Difference in guest-inclusion abilities of anti- and syn-rotamers

Article abstract of DOI:10.1039/b002220i

Guest inclusion abilities of two rotamers, anti- and syn-N,N′-bis-(2-tert-butylphenyl)naphthalene-1,4,5,8-tetra-carboxylic diimides 1 and 2, were investigated. Rotamers 1 and 2 were synthesised from 2-tert-butylaniline and naphthalene-1,4,5,8-tetracarboxylic dianhydride and separated by conventional column chromatography on silica gel. Recrystallisation of 1 from chloroform in the presence of a guest molecule (3 mole equivalents) was performed, and 15 guest molecules were included with a variety of host:guest ratios, 1:1 (chloroform, pyridine, 4-picoline, benzene, quinoline, diphenylacetylene, naphthalene, and p-toluidine), 1:2 (phenol, 3-ethylphenol, 4-methoxyphenol, indole, 5-methylindole, and tetrathiafulvalene), and 1:4 (benzothiazole). In contrast, 2 showed no inclusion of guest molecules under the same conditions as those applied to 1. In order to investigate the intermolecular interaction in the crystalline state of 1, 2 and 1·(indole)₂, X-ray diffraction of single crystals was measured and these structures were compared.

Full text of DOI:10.1039/b002220i

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Difference in guest-inclusion abilities of anti- and syn-rotamers
Keiki Kishikawa,*a Chiaki Iwashima,a Shigeo Kohmoto,a Kentaro Yamaguchib and
Makoto Yamamotoa
1
a Department of Materials Technology, Faculty of Engineering, Chiba University,
1-33 Yayoi-cho, Inage-ku, Chiba 263-8522, Japan
b Chemical Analysis Center, Chiba University, 1-33 Yayoi-cho, Inage-ku, Chiba 263-8522,
Japan
Received (in Cambridge, UK) 20th March 2000, Accepted 15th May 2000
Published on the Web 22nd June 2000
Guest inclusion abilities of two rotamers, anti- and syn-N,NЈ-bis-(2-tert-butylphenyl)naphthalene-1,4,5,8-tetra-
carboxylic diimides 1 and 2, were investigated. Rotamers 1 and 2 were synthesised from 2-tert-butylaniline and
naphthalene-1,4,5,8-tetracarboxylic dianhydride and separated by conventional column chromatography on silica
gel. Recrystallisation of 1 from chloroform in the presence of a guest molecule (3 mole equivalents) was performed,
and 15 guest molecules were included with a variety of host:guest ratios, 1:1 (chloroform, pyridine, 4-picoline,
benzene, quinoline, diphenylacetylene, naphthalene, and p-toluidine), 1:2 (phenol, 3-ethylphenol, 4-methoxyphenol,
indole, 5-methylindole, and tetrathiafulvalene), and 1:4 (benzothiazole). In contrast, 2 showed no inclusion of guest
molecules under the same conditions as those applied to 1. In order to investigate the intermolecular interaction in the
crystalline state of 1, 2 and 1ؒ(indole)2, X-ray diffraction of single crystals was measured and these structures were
compared.
Introduction
Recently, clathrate compounds have been utilised for studying
molecular channels,1 organic networks,2 molecular recognition3
and stereoselective reactions.4 In these studies, conformation of
thehostmoleculewasoneofthemostimportantfactorsaffecting
the guest-inclusion ability, and flexible changes into a suit-
able host were required to generate a stable host–guest complex.
An example of molecular recognition in solution using two
stable rotamers was reported by Rebek, Jr., and co-workers.
They described the difference in inclusion abilities between the
two rotamers and found no difference in host:guest ratio; both
rotamers gave 1:2 clathrate compounds with ethyl acetate.5 On
the other hand, the construction of differently hydrogen-
bonded networks using the same guest was reported by
Miyata and co-workers, in polymorphic cholic acid crystals, in
which the conformational change of the host was observed,
depending on the specific polymorphs, in their X-ray struc-
Fig. 1 Rotational isomerisation changes the capacities of the space
above the π-system.
