Guest inclusion in cyclic imides containing flexible tethers

Article abstract of DOI:10.1007/s10847-012-0196-7

Guest inclusion properties of two cyclic imides which have carboxylic acids connected through flexible tether, namely, 4-(1,3-dioxo-1,3-dihydro-isoindol-2- ylmethyl)-cyclohexanecarboxylic acid (1) and 4-(1,3-dioxo-1H,3H-benzo[de] isoquinolin-2-ylmethyl)-cyclohexanecarboxylic acid (2) are studied. The crystals of host 1 containing one molecule of 1, the crystals of 4,4′-bipyridine (bpy) cocrystal of 1 containing one molecule of 1 and half molecule of bpy (1a), the crystals of 1,4-dioxane solvate of 1 containing two molecule of 1 and one and half molecule of 1,4-dioxane (1b) and the crystals of quinoline solvate of 1 containing one molecule of 1 and one molecule of quinoline (1c) in their crystallographic asymmetric units are investigated. Intermolecular hydrogen bonded two dimensional (2D) sheet structure of 1 and 3D channel network of 1b are comprised of cyclic R ₂ ² (8) hydrogen bond motifs; whereas cleavage of dimeric carboxylic acid R ₂ ² (8) motifs occurs in the structures of 1a and 1c in which 3D host-guest networks are comprised of discrete O-H···N and cyclic R ₂ ² (7) interactions, respectively. Various types of weak interactions between the two symmetry nonequivalent host molecule are found to be responsible for the formation of channels (14 × 11 A) filled by guest 1,4-dioxane molecules in the crystal lattice of 1b. Two different solvates of 2 containing one molecule of 2 with a water molecule (2a) and one molecule of 2 with a quinoline molecule (2b) in their crystallographic asymmetric units, respectively, are also crystallized in different space groups. The quinoline molecules are held with host molecules by discrete O-H···N and C-H···O interactions and reside inside the voids formed by 3D repeated hexameric assemblies of host molecules in the crystal lattice of 2b.

Full text of DOI:10.1007/s10847-012-0196-7

J Incl Phenom Macrocycl Chem (2013) 76:269–281
DOI 10.1007/s10847-012-0196-7
ORIGINAL ARTICLE
Guest inclusion in cyclic imides containing flexible tethers
•
Devendra Singh Jubaraj B. Baruah
Received: 13 August 2011 / Accepted: 5 June 2012 / Published online: 23 June 2012
Ó Springer Science+Business Media B.V. 2012
Abstract Guest inclusion properties of two cyclic imides
which have carboxylic acids connected through flexible
tether, namely, 4-(1,3-dioxo-1,3-dihydro-isoindol-2-ylme-
thyl)-cyclohexanecarboxylic acid (1) and 4-(1,3-dioxo-1H,
3H-benzo[de]isoquinolin-2-ylmethyl)-cyclohexanecarbox-
ylic acid (2) are studied. The crystals of host 1 containing
one molecule of 1, the crystals of 4,40-bipyridine (bpy)
cocrystal of 1 containing one molecule of 1 and half
molecule of bpy (1a), the crystals of 1,4-dioxane solvate of
1 containing two molecule of 1 and one and half molecule
of 1,4-dioxane (1b) and the crystals of quinoline solvate of
1 containing one molecule of 1 and one molecule of
quinoline (1c) in their crystallographic asymmetric units
are investigated. Intermolecular hydrogen bonded two
dimensional (2D) sheet structure of 1 and 3D channel
network of 1b are comprised of cyclic R22(8) hydrogen
bond motifs; whereas cleavage of dimeric carboxylic acid
R22(8) motifs occurs in the structures of 1a and 1c in which
3D host–guest networks are comprised of discrete O–HꢀꢀꢀN
and cyclic R22(7) interactions, respectively. Various types of
weak interactions between the two symmetry nonequiva-
lent host molecule are found to be responsible for the
respectively, are also crystallized in different space groups.
The quinoline molecules are held with host molecules by
discrete O–HꢀꢀꢀN and C–HꢀꢀꢀO interactions and reside
inside the voids formed by 3D repeated hexameric
assemblies of host molecules in the crystal lattice of 2b.
