Dansylated resorcinarenes

Article abstract of DOI:10.1039/b615772f

The synthesis, X-ray crystal structures and spectroscopic characterization (UV-Vis absorption and fluorescence emission) of regioselective tetradansylated resorcinarene 2 and octadansylated resorcinarene 3 are described. In solution, the resorcinarene bac

Full text of DOI:10.1039/b615772f

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www.rsc.org/njc | New Journal of Chemistry
Dansylated resorcinarenes
a
a
a
a
˚
Ngong Kodiah Beyeh, Jukka Aumanen, Antti Ahman, Minna Luostarinen, Heidi
ab
Mansikkamaki, Maija Nissinen,a Jouko Korppi-Tommola*a and Kari Rissanen*a
¨
Received (in Montpellier, France) 30th October 2006, Accepted 4th January 2007
First published as an Advance Article on the web 25th January 2007
DOI: 10.1039/b615772f
The synthesis, X-ray crystal structures and spectroscopic characterization (UV-Vis absorption and
fluorescence emission) of regioselective tetradansylated resorcinarene 2 and octadansylated
resorcinarene 3 are described. In solution, the resorcinarene backbone of 2 shows a boat
conformation with C2v symmetry, while the octasubstituted 3 shows at room temperature a time-
averaged C4v symmetry, which turns into stable boat conformation at low temperatures. The four
hydroxyl groups of 2, not present in 3, form hydrogen bonds to the sulfoxide oxygens of the
dansyl moieties and stabilize the C2v conformation in solution. The X-ray crystal structures of 2
and 3 confirm the C2v symmetry of both compounds in the crystalline state and revealed that the
tetradansyl resorcinarene has two rather strong intramolecular O–HÁ Á ÁOQS hydrogen bonds. In
addition 2 forms a directly hydrogen-bonded dimeric assembly via four intermolecular O–HÁ Á ÁO
and O–HÁ Á ÁOQS hydrogen bonds. In the solid state both 2 and 3 exhibit a multitude of intra-
and intermolecular p–p interactions between the adjacent dansyl moieties and also with the
aromatic parts of the macrocyclic skeleton. The absorption and fluorescence spectra of 2 and 3,
together with a reference compound, dansylphenolate 4, were recorded. In chloroform, with the
same dansyl concentration and absorption at excitation wavelength, fluorescence from 4 was
clearly stronger than that from either 2 or 3, an indication of excited-state dansyl–dansyl
interactions in the dansyl substituted resorcinarenes. The absorption and emission bands of the
dansyl units were gradually substituted by the absorption and emission bands of the protonated
dansyl units when 2 and 3 were titrated with trifluoroacetic acid.
macromolecules.14 To the best of our knowledge, the spectro-
Introduction
scopic characterization of the dansyl substituted resorcinar-
enes have not been reported. Here we report the synthesis and
X-ray structures, supplemented by spectroscopic characteriza-
tion (UV-Vis absorption and fluorescence emission) in
solution, of tetradansyl resorcinarene 2 and octadansyl resor-
cinarene 3 in comparison to the monodansyl reference com-
pound, dansyl phenolate 4.
Resorcinarenes,1 are suitable building blocks of various
supramolecular structures such as open inclusion complexes,2
dimeric,3 and hexameric,4 capsules as well as nanotubes.5
Alkylation and acylation of the resorcinarene hydroxyl groups
have been used for the synthesis of cavitands, carcerands,
hemicarcerands, and velcrands.6 Resorcinarenes can be com-
pletely acylated and alkylated to esters and ethers,7 and
regioselectively acylated via partial acylation by using ester
functions as protecting groups.8 The cyclic array of hydrogen
bonds does not exist in hydroxyl group persubstituted resor-
cinarenes and usually these molecules undergo a conforma-
tional change from crown (C4v) to boat (C2v).9
Results and discussion
Synthesis and NMR investigations
The reaction of resorcinarene 1 with dansyl chloride in aceto-
nitrile (MeCN) in the presence of triethylamine (Et3N) as base
(1 : 4 : 4 molar ratio) resulted in tetradansylated resorcinarene
2 in moderate 45% yield. Corresponding reaction with
equimolar amounts of the reagents per hydroxyl group
(1 : 8 : 8; 1–dansyl chloride–Et3N) resulted in complete
dansylation of resorcinarene 1 to give octadansylated resorci-
narene 3 in 76% yield (Scheme 1).
