Job plot methods (15).
Interestingly, both methods indicated the presence of only
one complexation species with molar ratio M/L: 1/1,
which corresponds to the previously reported data in case
of Co2þ(6e). The stability constants obtained by the two
different methods are comparable and are presented in
Table 4, showing a good stability of these complexes.
Conclusions
In this study, selective introduction of heterocycles into
the lower rim of tert-butylcalix[4]arene via ester bond
formation was studied. Different approaches were tested
but the direct esterification of the OH groups of the tert-
butylcalix[4]arene by heterocyclic acyl chloride deriva-
tives was the most effective. By this way, only 1,3-
disubstituted tert-butylcalix[4]arenes with 2,20-dipyridine
or fluorescent indolizine units were afforded. In contrast to
the bulky heterocyclic moieties, during the optimisation of
esterification reaction, also a trisubstituted derivative of
tert-butylcalix[4]arene with chloroacetyl chloride was
obtained.
The complexes of heterocyclic derivative 10 with
Ni2þ, Co2þ and Cu2þ were investigated by UV–Vis
titrations, providing the insight into the ratio between the
metal and ligand in the studied complexation system.
From the obtained results, it may be concluded that all
three metal ions form only one complexation species with
molar ratio 1:1 between metal and compound 10.
Expanded complexation studies and investigation of
the electric, fluorescence and transport properties of the
synthesised compounds are currently under progress.
Figure 4. X-ray molecular structure of compound 11. Thermal
ellipsoids are drawn at 40% probability level. Non-relevant
hydrogen atoms, as well as the tert- Bu atoms, are omitted for
clarity. Symmetry code for equivalent atoms: x, 1 2 y, z.
Experimental
Melting points were recorded on an A. Kru¨ss Optronic
Melting Point Meter KSPI (Kruss, Hamburg, Germany)
and are uncorrected. Proton and carbon nuclear magnetic
resonance (dH, dC) spectra were recorded on a Bruker
Avance 400 DRX (400 MHz, Bruker BioSpin GmbH,
Rheinstetten, Germany). All chemical shifts are quoted
on the d-scale in ppm using TMS or residual solvents
(CHCl3, DMSO) as internal standards. Coupling con-
stants are given in Hz. IR spectra were recorded on an FT-
IR Shimadzu (Shimadzu, Japan) or Jasco 660 plus (Jasco
Inc, Easton, USA) FT-IR spectrophotometers. Low-
resolution mass spectra were recorded on a Bruker
micrOTOF-Q II Electrospray Ionization Mass Spec-
trometer (Bruker Daltonics Inc, Bremen, Germany), ESI
in the positive mode; m/z values are reported in Daltons.
TLC was carried out on Merck silica gel 60F254 plates
(Merck, USA). Column chromatography was carried out
on silica gel (Roth 60, 0.04–0.063 mm). Visualisation of
the plates was achieved using a UV lamp (lmax ¼ 254 or
Table 3. Torsion angles to define the calixarene conformation
in compound 11.
Torsion angle
f (8)
x (8)
C–D
D–A
A–B
B–C
63.7 (4)
97.2 (4)
117.2 (4)
2122.4 (4)
297.2 (4)
263.7 (4)
122.4 (4)
2117.2 (4)
to 310 nm for CoL, 313 nm for NiL and 311 nm for CuL
correspondingly (for details, see Supplementary Infor-
mation, available online).
As shown in Figure 6, increases in absorbance at
around 310 nm and reduction in free ligand absorbance at
260 nm with the formation of two clear isosbestic points
were observed, which indicates that the ligand and its
metal complex are in equilibrium in solution. The

Supramolecular Chemistry
7
Figure 5. The view of crystal structure of 11 along b crystallographic axis.
1'
N
2'
N
O
3'
6'
N
N
5'
4'
8
7
6
, d
5
Me
9
N
N
4
XOC
O
1
3
O
5. X=OEt
12. X=OH
13. X=Cl
O
O
(i) a, (ii) b
(iii) c
2
1"
4"
OH
OH
O
O
6"
5"
2"
3"
1
Me
Me
tBu
tBu
tBu
tBu
14
Scheme 3. Reaction of tert-butylcalix[4]arene with indolizinylacyl chloride 13. (a) MeOH, EtOH, NaOH 4 M, 608C; (b) citric acid;
(c) (COCl)2, DMF, C6H6; (d) Et3N, MeCN, rt.
365 nm). Spectrophotometric measurements were carried
out at 258C in EtOH solution using a Cintra 101
spectrophotometer (GBC Scientific Equipment Pty Ltd,
Braeside, Australia) in the range 200–400 nm. All
commercially available products were used without
further purification unless otherwise specified.