Keywords Cyclic imides ꢀ Flexible tethered carboxylic
acids ꢀ Cocrystals ꢀ Channel formation ꢀ Guest inclusion ꢀ
Structural study
Introduction
Rational design of molecular assemblies using organic
functional solids to generate a variety of supramolecular
architectures has gained impressive research interest in the
field of crystal engineering and supramolecular chemistry
[1–10]. Host–guest crystalline materials are of special
interest in solid state due to their different physical prop-
erties from corresponding hosts [11–16] which makes them
useful as pharmaceutical applications [17–20]. In particu-
lar, the development of host–guest microporous materials
with channels and cavities are important because they have
possible applications in the areas of heterogeneous catal-
ysis, size selective separation, gas absorption and biomi-
metics [21–28]. In the field of supramolecular chemistry,
cyclic imide derivatives are proved as versatile scaffolds to
design the crystals of specific molecular arrangements
[29–39]. Cyclic imides attached to aromatic rings possess
dipolar nature and this effect provide extra stability to the
packing arrangement [40, 41]. The basic difference
between phthalimide and naphthalimide as hosts from
other related cyclic imides that are without an aromatic part
is that the former two are bipolar; can lead to interesting
layered structures. Attachment of a carboxylic acid through
˚
formation of channels (14 9 11 A) filled by guest 1,4-
dioxane molecules in the crystal lattice of 1b. Two dif-
ferent solvates of 2 containing one molecule of 2 with a
water molecule (2a) and one molecule of 2 with a quinoline
molecule (2b) in their crystallographic asymmetric units,
Electronic supplementary material The online version of this
article (doi:10.1007/s10847-012-0196-7) contains supplementary
material, which is available to authorized users.
D. Singh ꢀ J. B. Baruah (&)
Department of Chemistry, Indian Institute of Technology
Guwahati, Guwahati 781 039, Assam, India
e-mail: juba@iitg.ernet.in
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Chart 1 Structures of cyclic imide tethered carboxylic acids 1 and 2 and guest molecules
a hydrophobic part with flexibility to such part would
enhance possibilities to adopt different structures through
conformations guided by the competition between various
weak interactions. From this point of view, imides attached
to aromatic rings such as phthalimides, naphthalimides
draw special interest as they serve as model for under-
standing hierarchical weak interactions [42]. Extensive
study on supramolecular chemistry of derivatives of such
compounds is available [43–54], but the effect on use of
hydrophobic unit such as cyclohexyl group with confor-
mational flexibility coupled with imide group would be of
great interest [55]. Such study may also help to design new
hosts with specific properties as obtained from calix-arene
functionalized phthalimide derivatives [56–58].
through hydrogen bond, and also to interact with the cyclic
imide part by interactions such as hydrogen bonding
(strong or weak) or through an aromatic part by weak
C–Hꢀꢀꢀp or p–p interactions. Carboxylic acid groups can
form cyclic or discrete hydrogen bond motifs in several
ways when they interact to each other or with guest mole-
cules such as pyridine, quinoline and 1,4-dioxane [59–61].
Some of the host–guest cyclic or discrete hydrogen bond
motifs expected to observe from such study, are shown in
Chart 2. There are examples in literature in which macro-
cycles are functionalized across two ends and extended
structures are demonstrated, in such cases the advantages of
various hydrogen bond parameters based on distances and
angles are used to establish the formation of such structure,
here also we adopt a similar methodology by determining
the structures of various host–guest systems [62–64].
With this objective, we have studied the host–guest
chemistry of phthalimide and naphthalimide derivatives 1
and 2 which have intervening cyclohexyl moiety which can
have flexible geometry while anchoring imide and car-
boxylic acid functionality at 1,4 transpositions with guest
molecules like water, 1,4-dioxane, quinoline, 4,40-bipyri-
dine (Chart 1). The guest molecules chosen such that they
have the prerequisites to interact with carboxylic acids
Results and discussion
Two cyclic imide tethered with a cyclohexyl intervening
groups containing carboxylic acids, 1 and 2, are obtained
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271
in the lattice which further grow the dimension of supra-
molecular architecture from 1D zigzag chains to 2D sheets as
viewed along a-axis. Moreover, three different types of cyclic
hydrogen bond motifs, namely R22(8), R22(12) and R22(11)
which are formed by the combination of different intermo-
lecular hydrogen bonding interactions [60, 61], are also
observed in the lattice. Earlier in the case of N-phthaloylgly-
cine, we have demonstrated that the dimeric part can be
retained by phenolic guests such as resorcinol [52], such type
of assemblies in pyromellitic diimide help in molecular rec-
ognition of poly aromatic hydrocarbons [35].