The photochemistry of the dansyl group and its interactions
with cations and anions as well as its function as a light
harvesting chromophore has been reported for several mole-
cules such as calixarenes,10 crown ethers,11 dendrimers,12 and
cyclodextrins.13 The dansyl substituent when covalently bound
to a host molecule shows intense absorption bands in the near
UV and a strong fluorescence in the visible region and is
extensively used for sensing and labeling of proteins and
As a reference for the spectroscopic characterizations of 2
and 3, a model compound was prepared by the base-catalyzed
acylation of phenol with dansyl chloride in CH2Cl2 giving
dansyl phenolate 4 which was purified by column chromato-
graphy (Scheme 2).
a NanoScience Center, Department of Chemistry, University of
Jyvaskyla, P. O. Box 35, 40014 Jyvaskyla, Finland. E-mail:
¨
¨
¨
¨
Kari.Rissanen@jyu.fi; Fax: +358-14-2602651; Tel: +358-14-
2602672
b BASF Aktiengesellschaft, GVC/P–A 030, 67056 Ludwigshafen,
Germany
The structure and composition of resorcinarenes 2 and 3, as
well as reference compound 4, were confirmed by NMR
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Fig. 1 1H NMR spectrum of resorcinarene 2 in acetone-d6 at 303 K.
Four singlets of the aromatic protons of resorcinol rings indicate a
C2v-symmetric conformation. Coupling with the diastereotopic pro-
tons of the methylene group causes the doublet of doublet for the
methine protons. DAN stands for dansyl.
showed a major peak at m/z 1612.78 corresponding to the
sodium adduct of 2.
1
The H NMR spectrum of the persubstituted octadansyl 3
(Fig. 2) in CDCl3 at 323 K shows one sharp and one broad (at
6.5 ppm) overlapping signals for the aromatic protons of the
resorcinarene skeleton. This is due to a fast dynamics of the
resorcinarene skeleton resulting in a spectrum consistent with
time-averaged C4v symmetry. The dynamics is verified at
243 K where this signal splits into four separate peaks
indicating the formation of the rigid C2v boat conformation
(Fig. 2). The ESI-TOF mass spectrum showed a major peak at
m/z 2546.40 corresponding to the sodium adduct of 3.
Scheme 1 Partial and complete dansylation of resorcinarene 1 by
dansyl chloride.
Scheme 2 Synthesis of dansyl phenolate 4.
X-Ray crystal structures
The tetradansylated resorcinarene 2 crystallizes in a boat
conformation (Fig. 3). Due to the bulky dansyl groups the
position of the free hydroxyl groups is too far away from the
adjacent resorcinol oxygens to allow intramolecular hydrogen
bonding that are usually required for the crown conformation.
Instead two intramolecular hydrogen bonds are formed to
sulfonyl oxygens (SQOÁ Á ÁO distances 2.781(9) and 2.798(8) A,
Fig. 3, top). The resorcinol rings containing unsubstituted
hydroxyl groups are almost parallel (4.21 dihedral angle and
4.9 A centroid-to-centroid distance) while the sulfonylated
rings are nearly coplanar (172.71 dihedral angle between the
resorcinol rings).
