Face-to-face structures formed by 3D hydrogen-bonded networks of tris(4-carboxyphenyl)cyclotriguaiacylene

Article abstract of DOI:10.1007/s10870-012-0355-0

A novel tris(4-carboxyphenyl)cyclotriguaiacylene 2 was synthesized by hydrolysis of a novel tris[(4-(methoxycarbonyl) phenyl]cyclotriguaiacylene. The structure was determined by ¹H NMR, ¹³C NMR and mass spectroscopic techniques. The crystal structure of 2 was shown by X-ray crystallography to have a face-to-face structure of a pair of molecules of 2. The structure was constructed from 3D hydrogen-bonded network structure. Springer Science+Business Media, LLC 2012.

Full text of DOI:10.1007/s10870-012-0355-0

J Chem Crystallogr (2012) 42:1075–1079
DOI 10.1007/s10870-012-0355-0
COMMUNICATION
Face-to-Face Structures Formed by 3D Hydrogen-Bonded
Networks of Tris(4-carboxyphenyl)cyclotriguaiacylene
•
Yoshimasa Makita Tomofumi Danno
•
•
Tomoyuki Fujita Keisuke Ikeda
•
•
Shin-ichi Fujiwara Akiya Ogawa
Received: 5 April 2012 / Accepted: 4 August 2012 / Published online: 23 August 2012
Ó Springer Science+Business Media, LLC 2012
Abstract A novel tris(4-carboxyphenyl)cyclotriguaiacylene
2 was synthesized by hydrolysis of a novel tris[(4-(methoxy-
carbonyl)phenyl]cyclotriguaiacylene. The structure was
acceptor. For example, Hardie and co-workers [35–44]
have widely reported CTV-based ligands that can be
coordinated to transition metals to form coordination
polymers or discrete metallo-supramolecular assemblies.
Zheng and co-workers [45] have recently reported a CTV-
based metal–organic nanotube. However, CTV fragments
themselves rarely act as hosts for small organic molecules
in a manner analogous to the ubiquitous calixarenes.
Therefore, the host–guest chemistry of CTV fragments is
mainly focused on covalently linked cage-like molecules
such as cryptophanes [22–27] and hemicryptophanes
[46–55]. Cryptophanes, which are constructed from two
CTV fragments covalently preorganized in a face-to-face
fashion, exhibit good binding properties for small guest
molecules. Although a number of crystalline hydrogen-
bonded assemblies featuring CTV fragments arranged in a
back-to-back fashion have been reported [56–59], docu-
mentation of hydrogen-bonded assemblies of CTV-related
host molecules arranged in a face-to-face fashion is limited
[60]. We report herein face-to-face structures formed by
3D hydrogen-bonding networks with the related ligand
tris(4-carboxyphenyl)cyclotriguaiacylene 2 (Fig. 1).
1
determined by H NMR, 13C NMR and mass spectroscopic
techniques. The crystal structure of 2 was shown by X-ray
crystallography to have a face-to-face structure of a pair of
molecules of 2. The structure was constructed from 3D
hydrogen-bonded network structure.
Keywords Cyclotriguaiacylene Á Cyclotriveratrylene Á
Hydrogen-bonded networks Á Face-to-face structure
Introduction
The design of an infinite network structure by using
coordinate and/or hydrogen-bonding interactions has
attracted considerable interest in the area of crystal engi-
neering and host–guest chemistry [1–21]. In particular, the
developments of network structures that include molecular
cages is expected for multiple inclusion materials [22–27].