tures.6 However, there is no report on guest-inclusion ability
dependent on the host conformation in clathrate chemistry. In
this paper, we report on the difference in the inclusion abilities
between the two stable rotamers, anti- and syn-N,NЈ-bis-(2-
tert-butylphenyl)naphthalene-1,4,5,8-tetracarboxylic diimides
the N–C single bond. The rotational barrier is supposed to be
more than 28 kcal molϪ1.†5,7c
Fig. 2 shows the space-filling models8 (side view) of 1 and 2,
1 and 2. This is the first example of a clathrate host which
and the dimensions (a–e) of the concave surfaces are indicated.
exhibits quite different guest-inclusion ability from its con-
Isomer 1 [Fig. 2(a)] has a space on both sides of the naph-
formational isomer. Compound 1 has a broad inclusion ability,
thalene ring. The length a (4.0 Å) is longer than the thickness
though its isomer 2 does not include any guest molecules.
of aromatic π-planes (3.55 Å9), and c (6.2 Å) is similar to the
The N-phenylimide derivatives are easily available and are
width of a benzene ring. Therefore, concave surfaces of 1
should be suitable for inclusion of aromatic compounds. While,
useful compounds for studying conformational isomerisation
because of their simple structure and thermal stability.7 In
in the case of 2 [Fig. 2(b)], the width of concave surface d (4.1 Å)
order to examine the different inclusion abilities, the conformers
is too narrow to include an aromatic compound using π–π
1 and 2 are designed as follows. 1) A large electron-deficient
interaction, dimension b is shorter than the thickness of aro-
π-system is introduced at its centre so that strong π–π inter-
matic π-planes although the length e (7.5 Å) is sufficient for
action with electron-rich aromatic compounds is possible
inclusion. From these observations, the isomer 2 is unsuitable
(Fig. 1). 2) N-(2-Substituted phenyl) groups are put at both
for inclusion of a guest molecule.
edges of the π-system to change the capacity of the space above
the π-system. 3) Each of the rotamers 1 and 2 is stabilised by the
large rotational barrier of the N-2-tert-butylphenyl groups with
† 1 cal = 4.184 J.
DOI: 10.1039/b002220i
J. Chem. Soc., Perkin Trans. 1, 2000, 2217–2221
This journal is © The Royal Society of Chemistry 2000
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Table 1 Included guest molecules and host:guest ratios in the clath-
rate host 1
Ratio of host:guesta
1:1
Guest molecules (HOMO energy level, eVb)
chloroform (Ϫ12.9), pyridine (Ϫ9.9), 4-
picoline (Ϫ9.9), benzene (Ϫ9.7), quinoline
(Ϫ9.2), diphenylacetylene (Ϫ8.8), naph-
thalene (Ϫ8.7), p-toluidine (Ϫ8.4)
1:2
1:4
phenol(Ϫ9.1),3-ethylphenol(Ϫ9.0),4-meth-
oxyphenol (Ϫ8.6), indole (Ϫ8.4), 5-methyl-
indole (Ϫ8.4), tetrathiafulvalene (Ϫ8.1)
benzothiazole (Ϫ9.0)
1
a The ratios were determined by H NMR spectroscopy and elemental
analysis. b The HOMO energy levels were calculated by AM1.
Fig. 2 Space-filled models of 1 (a) and 2 (b).
Results and discussion
Condensation of 2-tert-butylaniline and naphthalene-1,4,5,8-
tetracarboxylic dianhydride by heating at 120 ЊC in DMF in the
presence of acetic acid for 3 h gave the two stable rotational
isomers, anti- and syn-N,NЈ-bis-(2-tert-butylphenyl)naph-
thalene-1,4,5,8-tetracarboxylic diimide (1 and 2) which were
separated by conventional column chromatography on silica gel
and elution with benzene–chloroform (Scheme 1). Recrystal-
Fig. 3 Crystal structure of 1. Hydrogen atoms are omitted for clarity.
(a) CH ؒ ؒ ؒ π interaction between the carbonyl and tert-butyl groups.
O(2) ؒ ؒ ؒ C(17*) = 3.60, O(2) ؒ ؒ ؒ C(20*) = 3.63 Å. (b) CH ؒ ؒ ؒ O inter-
action of the carbonyl group with the hydrogen of the naphthalene
ring. O(1) ؒ ؒ ؒ C(11*) = 3.39 Å.
quinoline, diphenylacetylene, naphthalene, and p-toluidine,
which have no acidic proton (the atomic net charge10 < ϩ0.181)
in the molecule and/or a low HOMO energy level,10 are
included with a host:guest ratio 1:1. A host:guest ratio of 1:2
was observed with phenol, 3-ethylphenol, 4-methoxyphenol,
indole, 5-methylindole, and tetrathiafulvalene, which have an
acidic proton (the atomic net charge: ϩ0.215 to ϩ0.247) in the
molecule and/or a high HOMO energy level. Furthermore,
benzothiazole was included with a ratio 1:4. From the results
of inclusion experiments, chloroform has the lowest insertion
ability in this series.