spectroscopy, mass spectrometry, X-ray crystallography and
elemental analysis. The 1H NMR spectrum of resorcinarene 2
in acetone-d6 at 303 K (Fig. 1) contains a doublet of doublets
corresponding to the methine protons. The splitting of the
signal is due to the coupling with the diastereotopic protons of
the neighboring methylene groups that appear in turn as two
well-separated multiplets. Also, the protons of the methylene
groups more remote from the methine carbons appear as two
well-separated multiplets. In addition, the spectrum of 2
contains a singlet for the methyl groups of the dansyl, four
singlets for the aromatic protons of the resorcinol rings
indicating the boat conformation, one singlet for the free
OH-groups and four doublets and two overlapping triplets
for the aromatic protons of the dansyl groups. This spectrum
is in line with structure 2 as shown in Scheme 1 and indicates a
C2v-symmetric conformation of the resorcinarene skeleton.
The resorcinarene skeleton of 2 contains four hydroxyl groups
that can form hydrogen bonds to the sulfoxide groups of the
dansyls and stabilize the boat conformation in solution at
room temperature (Fig. 1). The ESI-TOF mass spectrum
All four dansyl groups are in a propeller-like orientation
beside the core resorcinarene leaving enough space for inter-
molecular hydrogen bonds. Indeed, two molecules of 2 form
directly hydrogen bonded dimeric assemblies where two out of
four intermolecular hydrogen bonds form between opposing
hydroxyl groups (OÁ Á ÁO distance 2.802(9) A) and the other
two are between opposing sulfonyl oxygen and hydroxyl
groups (SQOÁ Á ÁO distance 2.874(8) A, Fig. 3, bottom). Due
to the boat conformation, the cavity of the resorcinarene is
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Fig. 2 1H NMR spectrum of resorcinarene 3 in CDCl3 at different
temperatures. At 323 K the compound shows two overlapping signals
for the aromatic protons which broaden as the temperature is reduced
and finally splits into four singlets at 243 K to confirm a C2v symmetry
conformation. The single peak at higher temperatures can be
explained as a result of the fast dynamics resulting in the time-average
C4v symmetry.
very small and there is no room for a possible guest molecule
inside the dimeric assembly.
Fig. 3 ORTEP-plot (top) presentation of X-ray crystal structure of
tetra-substituted resorcinarene 2. Dimeric assembly of 2 (bottom).
Intermolecular hydrogen bonds are shown as dotted lines and hydro-
gen atoms are omitted for clarity. Solvent molecules are omitted for
clarity.
In the structure 2 intramolecular edge-to-face p–p inter-
actions show close proximity of the dansyl group and aromatic
resorcinol rings of the resorcinarene skeleton. The shortest
carbon to ring centre distance between carbons of resorcinol
rings and dansyl moieties are 3.65 and 3.84 A. Unlike in
octadansyl resorcinarene 3 (see below) the dansyl groups in
2 are not packed close to each other, hence no intramolecular
p–p interactions were detected between dansyl groups. How-
ever, in solution the p–p interactions of the dansyl groups
affect the photoactive properties of both 2 and 3 by quenching
of the fluorescence of the dansyl group (below).
bottom). Also in this case the p–p interactions affect the crystal
packing. The phenyl group of the molecule is offset face-to-
face stacked with the phenyl group of another nearby mole-
cule, the distance between the centre of the aromatic ring and
the nearest carbon atom of the adjacent group being 3.54 A. In
addition the phenyl group is edge-to-face stacked with aro-
matic part of the dansyl group of the same nearby molecule,
the shortest distance between the carbon of the phenyl group
and the centroid of the dansyl part being 3.95 A. Two
CHÁ Á ÁOQS hydrogen bonds are detected between the methyl
hydrogens of the amine and oxygens of the sulfonyl group
[distance 3.141(3) A] (Fig. 4, bottom right).