Cyclotriveratrylene (CTV) is a well-known macrocyclic
host with a rigid pyramidally shaped crown conformation
that gives it a shallow bowl-shaped cavity [28–34]. CTV
can be incorporated into 1D, 2D, or 3D network structures
either as a chelating ligand, or as a hydrogen bond
Experimental Section
Synthesis of tris[(4-(methoxycarbonyl)phenyl]
cyclotriguaiacylene 1
Y. Makita (&) Á S. Fujiwara
Department of Chemistry, Osaka Dental University,
8-1 Kuzuhahanazono-cho, Hirakata, Osaka 573-1121, Japan
e-mail: makita@cc.osaka-dent.ac.jp
Cyclotriguaiacylene (409 mg, 1.00 mmol), Cs2CO3 (1.45 g,
4.45 mmol), and methyl 4-fluorobenzoate (915 mg,
5.94 mmol) were dissolved in DMF (2.0 mL) under nitrogen
atmosphere. The resulting heterogeneous mixture was stirred
at120 °C for 24 h. The residue was taken upwitha solutionof
3 M HCl and chloroform. The separated organic layer was
T. Danno Á T. Fujita Á K. Ikeda Á A. Ogawa
Department of Applied Chemistry, Graduate School
of Engineering, Osaka Prefecture University, 1-1 Gakuen-cho,
Nakaku, Sakai, Osaka 599-8531, Japan
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MeO
OMe
O
O
O
OMe
COOH
COOH
HOOC
Fig. 1 Chemical structure and X-ray crystal structure of a tris(4-carboxyphenyl)cyclotriguaiacylene molecule 2. Hydrogen atoms have been
omitted for clarity
Measurements
washed with brine, dried over anhydrous NaSO4, filtered, and
evaporated to dryness. The residue was purified by silica gel
column chromatography by using chloroform–ethyl acetate-
hexane (5:1:4) as the eluent to give 243 mg (30 %) of racemic
tris[(4-(methoxycarbonyl)phenyl]cyclotriguaiacylene as a
white solid. Mp 135.1–136.4 °C; 1H NMR (CDCl3,
400 MHz, rt): d 3.62 (d, 3H, J = 13.6 Hz), 3.68 (s, 9H), 3.88
(s, 9H), 4.79 (d, 3H, J = 14.0 Hz), 6.84 (s, 3H), 6.91 (d, 6H,
J = 8.8 Hz), 7.05 (s, 3H), 7.95 (d, 6H, J = 8.4 Hz); 13C
NMR (CDCl3, 100 MHz, rt): d 36.6, 52.1, 56.2, 114.6, 116.2,
123.3, 124.2, 131.7, 132.1, 137.1, 142.4, 150.4, 162.2,
166.8 ppm. HRMS (ESI-TOF) Calcd. for C48H42Na1O12:
833.2574 ([M?Na]?); Found: 833.2573 [M?Na]?.
X-ray diffraction data on single crystals were collected on a
Rigaku R-AXIS RAPID diffractometer with graphite
˚
monochromated Mo Ka radiation (k = 0.71075 A) at
123 K. The structure was solved by a direct method with
SHELXS-97. The disordered solvent molecules were
removed by the SQUEEZE routine (PLATON) and the
outputs from the SQUEEZE calculations were attached to a
CIF file [61]. All non-hydrogen atoms were refined
anisotropically. The hydrogen atoms were attached in a
riding model. They were included at their calculated
positions.
Synthesis of tris(4-carboxyphenyl)cyclotriguaiacylene 2
Results and Discussion
A mixture of tris[(4-(methoxycarbonyl)phenyl]cyclotr-
iguaiacylene (120 mg, 0.15 mmol) and NaOH (25.1 mg,
0.63 mmol) in methanol (1.0 mL) was refluxed for 7 h and
then allowed to cool to ambient temperature. 3 M HCl was
added to the reaction mixture and the organic layer was
extracted by ethyl acetate three times. The separated
organic layer was washed with brine, dried over anhydrous
NaSO4, filtered, and evaporated to dryness. The residue
was precipitated in hexane and filtered off to give 98.4 mg
(86 %) of racemic 2 as a white solid. Mp 267.7–268.9 °C
1H NMR (CD3OD, 400 MHz, rt): d 3.63 (s, 9H), 3.65–3.67
(brs, 3H), 4.78–4.82 (brs, 3H), 6.83 (d, 6H, J = 8.4 Hz),
7.07 (s, 3H), 7.23 (s, 3H), 7.90 (d, 6H, J = 8.0 Hz); 13C
NMR (CD3OD, 100 MHz, rt): d 36.7, 56.4, 115.8, 116.7,
124.8, 125.2, 132.7, 133.9, 139.1, 143.1, 151.6, 163.9,
169.5 ppm. HRMS (ESI-TOF) Calcd. for C45H36Na1O12:
791.2104 ([M?Na]?); Found: 791.2106 [M?Na]?.
Tris[(4-(methoxycarbonyl)phenyl]cyclotriguaiacylene
1
was prepared by a nucleophilic aromatic substitution
(SNAr) reaction onto cyclotriguaiacylene in 30 % yield as
a racemic compound. The hydrolysis reaction of 1
Crystallization
Slow evaporation of a chloroform and methanol solution of
2 resulted in single crystals suitable for X-ray crystal
structure analysis.