(rt) for 20 min. Chloroacetyl chloride (7.5 mmol, 5 equiv.,
0.61 ml for compound 2; 12 mmol, 8 equiv., 0.98 ml for
compound 3) or bromoacetyl bromide (7.5 mmol, 5 equiv.,
0.67 ml for compound 4) was added dropwise for 15 min
(magnetic stirring) and the resulting mixture was then
stirred over night at rt. The solid was collected by filtration
to give a powder which was then washed with methanol.
The solution was concentrated in vacuo and the residue
was dissolved in CHCl3 and extracted with saturated
solutions of NaHCO3, NaCl and finally water. The organic
layer was dried (Na2SO4), filtered and concentrated in
vacuo. The residue was mixed with the solid obtained after
initial filtration and purified by crystallisation from
methanol–chloroform (1:1, v/v).
General procedure for preparation of compounds 2–4
Tert-butylcalix[4]arene (1.5 mmol, 1 equiv., 1 g) and TEA
(9 mmol, 6 equiv., 1.29 ml for compounds 2 and 4;
13.5 mmol, 9 equiv., 1.93 ml for compound 3) were added
to 30 ml of anhydrous acetonitrile, and the obtained
suspension was stirred under nitrogen at room temperature

8
R. Danac et al.
Figure 6. UV–Vis titration curves for diester 10 with Ni2þ
.
acetonitrile. The product was purified by crystallisation
(CHCl3: MeOH 3:1, v/v).
Table 4. Log b values for the complex formation of Co2þ, Ni2þ
and Cu2þ and ligand 10s.
Reaction
Log ba
Log bb
General procedure for preparation of compounds 9
Co2þ þ L ¼ [CoL]2þ
Ni2þ þ L ¼ [NiL]2þ
Cu2þ þ L ¼ [CuL]2þ
6.8
6.9
7.1
6.7
6.9
7.3
To a solution of 2.20-dipyridine-4-carboxylic acid or 2.20-
dipyridine-5-carboxylic acid (0.5 mmol, 1 equiv., 0.1 g) in
5 ml of benzene or dichloromethane (DCM) were added
0.127 g (1 mmol, 2 equiv.) of oxalyl chloride and catalytic
DMF. After 1 h at rt, the solvent and excess oxalyl chloride
were removed in vacuo to afford the corresponding 2,20-
dipyridine carbonyl chlorides 9 which were used in the
next step without any further purification.
a Mole ratio method.
b Job method.
General procedure for preparation of compound 6
A solution of pyridine (1.05 mmol, 2.1 equiv., 0.082 g) or
ethyl-3-(4-methylbenzoyl)-7-(pyridine-4-yl)-indolizine-1-
carboxylate 5 (12) (0.40 g) and 5,11,17,23-tetra-tert-butyl-
25,27-di(chloroacetyloxy)-26,28-dihydroxy-calix[4]arene
2 (0.5 mmol, 1 equiv., 0.39 g) in anhydrous acetonitrile
(20 ml) was magnetically stirred for 20 h at reflux. The
resulting yellow precipitate was removed by filtration and
then washed with acetonitrile. The product was purified by
crystallisation (CHCl3: MeOH 3:1, v/v).
General procedure for preparation of compounds 10–11
and 14
Tert-butylcalix[4]arene (0.3 mmol, 1 equiv., 0.2 g) and
TEA (1.8 mmol, 6 equiv., 0.26 ml) were added to 7 ml of
anhydrous acetonitrile, and the obtained suspension is
stirred under nitrogen at rt for 20 min. 2,20-Dipyridine-4-
carbonyl chloride or 2,20-dipyridine-5-carbonyl chloride
(1.5 mmol, 5 equiv., 0.34 g) or ethyl 3-(4-methylbenzoyl)-
7-(pyridine-4-yl)indolizine-1-carbonyl chloride 13
(1.5 mmol, 5 equiv., 0.57 g) suspended in 5 ml of
acetonitrile was added dropwise over 15 min (magnetic
stirring), and the resulting mixture was then stirred over
night at rt. The solid was collected by filtration to give a
powder which was then washed with methanol. The
solution was concentrated in vacuo and the residue was
dissolved in CHCl3 and extracted with saturated solutions
General procedure for preparation of compound 7
A solution of monoindolizine 5 (12) (2.1 mmol, 2.1 equiv.,
0.80 g) and 5,11,17,23-tetra-tert-butyl-25,27-di(bromoa-
cetyloxy)-26,28-dihydroxy-calix[4]arene 4 (1 mmol, 1
equiv., 0.88 g) in anhydrous acetonitrile (20 ml) was
magnetically stirred for 20 h at reflux. The resulting yellow
precipitate was removed by filtration and then washed with

Supramolecular Chemistry
9
of NaHCO3, NaCl and water. The organic layer was dried
(Na2SO4), filtered and concentrated in vacuo. The residue
was mixed with the solid obtained after initial filtration
and purified by crystallisation from methanol–chloroform
(1:1, v/v; for compounds 10 and 11) or column
chromatography using CHCl3:MeOH (9.8:0.2; for com-
pound 14).