As in 2, the octadansylated resorcinarene 3 with a twofold
crystallographic symmetry also assumes a boat conformation
in the solid state (Fig. 4, top) because there are no possibilities
for intramolecular hydrogen bonds and due to the arrange-
ment of the bulky dansyl groups. The boat conformation is
described by the dihedral angles between opposite resorcinol
rings, which are 1.6 and 144.31 and the distances between the
parallel resorcinol ring centers, 5.03 A. In this case bulky
dansyl moieties are bent beside and above of the upper part of
the resorcinarene skeleton covering half of the molecule. Due
to the spatial proximity, the dansyl groups show intramole-
cular p–p interactions with each other and with the resorcinol
rings. One acetonitrile molecule is located at the lower rim
between the four hydrophobic alkyl chains and its nitrogen
atom is pointing towards the interior of the alkyl chain cage.
Similar inclusions of a solvent molecule or an anion at the
lower rim have been reported earlier for numerous resorcinar-
ene crystal structures.3,15
Absorption and fluorescence properties
The absorption and fluorescence spectra in chloroform with
the same dansyl concentrations for 2, 3 and 4 are shown in
Fig. 5. The reference compound 4 in chloroform exhibits
intense absorption bands in the near UV spectral region
(lmax = 350 nm) and a strong fluorescence band in the visible
region (lmax = 514 nm) where also the respective bands of
resorcinarene 3 were observed, i.e. no spectral shifts were
observed in the absorption and fluorescence bands between
the resorcinarene 3 and reference compound 4. The absorption
and fluorescence bands of resorcinarene 2 are however slightly
redshifted.
Reference compound 4 gave suitable single crystals for
X-ray analysis from propanol–CH2Cl2 solution (Fig. 4,
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Fig. 5 Absorption and fluorescence spectra (lexc = 350 nm) of
resorcinarene 2 (Á Á Á at 2.5 Â 10À5 mol LÀ1), 3 ( Á Á – at 1.25 Â 10À5
mol LÀ1) and 4 (— at 1.0 Â 10À4 mol LÀ1) in chloroform.
protonated dansyls. The behavior is similar to that Valeur
et al.10a observed with dansylated calixarenes and Vogtle
Fig. 4 Top view of the X-ray crystal structure of completely dansy-
lated resorcinarene 3 (ORTEP-plot, presentation). ORTEP-plot of the
X-ray crystal structure of reference compound 4 (bottom left) and
crystal packing showing the C–HÁ Á Áp and p–p interactions and
C–HÁ Á ÁOQS hydrogen bonds (bottom right). All solvent molecules
are omitted for clarity.
¨
et al.12 with dansylated dendrimers. Different fluorescence
measurements of the acid titration of compounds 2, 3 and 4
were done with excitation at lexc = 350 nm (lmax), and lexc
=
313 nm (isosbestic point). The fluorescence of all the com-
pounds with both excitation wavelengths decreases with an
increase in trifluoroacetic acid concentration. The decrease in
the fluorescence emission of the compounds with excitation at
the isosbestic point is proof that the protonation of the dansyl
group is responsible for this behaviour. The absorption and
fluorescent spectra of the acid titration of resorcinarene 3 in
chloroform are shown in Fig. 6.
The fluorescence intensity of the reference compound 4 is
clearly higher than that of the resorcinarene derivatives 2 and
3. The intermolecular hydrogen bonding involving the sulfonic
oxygen of the dansyl group and the hydroxyl groups of the
resorcinarene core might have a role to play in the slight
redshifting and reduced fluorescence emission of the resorci-
narene 2 given that the dansyl concentration are the same as in
resorcinarene 3. The fact that the monosubstituted dansyl
phenolate 4 shows about two times stronger fluorescence
(scaled to same absorbance and same dansyl concentrations
in solution) than the multisubstituted resorcinarenes 3 suggests
strong intramolecular excited-state interactions taking place in
the resorcinarene core. Quenching of fluorescence in dansyl
resorcinarenes may be due to the efficient couplings of the
exited singlet states to the low-frequency vibrational modes of
the resorcinarene structures.16 A more probable explanation is
the excited-state energy transfer between the dansyls of the
resorcinarenes resulting in reduced emission.10a These
processes were not studied here, but will be the focus
of a subsequent study using femtosecond fluorescence spectro-
scopy.