The cocrystal 1a crystallized in monoclinic P21/n space
group and its crystallographic asymmetric unit consists of
one molecule of 1 and half molecule of bpy that lies on
inversion center (Fig. 2). In the structure of 1a, –COOH
groups of 1 do not enclose cyclic R22(8) hydrogen bond motif
but participate in discrete acceptor C–HꢀꢀꢀO (C4–H4AꢀꢀꢀO2;
˚
d
DꢀꢀꢀA 3.58 A, \D–HꢀꢀꢀA 148.42°) interaction with one of the
Chart 2 Some hydrogen bond motifs between carboxylic acid
groups and guest molecules
methylene hydrogen atoms of cyclohexane ring and discrete
˚
donor O–HꢀꢀꢀN (O1–H1ꢀꢀꢀN2; dDꢀꢀꢀA 2.74 A, \D–HꢀꢀꢀA
166.40°) interactions with nitrogen atoms of bpy molecules
by direct [1 ? 1] cyclo-condensation reactions of trans-4-
(aminomethyl)cyclohexanecarboxylic acid with corre-
sponding anhydrides. Crystallization of 1 under different
conditions led to the formation of four different types of
crystals of 1. The guest free crystals of 1 are obtained by
crystallizing 1 from dry ethanol solvent, crystals of co-
crystal 1a are obtained in a mixture of dry ethanol and dry
chloroform solvents containing 1 and bpy in 2:1 ratio, and
the crystals of two different solvates, 1c and 1d, are
obtained from 1,4-dioxane and quinoline solution of 1,
respectively (Scheme 1). All the parent compounds are
characterized by recording their NMR, IR, mass spectra.
The compositions of each solvates are ascertained from
their proton NMR integrations. Each of the compounds has
their characteristic IR signature of the parent compounds
and of the guest molecules.
˚
which makes discrete chains of 32.07 A length (measured
from the center of the aromatic imide ring to the center of the
aromatic imide ring) involving two molecules of 1 and one
molecules of bpy. The bpy molecules also interact to host
molecules via bifurcated C–Hꢀꢀꢀp (dC31ꢀꢀꢀp 3.61 and dC31ꢀꢀꢀp
˚
3.79 A) interactions and further connect the discrete chains
in another dimension of the lattice. Beside that, the host
molecules also assemble in the lattice through C–HꢀꢀꢀO
˚
(C13–H13ꢀꢀꢀO3; dDꢀꢀꢀA 3.18 A, \D–HꢀꢀꢀA 137.61°) and
˚
C–Hꢀꢀꢀp (dC8ꢀꢀꢀp 3.59 A) interactions to generate 3D network
structure of 1a where repeated tetrameric assemblies of host
molecules encapsulate the bpy molecules inside these
assemblies as viewed along a axis. Bipyridine or terpyridines
are used to make porous building blocks with aromatic
polycarboxylic acids [65–67]. We have also shown earlier
that different orientations of the weak interactions lead to
polymorphic structures in pyridine and quinoline solvates of
cyclic imide tethered carboxylic acids [37].
The compound 1 crystallized in monoclinic P21/c space
group, posseses one molecule of 1 in its crystallographic
asymmetric unit (Fig. 1). In the crystal lattice of 1, –COOH
groups interact to each other by the combination of two
ꢀ
The solvate 1b crystallized in Triclinic P1 space group.
˚
The asymmetric unit of this has two molecule of 1 with one
and half molecule of 1,4-dioxane. The 1,4-dioxane guest
molecule which appears as its half in the asymmetric unit,
lies on the inversion center and has no interactions with host
molecules or another guest molecule (Fig. 3). Another guest
molecule interacts with both the host molecules via two
donor–acceptor O–HꢀꢀꢀO (O2–H2ꢀꢀꢀO1; dDꢀꢀꢀA 2.66 A,
\D–HꢀꢀꢀA 177.54°) interactions creating 1D zigzag chains
˚
with lengths of 21.75 A (measured from the center of the
aromatic imide ring to the center of the aromatic imide ring).