(s, 18H, tBu-H), 1.38 (s, 9H, t Bu-H), 1.42 (s, 9H, t Bu-H),
3.29 (d, 2H, ArCH2Ar, J ¼ 14 Hz), 3.54(d, 2H, ArCH2Ar,
J ¼ 14 Hz), 3.72 (d, 2H, ArCH2Ar, J ¼ 16.8 Hz), 3.74 (d,
2H, ArCH2Ar, J ¼ 16.8 Hz), 3.83 (s, 1H, OH), 3.99 (s, 2H,
CH2Cl), 4.29 (d, 2H, CH2Cl, J ¼ 14 Hz), 4.31(d, 2H,
CH2Cl, J ¼ 14 Hz), 6.70 (d, 2H, Ar-H, J ¼ 2.4 Hz), 7.07
(d, 2H, Ar-H, J ¼ 2.4 Hz), 7.16 (s, 2H, Ar-H), 7.25 (s, 2H,
Ar-H); 13C NMR (CDCl3): 31.1 (6 £ CH3, 2 £ ArCH2Ar),
31.5 (3 £ CH3), 31.7 (3 £ CH3), 32.1 (2 £ C(CH3)3), 34.3
(C(CH3)3), 34.5 (C(CH3)3), 36.7 (2 £ ArCH2Ar), 40.5
(CH2Cl), 40.9 (2 £ C H2Cl), 126.2 (2 £ Ar-CH), 126.31
(2 £ Ar-CH), 126.33 (2 £ Ar-CH), 126.5 (2 £ Ar-CH),
128.3 (2 £ Ar-Cq), 131.4 (2 £ Ar-Cq), 131.6 (2 £ Ar-Cq),
133.9 (2 £ Ar-Cq), 143.2 (Ar-Cq), 143.4 (2 £ Ar-Cq),
144.7 (Ar-Cq), 149.0 (2 £ Ar-Cq-OCOR), 149.8 (2 £ Ar-
Cq-OCOR), 152.1 (Ar-Cq-OH), 165.7 (2 £ CvO), 166.6
(CvO); IR (KBr, cm21): 3522, 2951, 1768, 1477, 1153,
871; MS (ESIþ): 899 (M þ Naþ), 915 (M þ Kþ); anal.
calcd. for C50H59Cl3O7: C, 68.37; H, 6.77. Found: C,
68.29; H, 6.85.
General procedure for preparation of compound 12
Ethyl 3-(4-methylbenzoyl)-7-(pyridine-4-yl) indolizine-1-
carboxylate 5 (12) (2.1 mmol, 2.1 equiv., 0.80 g) was
hydrolysed in EtOH:MeOH:4 M KOH (25:25:8, 150 ml) at
608C for 3 h. After cooling, the reaction mixture was
poured into ice water (100 ml) and acidified by slow
addition of 10% citric acid until pH 6. The resulted solid
was separated by filtration and dried to give 3-(4-
methylbenzoyl)-7-(pyridine-4-yl)indolizine-1-carboxylic
acid 12 as a yellow solid, which was used in the next step
without any further purification due to the poor solubility
in common solvents.
5,11,17,23-Tetra-tert-butyl-25,27-di(bromoacetyloxy)-26,
28-dihydroxy-calix[4]arene 4
General procedure for preparation of compound 13
To a solution of 3-(4-methylbenzoyl)-7-(pyridine-4-
yl)indolizine-1-carboxylic acid (0.5 mmol, 1 equiv.,
0.1 g) in 5 ml of benzene or dry DCM were added
0.071 g (1 mmol, 2 equiv.) of oxalyl chloride and catalytic
amount of DMF. After 1 h at rt, the solvent and excess
oxalyl chloride were removed in vacuo to afford the
corresponding indolizinylacyl chloride 13, which was used
in the next step without any further purification.