The solubility limitations of the resorcinarenes (not soluble
in polar solvents) limit their potential applications as sensors.
Vogtle et al.12 reported a study on dendrimers where the
¨
energy transfer occurred from dansyl units to the eosin dye.
The resorcinarenes are not capable of complexing the eosin
dyes due to the large size of the eosin dyes and the lack of
electron donor atoms in the resorcinarene skeleton. Resorci-
narenes are, however, known to complex tetraalkylammonium
ions.15c The effect of this complexation in the fluorescence
emission of the octadansylated resorcinarene 3 was investi-
gated by titrating tetramethylammonium bromide in water
with the resorcinarene 3 in chloroform. The formed complex is
more soluble in chloroform than the free octadansyl resorci-
narene 3 and the complexation has an effect on the photo-
physics of the dansyl groups. The non-polar wet chloroform
layer was then measured. The addition of the tetramethyl-
ammonium bromide had no influence on the absorption
behaviour but the fluorescence intensity shows a concentration
dependent decrease with increasing tetramethylammonium
bromide concentration as shown in Fig. 7.
It is known that the absorption and fluorescence properties
of the dansyl group are very sensitive to acid because of the
protonation of the nitrogen in the dansyl unit at low
pH.10a,12,17 Upon addition of trifluoroacetic acid, the absorp-
tion of compounds 2, 3 and 4 (at 260 and 350 nm) decreases
continuously. A new absorption peak appears at 288 nm with
a shoulder at 323 nm which gains intensity with addition of the
acid. These new absorption peaks correspond to the proto-
nated dansyl unit. Two isosbestic points observed at 270 and
313 nm indicate an A to B transformation of dansyls to
Conclusion
The dansylation of resorcinarene 1 resulted in partially and
completely substituted resorcinarenes 2 and 3 depending on
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Fig. 6 Absorption and fluorescent titration of resorcinarene 3 with
trifluoroacetic (TFA) acid in chloroform, [3] = 1.25 Â 10À5 mol LÀ1
Fig. 7 Absorption and fluorescent titration of octadansylated resor-
cinarene 3 in chloroform with trimethylammonium bromide (TMA-
,
[TFA] = 1.0 Â 10À3 mol LÀ1, lexc = 313 nm (isosbestic point). From
Br) in H2O, [3] = 1.25 Â 10À5 mol LÀ1, [TMA-Br] = 1.0 Â 10À3 mol LÀ1
,
a–g: 0, 0.8, 1.6, 2.4, 3.2, 4.0, 6.0, 8.0 equiv.
lexc = 350 nm (lmax). From a–e: 0, 0.8, 1.6, 3.2, 4.0 equiv.
the ratio of the used starting compounds; resorcinarene,
dansyl chloride and the base. Resorcinarene 2 adopts a boat
conformation in solution and in solid state while resorcinarene
3 adopts a time-averaged C4v symmetry due to fast dynamics
of the resorcinarene skeleton at room temperature in solution
that stabilizes to rigid C2v symmetry at low temperatures and
in the solid state. The relative fluorescence intensity increases
with the increase in number of dansyl units in the resorcinar-
enes but is clearly less than the intensity of the reference
compound 4. This indicates excited state interactions of the
dansyl groups in 2 and 3 resulting in quenching of the
fluorescence. Direct conversion of the dansyl to the protonated
form was observed on acid titration with trifluoroacetic acid
leading to a decrease in the absorption and fluorescence
spectra of all the compounds. Complexation of tetramethyl-
ammonium bromide had a slight effect on the fluorescence but
not on the absorption behaviour of octadansylated resorci-
narene 3.
Micromass LCT ESI-TOF mass spectrometer and VG Auto
Spec. EI (Electron Impact) ion source spectrometer.