The guest-inclusion ability is dramatically changed by the
rotational isomerisation of the host molecule. In contrast to
the effective inclusion exhibited by 1, the isomer 2 showed no
inclusion of guest molecules under the same conditions as those
applied to 1.
In order to investigate the intermolecular interaction in the
crystalline state of 1, X-ray diffraction of a single crystal was
measured. Inspection of the crystal structure of 1 [Fig. 3(a)]
revealed that only the following weak CH ؒ ؒ ؒ O interactions
[<4 kJ molϪ1 11a 2–20 kJ molϪ1 (ref. 11b)] were responsible for
,
Scheme 1 Synthetic route to the rotamers.
creation of the network structure. CH ؒ ؒ ؒ O interactions
between the carbonyl oxygen and tert-butyl group [O(2) ؒ ؒ ؒ
H–C(17*) and O(2) ؒ ؒ ؒ H–C(20*)] were observed [O(2) ؒ ؒ ؒ
C(17*): 3.60 Å, O(2) ؒ ؒ ؒ C(20*): 3.63 Å]. The interaction was
estimated to be weak since the observed distances were longer
than the typical interatomic distance between an oxygen and a
lisation of 1 and 2 from benzene–chloroform gave yellow and
pale red prismatic crystals, respectively.
We attempted to make clathrate compounds of 1 with vari-
ous aromatic molecules by recrystallisation of 1 from chloro-
form in the presence of a guest molecule (3 mole equivalents).
As a result, 15 guest molecules were included in a variety of
host:guest ratios, 1:1, 1:2, and 1:4, which were determined
carbon atom, which is in the range 3.20–4.0011a (3.00–4.0011b
)
Å. Another CH ؒ ؒ ؒ O interaction occurs between the other
carbonyl oxygen and the naphthalene hydrogen [O(1) ؒ ؒ ؒ
H–C(11*), Fig. 3(b)], which is supposed to be stronger than the
above mentioned [O(1) ؒ ؒ ؒ C(11*): 3.39 Å]. Thus, CH ؒ ؒ ؒ O
1
by H NMR spectroscopy and elemental analysis (Table 1).
Chloroform, pyridine, 4-methylpyridine (4-picoline), benzene,
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Fig. 5 Crystal structure of 2. Hydrogen atoms are omitted for clarity.
(a) CH ؒ ؒ ؒ O interaction between the carbonyl and tert-butyl groups.
O(2**) ؒ ؒ ؒ C(32) = 3.77, O(2**) ؒ ؒ ؒ C(33) = 3.66, O(2**) ؒ ؒ ؒ C(34) =
3.80, O(4) ؒ ؒ ؒ C(22*) = 3.64, O(4) ؒ ؒ ؒ C(24*) = 3.62 Å. (b) CH ؒ ؒ ؒ O
(ؒؒؒؒؒؒؒ) interaction between the molecules. O(1) ؒ ؒ ؒ C(11*) = 3.26,
O(3*) ؒ ؒ ؒ C(6) = 3.31 Å.
Fig. 4 Crystal structure of 1ؒ(indole)2. Hydrogen atoms are omitted
for clarity. (a) π ؒ ؒ ؒ π (ԽԽԽԽԽ) and CH ؒ ؒ ؒ π interactions (------) between 1
and indole. Distance between each atom of the indole molecule and the
naphthalene plane is in the range 3.3–3.7 Å. C(16) ؒ ؒ ؒ C(24*) = 3.91,
C(16) ؒ ؒ ؒ C(25*) = 3.84 Å. (b) NH ؒ ؒ ؒ O (ؒؒؒؒؒؒؒ) CH ؒ ؒ ؒ O (------)
hydrogen bonding. O(2) ؒ ؒ ؒ N(2*) = 2.80, O(1) ؒ ؒ ؒ C(23*) = 3.19 Å.