Fig. 2 Stick representation of the face-to-face structure of a pair of
molecules of (M,M)-2 and a disordered solvent molecule. Hydrogen
atoms have been omitted for clarity
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J Chem Crystallogr (2012) 42:1075–1079
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1H NMR spectrum. The diameter of the cavity of the
Table 1 Crystal data of tris(4-carboxyphenyl)cyclotriguaiacylene 2
˚
face-to-face structure was about 10.2 A. The disordered
Empirical formula
Formula weight
Crystal system
Space group
Z
C45 H36O12
768.77
solvent molecule was observed in the cavity of the face-to-
face structure and removed by the SQUEEZE routine
(PLATON). The crystal data of 2 are shown in Table 1.
The crystalline structure of 2 belongs to the trigonal system
and space group R-3c. The two CTV fragments were
interdigitated with each other. All of these structures were
Trigonal
R-3c
12
˚
a (A)
14.7891(3)
14.7891(3)
57.3970(11)
90.0000
90.0000
120.0000
10871.9(4)
0.71075
0.0722
˚
b (A)
˚
stabilized through CH–p interactions [d(CÁÁÁC=C) = 3.8 A]
˚
c (A)
between a phenyl ring of the carboxy phenyl group and a
˚
a (deg)
b (deg)
c (deg)
methoxy carbon. The CH–O interaction [d(CÁÁÁO) = 3.8 A]
was observed in a carboxy group and the phenyl group of
CTV. Crystal lattice structure of 2 was shown in Fig. 3. The
racemic face-to-face structures of (P,P)- or (M,M)-structures
were alternately-stacked along the c axle. The face-to-face
structures were stabilized through p–p interactions
3
˚
V(A )
l(Mo Ka) (mm-1
)
R1
wR2
Goodness of fit (GOF) for F2
0.2087
˚
[d(C=CÁÁÁC=C) = 3.4 A] between phenyl rings of CTV
1.075
fragments and hydrogen-bonded networks of carboxy groups.
To clarify the 3D hydrogen-bonded networks of carboxy
groups, the crystal structures which have been omitted a
pair of face-to-face structures of 2 was shown in Fig. 4.
The intermolecular hydrogen bonds were stabilized by six
furnished tris[(4-(methoxycarbonyl)phenyl]cyclotriguaiac-
ylene 2 in 86 % yield. The resulting racemic 2 was char-
acterized by 1H and 13C NMR spectroscopy and
electrospray ionization (ESI) mass spectroscopy. The
analysis data were in full agreement with the structures
presented. Colorless crystals of 2Ásolvent were obtained
from slow evaporation of a chloroform/methanol solution
of 2. The crystal structure of 2Ásolvent was determined by
single-crystal X-ray diffraction techniques. The funda-
mental face-to-face structure of a pair of molecules of 2
and a disordered solvent molecule are shown in Fig. 2. The
composition of 2Ásolvent was estimated 2Á(0.5CHCl3) by
˚
carboxyl groups (the OÁÁÁO distances are 2.69 and 2.99 A,
respectively). The 3D hydrogen-bonded networks were
probably concerned in densely-stacked face-to-face struc-
tures of 2.
Conclusions
We have directly synthesized novel densely-stacked face-
to-face structures formed by 3D hydrogen-bonded
Fig. 3 Crystal lattice of 2.
a Packing in layers in the ab
plane. b Packing in layers in the
ac plane
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J Chem Crystallogr (2012) 42:1075–1079
Fig. 4 Stick representation of crystal structure of 2. a A pair molecules of face-to-face structures. b Details of the hydrogen-bonding interactions
between six carboxylic acids
14. Kobayashi K, Sato A, Sakamoto S, Yamaguchi K (2003) J Am
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networks involving 2. The results reported herein provide
an unusual example of a face-to-face arrangement of CTV
15. Saied O, Maris T, Wuest JD (2003)
125:14956–14957
J Am Chem Soc
fragments. The inner cavity of face-to-face structures can
trap small molecules. Further research on chiral crystalline
molecular flasks chemistry is currently under way by using
the stacked face-to-face structure as a platform.
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Acknowledgments We thank Mr. S. Katao for his support in car-
rying out the X-ray crystal structure analysis at the Nara Institute of
Science and Technology under the Kyoto Advanced Nanotechnology
Network program. This work was supported by a Grant-in-Aid for
Young Scientists (B) (23792302).
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