Compound 4 was obtained as white powder in 71% yield
1
(0.97 g), mp 316–3198C; H NMR (CDCl3): d 1.06 (s,
18H, t Bu-H), 1.33 (s, 18H, t Bu-H), 3.54 (d, 4H, ArCH2Ar,
J ¼ 14.8 Hz), 3.83 (d, 4H, ArCH2Ar, J ¼ 14.8 Hz), 3.87
(s, 4H, CH2Br), 4.74 (s, 2H, OH), 6.98 (s, 4H, Ar-H), 7.06
(s, 4H, Ar-H); 13C NMR (CDCl3): 25.26 (2 £ CH2Br),
31.0 (6 £ CH3), 31.7 (6 £ CH3), 34.0 (2 £ C(CH3)3), 34.4
(2 £ C(CH3)3), 34.4 (4 £ ArCH2Ar), 125.4 (4 £ Ar-CH),
127.0 (4 £ Ar-Cq), 126.5 (4 £ Ar-CH), 131.7 (4 £ Ar-
Cq), 142.5 (2 £ Ar-Cq), 144.4 (2 £ Ar-Cq), 149.5 (2 £ Ar-
Cq-OCOR), 150.6 (2 £ Ar-Cq-OH), 164.9 (2 £ CvO); IR
(KBr, cm21): 3128, 2952, 2865, 1764, 1479, 1200, 745;
anal. calcd. for C48H58Br2O6: C, 64.72; H, 6.56. Found: C,
64.66; H, 6.66.
5,11,17,23-Tetra-tert-butyl-25,27-bis-(chloroacetyloxy)-
26,28-dihydroxy-calix[4]arene 2
Compound 2 was obtained as white powder in 75% yield
(0.92 g), mp 309–3118C; 1H NMR (CDCl3): d 1.14 (s, 18H,
tBu-H), 1.31 (s, 18H, tBu-H), 3.68 (d, 4H, ArCH2Ar,
J ¼ 15.2Hz), 3.76 (d, 4H, ArCH2Ar, J ¼ 15.2Hz), 3.85 (s,
4H, CH2Cl), 4.45 (s, 2H, OH), 7.00 (s, 4H, Ar-H), 7.09 (s,
4H, Ar-H); 13C NMR (CDCl3): 31.1 (6 £ CH3), 31.7
(6 £ CH3), 34.0 (2 £ C(CH3)3), 34.3 (2 £ C(CH3)3), 35.7
(4 £ ArCH2Ar), 40.3 (2 £ CH2Cl), 125.4 (4 £ Ar-CH),
126.7 (4 £ Ar-Cq), 126.9 (4 £ Ar-CH), 131.8 (4 £ Ar-Cq),
142.5 (2 £ Ar-Cq), 144.3 (2 £ Ar-Cq), 149.8 (2 £ Ar-Cq-
OCOR), 150.9 (2 £ Ar-Cq-OH), 164.7 (2 £ CvO); IR
(KBr, cm21): 3512, 2952, 1763, 1461, 1168, 1138, 1108;
MS (ESIþ): 823 (M þ Naþ), 839 (M þ Kþ); anal. calcd. for
C48H58Cl2O6: C, 71.90; H, 7.29. Found: C, 71.81; H, 7.20%.
5,11,17,23-Tetra-tert-butyl-25,26-bis-(chloroacetyloxy)-
27,28-dihydroxy-calix[4]arene 6
Compound 6 was obtained as white powder in 75% yield
1
(0.29 g), mp 332–3348C; H NMR (CDCl3): d 1.29 (s,
18H, t Bu-H), 1.32 (s, 18H, t Bu-H), 2.75 (d, 2H, ArCH2Ar,
J ¼ 16.0 Hz), 3.17 (d, 2H, ArCH2Ar, J ¼ 16.0 Hz), 3.31
(d, 1H, ArCH2Ar, J ¼ 14.0 Hz), 3.46 (d, 1H, ArCH2Ar,
J ¼ 14 Hz), 3.54 (d, 1H, ArCH2Ar, J ¼ 14.0 Hz), 3.87 (d,
2H, CH2Cl, J ¼ 16.8 Hz), 4.06 (d, 2H, CH2Cl,
J ¼ 16.8 Hz), 4.14 (d, 1H, ArCH2Ar, J ¼ 14.0 Hz), 5.98
(s, 2H, OH), 6.98 (d, 2H, Ar-H, J ¼ 2 Hz), 7.15 (d, 2H, Ar-
H, J ¼ 2 Hz), 7.23 (d, 2H, Ar-H, J ¼ 2 Hz), 7.28 (d, 2H,
Ar-H, J ¼ 2 Hz); 13C NMR (CDCl3): 31.2 (6 £ CH3), 31.6
(6 £ CH3), 34.1 (2 £ C(CH3)3), 34.5 (2 £ C(CH3)3), 37.6
(4 £ ArCH2Ar), 39.6 (2 £ CH2Cl), 125.4 (2 £ Ar-Cq),
5,11,17,23-Tetra-tert-butyl-25,26,27-tris-
(chloroacetyloxy)-28-hydroxy-calix[4]arene 3
Compound 3 was obtained as colourless crystals in 79%
1
yield (1.07 g), mp 326–3288C. H NMR (CDCl3): d 1.04