must be large, because several hydrogen atoms of the tert-butyl
groups simultaneously interact with a carbonyl oxygen. The
four molecules are strongly assembled into the pinwheel shape
and this interaction makes a rigid two-dimensional network in
the ab plane using interaction with two of the four carbonyl
groups in the molecule. Furthermore, the molecules are stacked
in the direction of the c axis [Fig. 5(b)]. The other two carbonyl
oxygen atoms have a CH ؒ ؒ ؒ O interaction with the hydrogen
atoms at the naphthalene ring [O(1) ؒ ؒ ؒ H(1*)–C(11*) and
O(3*) ؒ ؒ ؒ H(4)–C(6)]. The interactions are estimated to be
extremely strong from their short interatomic distances
[O(1) ؒ ؒ ؒ C(11*): 3.26, O(3*) ؒ ؒ ؒ C(6): 3.31 Å]. The parallel
geometry of the molecules is effective for making the strong
CH ؒ ؒ ؒ O hydrogen bonding. The above-mentioned two-
dimensional networks are firmly bonded to each other by
interaction is the main force that maintains the crystal structure
of 1. Accordingly, the weak network of 1 implies it has the
possibility to include guest molecules, if the interaction between
the host and guest is stronger than that between the host
molecules themselves.
The following features are characteristic in the X-ray crystal
structure of 1ؒ(indole)2 complex (Fig. 4), which gave the most
stable single crystal in this series of clathrate compounds.
Two indole molecules lie on both sides of the naphthalene ring
of 1, and the tert-butyl hydrogens of 1 are in contact with the
π-face of the indole molecule [C(16) ؒ ؒ ؒ C(24*): 3.91, C(16) ؒ ؒ ؒ
C(25*): 3.84 Å, Fig. 4(a)]. The crystal colour of 1ؒ(indole)2 com-
plex is dark red due to the charge-transfer complexation of
indole and the electron-poor naphthalene ring of 1. The dis-
tance between each atom of the indole molecule and the naph-
thalene plane is in the range of 3.2–3.7 Å. A UV spectrum of a
chloroform solution of indole and 1 showed a charge-transfer
band at λmax 407 nm. Typical hydrogen bonding [2.5–3.211a
(2.50–3.0011b Å, the energy range is 4–15 kcal molϪ1 (ref.
11a)) (20–40 kJ molϪ1 (ref. 11b))] and CH ؒ ؒ ؒ O hydrogen bond-
ing were observed between N(2*)–H and O(2) [N(2*) ؒ ؒ ؒ O(2):
2.80 Å], and between C(23**)–H and O(1) [C(23**) ؒ ؒ ؒ O(1):
3.19 Å] in the crystal [Fig. 4(b)]. The stabilisation energy from
the charge transfer and the hydrogen bonding in this complex
is larger than that from the CH ؒ ؒ ؒ O interactions in the host
crystal. This energy difference is the driving force for the con-
struction of the clathrate compounds of 1 with the guests.
Mixing of indole (white powder) and 1 (pale yellow powder)
gave a red solid, which showed peaks of 1ؒ(indole)2 complex in
the powder X-ray diffraction. This means that the indole mole-
cules insert into the crystal lattice of 1 to produce 1ؒ(indole)2
complex in the solid phase because of the stabilisation from the
complexation.
strong CH ؒ ؒ ؒ O interactions to generate
a rigid three-
dimensional network.
From these X-ray structural studies, we propose the follow-
ing explanation for the difference between the inclusion abilities
of isomers 1 and 2. The clathrate host 1 includes the various
guest molecules using strong interactions: NH ؒ ؒ ؒ O᎐C or
᎐
OH ؒ ؒ ؒ O᎐C hydrogen bonding and/or charge-transfer
᎐
complexation, because the network in the host crystal is only
constructed from the weak CH ؒ ؒ ؒ O interactions. In other
words, the network of the host–guest complex is more rigid and
stable than that in crystal of 1.12 Furthermore, the spaces on
both faces of the naphthalenetetracarboxylic diimide of 1,
produced by an anti-conformation of the two tert-butyl groups,
are suitable for the size of the guest molecules. In the case of
isomer 2, the syn-conformation of the two tert-butyl groups
makes different kinds of spaces on each side of the π-system
which are not an appropriate size for guest inclusion, and
isomer 2 generates the rigid three-dimensional network by itself
in its crystal. Accordingly, crystallisation of only compound
2 proceeds, regardless of the presence of other aromatic
compounds.