Synthesis
Tetradansylated resorcinarene 2. To a solution of resorci-
narene 1 (0.53 g, 0.81 mmol) in MeCN (20 ml), Et3N (0.45 ml,
3.24 mmol) was added in one portion with vigorous stirring. A
pink precipitate formed and the reaction mixture was stirred
for 15 min. A solution of dansyl chloride (0.88 g, 3.24 mmol) in
MeCN (25 ml) was added to the suspension in one portion and
the reaction mixture was vigorously stirred to facilitate dis-
solution of the precipitate. The reaction mixture was stirred at
room temperature for 72 h. The precipitate formed was filtered
off, washed with MeCN (30 ml) and water (50 ml). The crude
product was purified by column chromatography on silica
using chloroform as eluent to give resorcinarene 2 (0.58 g,
45%) as a yellowish powder: mp 236 1C (Found C, 64.76, H,
5.78, N, 3.57. C88H92N4O16S4 Á 2H2O requires C, 65.00, H,
5.95, N, 3.45%); lmax (CHCl3)/nm 260 (e/MÀ1 cmÀ1 16 500),
352 (4200); dH (500 MHz, acetone-d6, Me4Si, 30 1C) 0.69 (12
H, br, CH2CH3), 1.11 (4 H, m, CH2CH3), 1.34, (4 H, m,
CH2CH3), 1.83 (4 H, m, CHCH2), 2.76 (4 H, m, CHCH2), 2.90
(24 H, s, N(CH3)2), 4.42 (4 H, dd, J 4.5 and 6.0, CHCH2), 6.08
(2 H, s, Ar-H), 6.72 (2 H, s, Ar-H), 6.93 (2 H, s, Ar-H), 7.02 (2
H, s, Ar-H), 7.32 (4 H, d, J 7.25, Dan-H), 7.61 (8 H, m, Dan-
H), 7.96 (4 H, br, s, Ar-OH), 8.15 (4 H, d, J 6.0, Dan-H), 8.36
(4 H, d, J 8.75, Dan-H), and 8.69 (4 H, d, J 8.5, Dan-H); dC
(126 MHz, acetone-d6, Me4Si, 30 1C,) 14.4 (s), 21.7 (s), 36.1 (s),
38.05 (s), 45.7 (s), 114.2 (s), 116.7 (s), 119.7 (s), 120.4 (s), 124.4
(s), 126.6 (s), 129.5 (s), 129.8 (s), 130.8 (d), 131.3 (s), 132.8 (s),
133.6 (s), 138.6 (s), 145.9 (s), 153.0 (s) and 155.0 (d); m/z (ESI-
TOF) 1590.80 [M + H]+ (10%), 1612.78 [M + Na]+ (100),
1628.17 [M + K]+ (60).
Experimental
General remarks
Melting points were determined with a Mettler Toledo FP62
capillary melting point apparatus and are uncorrected.
Elemental analyses were carried out with a Varian ELIII
elemental analyzer. Absorbance measurements were per-
formed using a CARY 100 Conc. (UV-visible) Spectrophoto-
meter and a PERKIN ELMER LS 50 B Luminescence
Spectrometer for fluorescence measurements. 1H and 13C
NMR spectra were recorded on Bruker Avance DRX 500
(500 MHz for 1H and 126 MHz for 13C) spectrometer. 1H and
13C assignments were mainly based on HMQC and HMBC 2D
correlation spectra. All signals are expressed as d values in
ppm using residual solvent signal as internal standard. J values
are given in Hz. The mass spectra were carried out with a
Octadansylated resorcinarene 3. To a solution of resorcinar-
ene 1 (0.15 g, 0.23 mmol) in MeCN (10 ml), Et3N (0.26 ml,
1.85 mmol) was added in one portion with vigorous stirring.