10
R. Danac et al.
125.8 (2 £ Ar-CH), 125.9 (2 £ Ar-CH), 126.1 (2 £ Ar-
CH), 126.8 (2 £ Ar-CH), 128.2 (2 £ Ar-Cq), 130.5
(2 £ Ar-Cq), 133.8 (2 £ Ar-Cq), 144.2 (2 £ Ar-Cq),
144.3 (2 £ Ar-Cq), 149.7 (2 £ Ar-Cq-OCOR), 149.8
(2 £ Ar-Cq-OH), 166.0 (2 £ CvO); IR (KBr, cm21):
3492, 2960, 1773, 1482, 1202, 1143; MS (ESIþ): 823
(M þ Naþ); anal. calcd. for C48H58Cl2O6: C, 71.90; H,
7.29. Found: C, 71.85; H, 7.27.
(2 £ CvO); IR (KBr, cm21): 3568, 2952, 2866, 1740,
1458, 1224, 1209, 754; MS (ESIþ): 1012 (M þ Hþ), 1035
(M þ Naþ); anal. calcd. for C66H68N4O6: C, 78.23; H,
6.76; N, 5.53. Found: C, 78.18; H, 6.83; N, 5.55.
5,11,17,23-Tetra-tert-butyl-25,27-bis-[2-(pyrid-20-
yl)pyridin-5-carbonyloxy]-26,28-dihydroxy-calix[4]arene
11
Compound 11 was obtained as pale yellow crystals in 77%
1
yield (0.24 g), mp 284–2878C; H NMR (CDCl3): d 1.07
5,11,17,23-Tetra-tert-butyl-25,27-bis[4-[1-
(ethoxycarbonyl)-3-(4-methylbenzoyl) indolizin-7-yl]-1-
(2-acetyloxy)pyridinium]-26,28-dihydroxy-calix[4]arene
dibromide 7
(s, 18H, t Bu-H), 1.10 (s, 18H, t Bu-H), 3.58 (d, 4H,
ArCH2Ar, J ¼ 14.4 Hz), 3.92 (d, 4H, ArCH2Ar,
J ¼ 14.4 Hz), 4.95 (s, 2H, OH), 6.98 (s, 4H, Ar-H), 7.01
(s, 4H, Ar-H), 7.27 (m, 2H, H-50, CDCl3 overlapped
signal), 7.50 (dt, 2H, H-40, J ¼ 7.6 and 0.8 Hz), 8.43 (d,
2H, H-30, J ¼ 8.0 Hz), 8.55 (ad, 2H, H-60, J ¼ 4.4 Hz),
8.66 (dd, 2H, H-3, J ¼ 8.4 and 1.6 Hz), 8.74 (d, 2H, H-4,
J ¼ 8.4 Hz), 9.47 (as, 2H, H-6); 13C NMR (CDCl3): 31.1
(6 £ CH3), 31.4 (6 £ CH3), 33.8 (2 £ C(CH3)3), 34.1
(2 £ C(CH3)3), 34.2 (4 £ ArCH2Ar), 121.3 (2 £ C-4),
122.3 (2 £ C-30), 124.3 (2 £ C-50), 124.6 (2 £ C-5), 125.7
(4 £ Ar-CH), 126.5 (4 £ Ar-CH), 127.5 (4 £ Ar-Cq),
132.1 (4 £ Ar-Cq), 136.9 (2 £ C-40), 138.8 (2 £ Ar-Cq),
144.7 (2 £ Ar-Cq), 143.5 (2 £ C2), 149.2 (2 £ C60), 150.5
(2 £ Ar-C-OH), 151.3 (2 £ C6), 155.0 (2 £ C20), 160.2
(2 £ Ar-Cq-OCOR), 163.8 (2 £ CvO). IR (KBr, cm21):
3533, 2959, 1728, 1591, 1480, 1177, 1117, 757; MS
(ESIþ): 1012 (M þ Hþ), 1035 (M þ Naþ); anal. calcd. for
C66H68N4O6: C, 78.23; H, 6.76; N, 5.53. Found: C, 78.18;
H, 6.82; N, 5.55.