Conclusions
On the other hand, the single-crystal X-ray crystallography
of 2 (Fig. 5) showed a quite different network structure com-
pared with that of 1. The four molecules in the unit cell form a
pinwheel shape using the several CH ؒ ؒ ؒ O interactions between
the two carbonyl oxygen atoms and hydrogen atoms of the two
tert-butyl groups; [O(4) ؒ ؒ ؒ H–C(22*), O(4) ؒ ؒ ؒ H–C(24*),
O(2**) ؒ ؒ ؒ H–C(32), O(2**) ؒ ؒ ؒ H–C(33), and O(2**) ؒ ؒ ؒ
H–C(34).O(4) ؒ ؒ ؒ C(22*):3.64,O(4) ؒ ؒ ؒ C(24*):3.62,O(2**) ؒ ؒ ؒ
C(32): 3.77, O(2**) ؒ ؒ ؒ C(33): 3.66, and O(2**) ؒ ؒ ؒ C(34):
3.80 Å, Fig. 5(a)]. Each of the CH ؒ ؒ ؒ O hydrogen bonds is
weak. However, the total amount of the interaction energy
As the results of this study, we found the following facts. 1) The
guest-inclusion ability of a clathrate host can be changed by its
rotational isomerisation, if the conformations are fixed during
the crystal-packing process. 2) In this system, the charge-trans-
fer and hydrogen bonding are the driving force for generating
the 1:2 complex of 1. 3) A good fit between the shape of guest
and the available space above the π-system of the host is
important for complexation with aromatic guests. 4) The
network formed by CH ؒ ؒ ؒ O interactions in the crystal of 2
is more stable than that in the crystal of 1.
J. Chem. Soc., Perkin Trans. 1, 2000, 2217–2221
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anti-N,NЈ-Bis-(2-tert-butylphenyl)naphthalene-1,4,5,8-tetracarb-
oxylic diimide 1ؒ4-picoline 1:1 complex
Experimental
1H NMR spectra were obtained on a JEOL LA400 spec-
trometer. Microanalysis was performed with a Perkin-Elmer
240 elemental analyser. Infrared spectroscopy was performed
with Hitachi I-2000 spectrometer. Melting points were
measured on a Yanako MO-S3. Single crystal X-ray diffraction
was measured on a Rigaku AFC7 diffractometer. In micro-
Found: C, 75.68; H, 5.95; N, 6.71. Calc. for C40H37N3O4ؒ
0.5H2O: C, 75.93; H, 6.05; N, 6.64%.
anti-N,NЈ-Bis-(2-tert-butylphenyl)naphthalene-1,4,5,8-tetracarb-
oxylic diimide 1ؒbenzene 1:1 complex
analytical data, compound
2 and inclusion compounds
Found: C, 78.54; H, 5.90; N, 4.18. Calc. for C40H36N2O4ؒ
0.2H2O: C, 78.46; H, 5.99; N, 4.57%.
of 1 with guest molecules (chloroform, pyridine, 4-picoline,
benzene, quinoline, diphenylacetylene, naphthalene, phenol, 3-
ethylphenol and benzothiazole) include small amounts of water
as hygroscopic water.
anti-N,NЈ-Bis-(2-tert-butylphenyl)naphthalene-1,4,5,8-tetracarb-
oxylic diimide 1ؒquinoline 1:1 complex
Found: C, 77.93; H, 5.51; N, 6.29. Calc. for C43H37N3O4ؒ
0.2H2O: C, 77.85; H, 5.68; N, 6.33%.