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A pink precipitate formed and the reaction mixture was stirred
for 15 min. A solution of dansyl chloride (0.5 g, 1.85 mmol) in
MeCN (20 ml) was added to the suspension in one portion and
the reaction mixture was intensively stirred to facilitate dis-
solution of the precipitate. The reaction mixture was stirred at
room temperature for 24 h. The precipitate formed was filtered
off, washed with MeCN (30 ml) and water (50 ml). The crude
product was purified by recrystallization from MeCN–CH2Cl2
(5 : 1). The precipitate was filtered off and dried to give reso-
rcinarene 3 (0.44 g, 76%) as a yellowish powder: mp 242 1C
(Found C, 63.89, H, 5.37, N, 4.18. C136H136N8O24S8 Á H2O
requires C, 64.28, H, 5.47, N, 4.41%); lmax (CHCl3)/nm 260
(e/MÀ1 cmÀ1 16 800), 350 (4600); dH (500 MHz, CDCl3, Me4Si,
30 1C) 0.54 (20 H, br s, CH2CH3), 1.35 (8 H, m, CHCH2), 2.87
(48 H, s, N(CH3)2), 4.23 (4 H, t, J 7.4, CHCH2), 6.39 (8 H, br,
s, Ar-H), 7.11 (8 H, d, J 7.8, Dan-H), 7.32 (8 H, t, J 8.0, Dan-
H), 7.46 (8 H, t, J 8.0, Dan-H), 7.90 (8 H, d, J 6.8, Dan-H),
8.08 (8 H, d, J 8.5, Dan-H), 8.48 and (8 H, d, J 8.5, Dan-H); dC
(126 MHz, CDCl3, Me4Si, 30 1C,) 13.4 (s), 20.4 (s), 36.3 (d),
45.0 (s), 114.5 (s), 115.4 (s), 119.2 (s), 123.1 (s), 126.8 (s), 128.8
(s), 129.5 (s), 129.7 (s), 130.4 (s), 131.7 (s) 131.9 (s) and 157.3
(d); m/z (ESI-TOF) 2524.47 [M + H]+ (30%), 2546.40
[M + Na]+ (100), 2562.34 [M + K]+ (15).
d, J 7.8, Dan-H), 7.46 (1 H, t, J 7.5, Dan-H), 7.69 (1 H, t, J 7.5,
Dan-H), 8.05 (1 H, d, J 6.0, Dan-H), 8.43 (1 H, d, J 7.8, Dan-
H) and 8.62 (1 H, d, J 6.5, Dan-H); dC (126 MHz, CDCl3,
Me4Si, 30 1C) 45.8 (s), 116.2 (s), 119.8 (s), 122.6 (s), 123.5 (s),
127.6 (s), 129.6 (s), 130.1 (s), 130.4 (s), 130.6 (s), 131.6 (d),
132.6 (s), 150.4 (s) and 152.7 (s); m/z (EI) 327 (M+, 25%), 186
(7), 170 (100), 127 (15).
X-Ray crystallography
The data for 2, 3 and 4 were recorded with a Nonius Kappa
CCD using graphite-monochromated Mo-Ka radiation
[l(Mo-Ka) = 0.71073 A)] and a temperature of 173.0 Æ 0.1 K.
The CCD data were processed with Denzo-SMN v0.95.373.18
All structures were solved by direct methods (SHELXS-97),19
and refinements based on F2, were made by full-matrix least-
squares techniques (SHELXL-97).20 No absorption correction
was applied. The hydrogen atoms were calculated to their
idealised positions with isotropic temperature factors (1.2 or
1.5 times the C temperature factor) and refined as riding
atoms. In the structure of 2 the R-values and esds for bond
lengths and angles are rather poor due to weakly diffracting
poor quality crystals and severe disorder of solvent molecules.