Compound 7 was obtained as yellow powder in 69% yield
1
(0.86 g), mp 280–2828C; H NMR (CDCl3): d 1.12 (s,
18H, t Bu-H), 1.18 (s, 18H, t Bu-H), 1.42 (t, 6H,
2 £ CH2CH3, J ¼ 7.2 Hz), 2.47 (s, 6H, 2 £ CH3), 3.42
(d, 4H, ArCH2Ar, J ¼ 13.2 Hz), 4.38 (d, 4H, ArCH2Ar,
J ¼ 13.2 Hz), 4.42 (q, 4H, 2 £ CH2CH3, J ¼ 7.2 Hz), 6.96
(s, 4H, Ar-H), 7.05 (s, 4H, Ar-H), 7.11 (s, 4H, 2 £ CH2N),
7.35 (ad, 6H, 2 £ H-300, 2 £ H-500, 2 £ H-60), 7.63 (s, 2H,
OH), 7.76 (d, 4H, 2 £ H-200, 2 £ H-1600, J ¼ 7.6 Hz), 7.90
(s, 2H, 2 £ H-20), 8.25 (as, 4H, 2 £ H-2, 2 £ H-6), 8.87 (as,
2 £ H-80), 9.78 (as, 4H, 2 £ H-3, 2 £ H-5), 10.02 (d, 2H,
2 £ H-50, J ¼ 7.2 Hz); 13C NMR (CDCl3): 14.6, 21.7,
31.4, 31.2, 31.8, 32.6, 33.8, 34.0, 34.3, 60.7, 109.7, 112.1,
119.9, 124.0, 125.5, 128.9, 129.3, 129.9, 130.6, 132.0,
136.3, 138.0, 143.0, 144.4, 147.2, 163.4 (2 £ COOEt),
185.8 (2 £ CvO); IR (KBr, cm21): 3186, 2958, 1758,
1701, 1618, 1202; anal. calcd. for C96H98N4O12: C, 69.47;
H, 5.95; N, 3.38. Found: C, 69.39; H, 5.97; N, 3.35.
3-(4-Methylbenzoyl)-7-(pyridine-4-yl)indolizine-1-
carboxylic acid 12
5,11,17,23-Tetra-tert-butyl-25,27-bis-[2-(pyrid-20-
yl)pyridin-4-carbonyloxy]-26,28-dihydroxy-calix[4]arene
10
Compound 12 was obtained as yellow solid in 90% yield
(0.67 g), mp 284–2868C; IR (KBr, cm21): 3427 (bb),
2922, 1698, 1606, 1213.
Compound 10 was obtained as pale pink crystals in 70%
1
yield (0.22 g), mp 305–3078C; H NMR (CDCl3): d 1.02
(s, 18H, t Bu-H), 1.17 (s, 18H, t Bu-H), 3.54 (d, 4H,
ArCH2Ar, J ¼ 14.4 Hz), 3.97 (d, 4H, ArCH2Ar,
J ¼ 14.4 Hz), 5.09 (s, 2H, OH), 6.94 (s, 4H, Ar-H), 7.04
(s, 4H, Ar-H), 7.26 (m, 2H, H-50, CDCl3 overlapped
signal), 7.80 (dt, 2H, H-40, J ¼ 7.6 and 1.6 Hz), 8.03 (dd,
2H, H-5, J ¼ 4.8 and 1.2 Hz), 8.40 (d, 2H, H-30,
J ¼ 8.0 Hz), 8.59 (d, 2H, H-60, J ¼ 4.4 Hz), 8.72 (d, 2H,
H-6, J ¼ 4.8 Hz), 9.47 (s, 2H, H-3); 13C NMR (CDCl3):
31.0 (6 £ CH3), 31.5 (6 £ CH3), 33.3 (4 £ CH2), 33.9
(2 £ C(CH3)3), 34.1 (2 £ C(CH3)3), 121.3 (2 £ C-3),
121.4 (2 £ C-30), 122.7 (2 £ C-5), 124.2 (2 £ C-50),
125.7 (4 £ Ar-CH), 126.3 (4 £ Ar-CH), 127.8 (4 £ Ar-
Cq), 131.7 (4 £ Ar-Cq), 136.9 (2 £ C-40), 137.7 (2 £ Ar-
Cq), 142.9 (2 £ Ar-Cq), 143.1 (2 £ C2), 149.2 (2 £ C4),
149.4 (2 £ C60), 150.3 (2 £ C6), 150.4 (2 £ Ar-C-OH),
154.9 (2 £ C20), 157.8 (2 £ Ar-Cq-OCOR), 163.8
5,11,17,23-Tetra-tert-butyl-25,27-bis-[3-(4-
methylbenzoyl)-7-(pyridin-4-yl)indolizine-1-
carbonyloxy]-26,28-dihydroxy-calix[4]arene 14
Compound 14 was obtained as yellow powder in 50%
1
yield (0.20 g), mp .3608C; H NMR (CDCl3): d 0.94 (s,
18H, t Bu-H), 1.35 (s, 18H, t Bu-H), 2.15 (s, 6H, 2 £ CH3)
3.31 (d, 2H, ArCH2Ar, J ¼ 12.4 Hz), 3.62 (d, 2H,
ArCH2Ar, J ¼ 10.4 Hz), 4.04 (d, 2H, ArCH2Ar,
J ¼ 12.4 Hz), 4.28 (d, 2H, ArCH2Ar, J ¼ 10.4 Hz), 6.17
(s, 2H, OH), 6.42 (as, 4H, 2 £ H-300, 2 £ H-500), 6.80 (bs,
2H, Ar-H), 6.88 (bs, 2H, Ar-H), 7.12 (bs, 2H, Ar-H), 7.24
(bs, 2H, Ar-H), 7.37 (d, 4H, 2 £ H-200, 2 £ H-600,
J ¼ 5.6 Hz), 7.56 (as, 2H, 2 £ H-6), 7.76 (as, 4H, H-30,
H-50), 8.17 (s, 2H, 2 £ H-2), 8.83 (ad, 6H, 2 £ H-20, 2 £ H-