Synthesis of anti- and syn-N,NЈ-bis-(2-tert-butylphenyl)naph-
thalene-1,4,5,8-tetracarboxylic diimides (1 and 2)
2-tert-Butylaniline (0.58 cm3, 3.7 mmol), naphthalene-1,4,5,8-
tetracarboxylic acid dianhydride (500 mg, 1.8 mmol), and acetic
acid (3.9 cm3, 68 mmol) were heated in DMF (10 cm3) for 5 h
at 120 ЊC. The solution was cooled to room temperature,
diluted with chloroform (100 cm3), and washed with water
(3 × 100 cm3). The organic solution was concentrated in
vacuo to give a red solid. The products were separated by
column chromatography on silica gel and elution with
benzene–chloroform to give the two isomers [1; 0.33 g (35%),
2; 0.29 g (30%)].
anti-N,NЈ-Bis-(2-tert-butylphenyl)naphthalene-1,4,5,8-tetracarb-
oxylic diimide 1ؒdiphenylacetylene 1:1 complex
Found: C, 80.46; H, 5.42; N, 3.98. Calc. for C48H40N2O4ؒ
0.3H2O: C, 80.72; H, 5.73; N, 3.92%.
anti-N,NЈ-Bis-(2-tert-butylphenyl)naphthalene-1,4,5,8-tetra-
carboxylic diimide 1ؒnaphthalene 1:1 complex
Found: C, 78.42; H, 5.56; N, 4.40. Calc. for C44H38N2O4ؒ
0.8H2O: C, 78.50; H, 5.93; N, 4.16%.
anti-N,NЈ-Bis-(2-tert-butylphenyl)naphthalene-1,4,5,8-tetracarb-
oxylic diimide 1ؒp-toluidine 1:1 complex
Found: C, 77.23; H, 5.95; N, 6.35. Calc. for C41H39N3O4: C,
77.21; H, 6.16; N, 6.59%.
Compound 1. Pale yellow crystals (Found: C, 76.98; H, 5.60;
N, 5.13. Calc. for C34H30N2O4: C, 76.96; H, 5.70; N, 5.28%);
mp >300 ЊC (from toluene–chloroform); νmax (KBr)/cmϪ1 2970
(C–H), 1720 (C᎐O), 1680 (C᎐O), 1450, 1350, 770; δ (400 MHz;
᎐
᎐
H
CDCl3) 1.31 (s, 18H), 7.02 (dd, J 8.0, 1.5 Hz, 2H), 7.38 (ddd,
J 8.0, 7.5, 1.5 Hz, 2H), 7.49 (ddd, J 8.2, 7.5, 1.5 Hz, 2H), 7.70
(dd, J 8.2, 1.5 Hz, 2H), 8.87 (s, 4H).
anti-N,NЈ-Bis-(2-tert-butylphenyl)naphthalene-1,4,5,8-tetracarb-
oxylic diimide 1ؒphenol 1:2 complex
Found: C, 75.78; H, 5.83; N, 3.80. Calc. for C46H42N2O6ؒ
0.5H2O: C, 75.91; H, 5.95; N, 3.85%.
Crystal data.‡ C34H30N2O4, M = 530.62, yellow, prismatic,
monoclinic, a = 11.061(2), b = 8.602(1), c = 14.653(3) Å,
β = 95.80(2)Њ, V = 1387.1(4) Å3, T = 296 K, space group P21/n
anti-N,NЈ-Bis-(2-tert-butylphenyl)naphthalene-1,4,5,8-tetracarb-
oxylic diimide 1ؒ3-ethylphenol 1:2 complex
(no. 14), Z = 2, µ(CuKα) = 7.61 cmϪ1
, 2362 reflections
measured, 2234 unique (Rint = 0.027) which were used in all
calculations. The final R and wR were 0.050 and 0.053.
Found: C, 75.51; H, 6.46; N, 3.51. Calc. for C50H50N2O6ؒ
1.1H2O: C, 75.56; H, 6.62; N, 3.52%.
Compound 2. Clear red crystals (Found: C, 74.98; H, 5.59; N,
5.24. Calc. for C34H30N2O4ؒH2O: C, 74.97; H, 5.54; N, 5.04%);
mp >300 ЊC (from chloroform); νmax (KBr)/cmϪ1 2970, 1680,
1450, 1350, 775 cmϪ1; δH (400 MHz; CDCl3) 1.30 (s, 18H), 7.06
(dd, J 7.7, 1.4 Hz, 2H), 7.39 (ddd, J 7.7, 7.7, 1.5 Hz, 2H), 7.49
(ddd, J 8.2, 7.7, 1.4 Hz, 2H), 7.71 (dd, J 8.2, 7.7, 1.4 Hz, 2H),
8.87 (s, 4H).
anti-N,NЈ-Bis-(2-tert-butylphenyl)naphthalene-1,4,5,8-tetracarb-
oxylic diimide 1ؒ4-methoxyphenol 1:2 complex
Found: C, 74.08; H, 5.88; N, 3.49. Calc. for C48H46N2O8: C,
74.02; H, 5.92; N, 3.60%.
anti-N,NЈ-Bis-(2-tert-butylphenyl)naphthalene-1,4,5,8-tetracarb-
oxylic diimide 1ؒindole 1:2 complex
Found: C, 78.51; H, 5.80; N, 7.33. Calc. for C50H44N4O4: C,
78.30; H, 5.75; N, 7.14%.