Acetonitrile molecule (occupancy factor 0.5) and disordered
chloroform (occupancy factors 0.5 : 0.5) were refined isotro-
pically. No hydrogen was determined for disordered chloro-
form. The anisotropic displacement parameters of C75, C76,
N18 and O62 were fixed (EADP) with the respective
parameters of C63, C64, N6 and O41. An electron density
1.06 e AÀ1 was found 1.4 A away from acetonitrile molecule
(C91). Residual electron density that could be assigned to two
severely disordered chloroforms and an acetonitrile molecule
were removed by SQUEEZE,21 since no chemically reasonable
model could be built for them. In the structure of 3, aceto-
nitrile molecules were refined isotropically with population
parameters of 0.5 and 0.25, respectively. Disordered propanol
molecule with occupancy factors 0.5 : 0.5 was refined
Dansyl phenolate 4. A solution of dansyl chloride (1.0 g, 3.7
mmol) and Et3N (2.1 ml, 14.8 mmol) in CH2Cl2 (10 ml) was
added to solution of phenol (0.12 g, 1.2 mmol) in CH2Cl2 (10
ml). The reaction mixture was stirred at room temperature for
20 h and the solvent was evaporated. The crude product was
purified by column chromatography on silica using dichloro-
methane–ethyl acetate–n-hexane (1.5 : 1.5 : 1, v/v) as eluent to
give reference compound 4 (0.34 g, 87%) (Found C, 65.07, H,
5.26, N, 4.29. C18H17NO3S Á 0.25H2O requires C, 65.14, H,
5.31, N, 4.22%); lmax (CHCl3)/nm 260 (e/MÀ1 cmÀ1 16 800),
350 (4600); dH (500 MHz, CDCl3, Me4Si, 30 1C) 2.91 (6 H, s,
N(CH3)2), 6.88 (2 H, m, Ar-H), 7.20 (3 H, m, Ar-H), 7.28 (1 H,
Table 1 Crystal data for 2, 3 and 4
Compound
Formula
2
3
4
C
88H92N4O16S4 Á CHCl3 Á
C
136H136N8O24S8 Á CH3(CH2)2OH Á
C
18H17NO3S
0.5CH3CN
1729.79
1.5CH3CN
2644.69
Mr
Crystal size/mm
Crystal system
Space group
a/A
b/A
c/A
a/1
327.39
0.10 Â 0.10 Â 0.20
0.10 Â 0.10 Â 0.25
Monoclinic
C2/c (no. 15)
29.3447(9)
22.6903(5)
22.2725(7)
90
109.033(1)
90
14 019.2(7)
4
1.253
0.82 Â 0.75 Â 0.60
Monoclinic
P21/c (no. 14)
8.2180(4)
11.3823(4)
17.5254(9)
90
101.113(2)
90
1608.6(1)
4
1.352
Triclinic
ꢀ
P1 (no. 2)
16.2474(7)
16.2674(7)
20.5931(7)
83.540(3)
76.736(3)
71.072(2)
5006.9(3)
2
b/1
g/1
V/A3
Z
Dc/Mg mÀ3
1.147
0.234
1816
m/mmÀ1
F(000)
0.199
5576
0.216
688
y-range/1
3.69–24.45
31 628/16 391/0.141
6033/1040
1.024
0.127/0.338
1.058, –0.807
2.94–24.50
22 643/11 601/ 0.153
5201/853
1.044
0.091/0.2217
0.725, À0.330
2.97–26.00
5830/3141/0.0287
2330/210
1.047
0.0399/0.0831
0.190, À0.398
Refl. collected/unique/Rint
Refl. (I 4 2s(I)) used in refinement/parameters
Goodness-of-fit on F2
R/Rw
Largest diff. peak, hole/e AÀ3
ꢀc
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New J. Chem., 2007, 31, 370–376 | 375

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isotropically and hydrogen atom of the hydroxyl group was
not determined. Other X-ray data are presented in Table 1.
CCDC reference numbers 606001–606003.
8 A. Shivanyuk, E. Paulus, K. Rissanen, E. Kolehmainen and V.
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376 | New J. Chem., 2007, 31, 370–376