60, 2 £ H-8), 10.17 (as, 2H, 2 £ H-5); 13C NMR (CDCl3):

Supramolecular Chemistry
11
21.5 (2 £ CH3), 30.9 (6 £ CH3), 31.4 (2 £ CH2), 31.7
(6 £ CH3), 31.8 (2 £ CH2), 34.0 (4 £ C(CH3)3), 113.9
(2 £ C-6), 116.7 (2 £ C-8), 104.6 (2 £ Ar-Cq), 121.1
(2 £ C-30, 2 £ C-50), 123.0 (2 £ Ar-Cq), 125.4 (4 £ Ar-
CH), 125.5 (4 £ Ar-CH), 125.9 (2 £ Ar-Cq), 127.9
(2 £ C-300, 2 £ C-500), 128.4 (2 £ C-2), 129.1 (2 £ C-200,
2 £ C-600), 129.8 (2 £ C-5), 131.2 (2 £ Ar-Cq), 135.5
(2 £ Ar-Cq), 137.0 (2 £ Ar-Cq), 140.4 (2 £ Ar-Cq), 141.6
(2 £ Ar-Cq), 142.1 (2 £ Ar-Cq), 142.8 (2 £ Ar-Cq), 145.0
(2 £ Ar-Cq), 148.8 (2 £ Ar-Cq), 150.1 (2 £ Ar-Cq), 150.8
(2 £ C-20, 2 £ C-60), 161.9 (2 £ COOR), 184.4
(2 £ CvO); IR (KBr, cm21): 3547, 2957, 2868, 1720,
1619, 1184, 1167, 1070; anal. calcd. for C88H84N4O8: C,
79.73; H, 6.39; N, 4.23. Found: C, 79.68; H, 6.44; N, 4.26.
determination and data integration were carried out using
the CrysAlis package of Oxford Diffraction (Oxford
Diffraction Limited, Abingdon, UK) (16). All structures
were solved by direct methods using SHELXS-97 (17) and
refined by full-matrix least squares on Fo2 with SHELXL-
97 (17) with anisotropic displacement parameters for non-
hydrogen atoms. All H atoms attached to carbon were
˚
introduced in idealised positions (dCH ¼ 0.96 A) using the
riding model with their isotropic displacement parameters
fixed at 120% of their riding atom. Positional parameters of
the H attached to O atoms were obtained from difference
Fourier syntheses and verified by the geometric parameters
of the corresponding hydrogen bonds. All carbon atoms of
tert- Bu groups in structures 3 and 11 presented too large
thermal ellipsoids, so that disordered models in combi-
nation with the available tools (PART, DFIX and SADI) of
SHELXL97 were applied in order to better fit the electron
density. The same approach was applied in order to fit two
disordered positions of BiPy fragment in structure 11. The
main crystallographic data together with refinement details
are summarised in Table 5.
X-ray crystallography
X-ray data for compound 3 were collected at the Aarhus
University using an Agilent SuperNova diffractometer
(Agilent Technologies, Santa Clara, USA) equipped with
an Atlas CCD detector. The crystal was cooled to 100K
using Oxford Cryosystems Cryostream 700 (Oxford
Cryosystems, Oxford, UK). Crystallographic measure-
ments for 10 and 11 were carried out with an Oxford-
Diffraction XCALIBUR E CCD diffractometer (Oxford
Diffraction Limited, Abingdon, UK) using graphite-
monochromated Mo-Ka radiation. The crystals were
placed 40 mm from the CCD detector. The unit cell
CCDC-864665 (3), CCDC-864663 (10) and CCDC-
864664 (11) contain the supplementary crystallographic
data for this contribution. These data can be obtained free
of charge via http://www.ccdc.cam.ac.uk/conts/retrieving.
html (or from the Cambridge Crystallographic Data
Table 5. Crystallographic data, details of data collection and structure refinement parameters for compounds 3, 10 and 11.