Crystal data.‡ C34H30N2O4, M = 530.62, red, prismatic,
monoclinic, a = 9.326(1), b = 16.890(3), c = 18.301(4) Å, β =
102.06Њ, V = 2819.1(9) Å3, T = 296 K, space group P21/n (no.
14), Z = 4, µ(CuKα) = 6.59 cmϪ1, 4669 reflections measured,
4369 unique (Rint = 0.028) which were used in all calculations.
The final R and wR were 0.062 and 0.063.
Crystal data.‡ C50H44N4O4, M = 764.92, red, prismatic,
monoclinic, a = 11.262(2), b = 11.874(9), c = 14.727(3) Å, β =
95.28(2)Њ, V = 1961.1000(4) Å3, T = 296 K, space group P21/c
(no. 14), Z = 2, µ(MoKα) = 0.83 cmϪ1
, 2097 reflections
measured, 1654 reflections which were used in all calculations.
The final R and wR were 0.060 and 0.066.
anti-N,NЈ-Bis-(2-tert-butylphenyl)naphthalene-1,4,5,8-tetracarb-
oxylic diimide 1ؒchloroform 1:1 complex
Found: C, 64.67; H, 4.81; N, 4.31. Calc. for C35H31N2O4ؒ
0.2H2O: C, 64.32; H, 4.84; N, 4.29%.
anti-N,NЈ-Bis-(2-tert-butylphenyl)naphthalene-1,4,5,8-tetracarb-
oxylic diimide 1ؒ5-methylindole 1:2 complex
Found: C, 78.76; H, 6.10; N, 7.07. Calc. for C52H48N4O4: C,
78.71; H, 5.99; N, 6.98%.
anti-N,NЈ-Bis-(2-tert-butylphenyl)naphthalene-1,4,5,8-tetracarb-
oxylic diimide 1ؒpyridine 1:1 complex
Found: C, 76.35; H, 5.69; N, 6.41. Calc. for C39H35N3O4ؒ
0.4H2O: C, 75.93; H, 5.85; N, 6.81%.
anti-N,NЈ-Bis-(2-tert-butylphenyl)naphthalene-1,4,5,8-tetracarb-
oxylic diimide 1ؒtetrathiafulvalene 1:2 complex
Found: C, 59.18; H, 4.13; N, 2.90. Calc. for C46H38N2O4S8: C,
58.82; H, 4.08; N, 2.98%.
‡ CCDC reference number 207/436.
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J. Chem. Soc., Perkin Trans. 1, 2000, 2217–2221

View Article Online
119, 2592; (e) K. Tanaka, A. Moriyama and F. Toda, J. Org. Chem.,
anti-N,NЈ-Bis-(2-tert-butylphenyl)naphthalene-1,4,5,8-tetracarb-
oxylic diimide 1ؒbenzothiazole 1:4 complex
1997, 62, 1192.
4 (a) F. Toda, H. Miyamoto, H. Koshima and Z. Urbanczyk-
Lipkowska, J. Org. Chem., 1997, 62, 9261; (b) F. Toda, H. Miyamoto
and H. Koshima, J. Am. Chem. Soc., 1996, 118, 11315.
5 K. D. Shimizu, T. M. Dewey and J. Rebek, Jr., J. Am. Chem. Soc.,
1994, 116, 5145.
Found: C, 68.69; H, 4.60; N, 7.66. Calc. for C62H50N6O4S4ؒ
0.5H2O: C, 68.93; H, 4.76; N, 7.78%.
6 K. Nakano, K. Sada and M. Miyata, Chem. Commun., 1996, 989.
7 (a) K. Kishikawa, R. Takeuchi, S. Kohmoto, M. Yamamoto, K.
Yamaguchi and K. Yamada, J. Chem. Soc., Perkin Trans. 1, 1998,
1143; (b) K. Kishikawa, K. Yoshizaki, M. Yamamoto, S. Kohmoto,
K. Yamaguchi and K. Yamada, J. Chem. Soc., Perkin Trans. 1, 1997,
1233; (c) K. Kishikawa, I. Tsuru, S. Kohmoto, M. Yamamoto and
K. Yamada, Chem. Lett., 1994, 1605; (d) A. Srivastava, V. Srivastava
and S. Verma, J. Org. Chem., 1994, 59, 3560; (e) D. P. Curran,
S. J. Geib and N. C. DeMello, J. Am. Chem. Soc., 1994, 116,
3131.
References
1 (a) K. Sada, N. Shiomi and M. Miyata, J. Am. Chem. Soc.,
1998, 120, 10543; (b) M. Gdaniec and T. Polonski, J. Am. Chem.
Soc., 1998, 120, 7353; (c) N. Hayashi, K. Kuruma, Y. Mazaki,
T. Imakubo and K. Kobayashi, J. Am. Chem. Soc., 1998, 120, 3799;
(d) K. A. Udachin and J. A. Ripmeester, J. Am. Chem. Soc., 1998,
120, 1080.
2 (a) K. Kishikawa, S. Tsubokura, S. Kohmoto, M. Yamamoto and
K. Yamaguchi, J. Org. Chem., 1999, 64, 7568; (b) K. Biradha,
D. Dennis, V. A. MacKinnon, C. V. Krishnamohan Sharma and
M. J. Zaworotko, J. Am. Chem. Soc., 1998, 120, 11894; (c) H. J. Choi
and M. P. Suh, J. Am. Chem. Soc., 1998, 120, 10622; (d) P.
Bhyrappa, S. R. Wilson and K. S. Suslick, J. Am. Chem. Soc., 1997,
119, 8492; (e) K. Biradha and M. J. Zaworotko, J. Am. Chem. Soc.,
1998, 120, 6431; ( f ) J. A. Swift, A. M. Pivovar, A. M. Reynolds and
M. D. Ward, J. Am. Chem. Soc., 1998, 120, 5887; (g) P. Brunet,
M. Simard and J. D. Wuest, J. Am. Chem. Soc., 1997, 119, 2737;
(h) G. B. Gardner, Y.-H. Kiang, S. Lee, A. Asgaonkar and
D. Venkataraman, J. Am. Chem. Soc., 1996, 118, 6946.
8 Chem3D (Cambridge software corporation) representations of the
most stable forms for compounds 1 and 2.
9 A. Bondi, J. Phys. Chem., 1964, 68, 443.
10 The AM1 semiempirical molecular orbital method implemented by
WinMOPAC version 1.0a (Fujitsu Limited) was used for all
calculations. M. J. S. Dewar, E. G. Zoebisch, E. F. Healy and J. J. P.
Stewart, J. Am. Chem. Soc., 1985, 107, 3902.
11 (a) G. R. Desiraju and T. Steiner, The Weak Hydrogen Bond, in
Structural Chemistry and Biology, Oxford University Press, Oxford,
1999; (b) G. A. Jeffrey, An Introduction to Hydrogen Bonding,
Oxford University Press, New York, 1997; (c) G. R. Desiraju and
C. V. Krishnamohan Sharma, in The Crystal as a Supramolecular
Entity, ed. G. R. Desiraju, John Wiley and Sons, New York, 1996.
12 R. Thaimattam, D. S. Reddy, F. Xue, T. C. W. Mak, A. Nangia and
G. R. Desiraju, J. Chem. Soc., Perkin Trans. 2, 1998, 1783.
3 (a) T. Dewa, K. Endo and Y. Aoyama, J. Am. Chem. Soc., 1998, 120,
8933; (b) L. R. MacGillivray and J. L. Atwood, J. Am. Chem. Soc.,
1997, 119, 6931; (c) D. R. Evans, T. Drovetskaya, R. Bau,
C. A. Reed and P. D. W. Boyd, J. Am. Chem. Soc., 1997, 119, 3633;
(d) L. R. MacGillivray and J. L. Atwood, J. Am. Chem. Soc., 1997,
J. Chem. Soc., Perkin Trans. 1, 2000, 2217–2221
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