Empirical formula
C50H59Cl3O7 (3)
C66H68N4O6 (10)
C132H142N8O14.8 (11)
Molecular weight, g/mol
Temperature (K)
878.32
100
0.71073
Monoclinic
1013.24
200
0.71073
2077.34
293
0.71073
Monoclinic
C2/m
25.613 (3)
17.9021 (15)
15.5182 (17)
90
125.531 (16)
90
˚
Wavelength (A)
Crystal system
Space group
Orthorhombic
Pnma
19.9520 (10)
13.7058 (10)
21.7492 (12)
90
ꢀ
P1
˚
a (A)
10.4314 (6)
13.3835 (10)
17.7391 (10)
69.535 (6)
87.247 (5)
84.853 (5)
2310.5 (3)
2
˚
b (A)
˚
c (A)
a (8)
b (8)
g (8)
90
90
3
˚
V (A )
5947.5 (6)
4
1.132
5790.6 (10)
2
1.191
Z
Dcalc (g/cm3)
1.262
0.249
m (mm21
)
min, u max (8)
0.072
0.078
u
2.29–26.00
0.21 £ 0.08 £ 0.05
34892/9069 (Rint ¼ 0.0755)
9069/0/553
0.0776
2.99–25.05
0.20 £ 0.20 £ 0.15
17115/5183 (Rint ¼ 0.0678)
5183/66/361
0.0860
3.00–26.00
0.10 £ 0.10 £ 0.05
14129/5872 (Rint ¼ 0.0768)
5872/46/407
0.0840
Crystal size (mm)
Reflections collected/unique
Data/restraints/parameters
R1 (I . 2s(I))a
wR2 (I . 2s(I))b
R1 (all data)a
0.1790
0.1345
0.2027
1.008
0.485 and 20.455
0.2018
0.1686
0.2364
1.007
0.432 and 20.406
0.1014
0.2602
0.1322
1.031
0.418 and 20.220
wR2 (all data)b
GOFc
Drmax and Drmin (e/A )
3
˚
a R1 ¼ SkFoj 2 jFck=SjFoj.
b
c
wR2 ¼ {S½wðF2o 2 Fc2Þ ꢀ=S½wðF2oÞ ꢀ}1=2
.
2
2
GOF ¼ {S½wðF2o 2 Fc2Þ ꢀ=ðn 2 pÞ}1=2, where n is the number of reflections and p is the total number of parameters refined.
2

12
R. Danac et al.
Lamartine, R., Meallier P.; Guittonneau, S.; Fenet, B.
Helv. Chim. Acta 1997, 80, 1229–1243; (c) Talanov, V.S.;
Roper, E.D.; Buie, N.M.; Talanova, G.G. Tetrahedron Lett.
2007, 48, 8022–8025; (d) Chang, K.C.; Senthivelan, A.;
Chung, W.S. Org. Lett. 2007, 9, 3363–3366.
Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax:
(þ44) 1223-336-033; or deposit@ccdc.ca.ac.uk).
Acknowledgements
(6) (a) Regnouf-de-Vains, J.B.; Lamartine, R. Tetrahedron Lett.
1996, 37, 6311–6314; (b) Creaven, B.S.; Gernon, T.L.;
McGinley, J.; Moore, A.M.; Toftlund, H. Tetrahedron 2006,
62, 9066–9071; (c) Arena, G.; Contino, A.; Longo, E.;
Sciotto, D.; Sgarlata, C.; Spoto, G. Tetrahedron Lett. 2003,
44, 5415–5418; (d) Arena, G.; Bonomo, R.P.; Contino, A.;
Sgarlata, C.; Spoto, G.; Tabbi, G. Dalton Trans. 2004,
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This study was supported by the National Council for Research in
Higher Education Institutions (CNCSIS), Ministry of Education,
Research and Innovation, Romania, through the IDEI Grant No.
2023/2008, European Regional Development Fund, Sectoral
Operational Programme ‘Increase of Economic Competitive-
ness,’ Priority Axis 2 (SOP IEC-A2-O2.1.2-2009-2, ID 570,
COD SMIS CSNR: 12473, Contract 129/2010-POLISILMET)
and European Union’s Seventh Framework Programme
(FP7/2007-2013) under agreement 264115 – STREAM. Authors
are also grateful to Dr Jacob Overgaard, Aarhus University, for
structure determination of compound 3.
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Supramolecular Chemistry
13
Ramona Danac,
Raluca Rusu,
AlexandruRotaru, AurelPui
and Sergiu Shova
New conjugates of
calix[4]arenes bearing
dipyridine and indolizine
heterocycles
1–13