The acceptor oxygen atom of –COOH group also partici-
pates in bifurcated hydrogen bonding and further interacts
with hydrogen atom of aromatic imide ring via C–HꢀꢀꢀO
˚
different discrete C–HꢀꢀꢀO (C12–H12ꢀꢀꢀO9; dDꢀꢀꢀA 3.28 A,
˚
˚
\D–HꢀꢀꢀA 130.41° and C20–H20ꢀꢀꢀO10; dDꢀꢀꢀA 3.48 A,
(C11–H11ꢀꢀꢀO1; dDꢀꢀꢀA 3.32 A, \D–HꢀꢀꢀA 177.54°) interac-
˚
\D–HꢀꢀꢀA 137.45°) interactions that facilitates again the
formation of cyclic R22(8) hydrogen bond between the two
–COOH groups of two symmetry nonequivalent host mole-
cules by the combination of two O–HꢀꢀꢀO (O1–H1ꢀꢀꢀO5;
tion. Two different C–HꢀꢀꢀO (C5–H5ꢀꢀꢀO3; dDꢀꢀꢀA 3.50 A,
˚
\D–HꢀꢀꢀA 156.35° and C8–H8BꢀꢀꢀO4; dDꢀꢀꢀA 3.58 A,
\D–HꢀꢀꢀA 159.12°) interactions between the carbonyl oxy-
gen atoms and methylene hydrogen atoms are also observed
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Scheme 1 Structure of host 1,
its bpy cocrystal 1a and its two
solvates 1b and 1c
Fig. 1 a A part of crystal
structure showing weak
interactions in 1. b Crystal
packing arrangement showing
2D sheets along a axis in the
structure of 1
˚
dDꢀꢀꢀA 2.66 A, \D–HꢀꢀꢀA 169.53° and O6–H6ꢀꢀꢀO2; dDꢀꢀꢀA
observed in the lattice. All these weak interactions found in
the crystal lattice of 1b, result in the construction of 3D host–
guest channel structure of 1b as viewed along a axis. The
2
˚
2.65 A, \D–HꢀꢀꢀA 173.79°) interactions. Two cyclic R2(10)
motifs also form in the lattice by the combination of two C–
˚
˚
channels of approximate 14 9 11 A dimensions are filled by
HꢀꢀꢀO (C11–H11ꢀꢀꢀO7; dDꢀꢀꢀA 3.41 A, \D–HꢀꢀꢀA 143.36°;
˚
C27–H27ꢀꢀꢀO4; dDꢀꢀꢀA 3.48 A, \D–HꢀꢀꢀA 146.19° and C14–
guest 1,4-dioxane molecules.
˚
H14ꢀꢀꢀO8; dDꢀꢀꢀA 3.49 A, \D–HꢀꢀꢀA 147.72° and C30–
The solvate 1c crystallized in Orthorhombic P212121
space group and its crystallographic asymmetric unit con-
sists of one molecule of 1 and one quinoline solvent mol-
ecule (Fig. 4). Due to the hierarchy of O–HꢀꢀꢀN interactions
over O–HꢀꢀꢀO interactions, the cyclic R22(8) hydrogen bond
motif is not observed in the crystal lattice of 1c and the
–COOH group of host molecule interacts with quinoline
molecule by a combination of O–HꢀꢀꢀN (O4–H4ꢀꢀꢀN3;
˚
H30ꢀꢀꢀO3; dDꢀꢀꢀA 3.42 A, \D–HꢀꢀꢀA 124.86°) interactions
exist between the carbonyl oxygen atoms and hydrogen atom
of aromatic imide ring of the host. Apart from that, one of the
carbonyl oxygen atoms of a host molecule and one of the
carboxyl oxygen atoms of another host molecule participate
in bifurcated hydrogen bonding and simultaneously interact
˚
via two C–HꢀꢀꢀO (C22–H22ꢀꢀꢀO4; dDꢀꢀꢀA 3.52 A, \D–HꢀꢀꢀA
˚
˚
144.09° and C3–H3AꢀꢀꢀO6; dDꢀꢀꢀA 3.41 A, \D–HꢀꢀꢀA
dDꢀꢀꢀA 2.74 A, \D–HꢀꢀꢀA 177.83°) and C–HꢀꢀꢀO (C23–
134.56°) interactions making a cyclic R22(14) hydrogen bond
motif in the lattice. Moreover, the pꢀꢀꢀp interactions between
the aromatic imide rings of one of the host molecules are also
H23ꢀꢀꢀO3; dDꢀꢀꢀA 3.28 A, \D–HꢀꢀꢀA 125.90°) interactions
˚
making a cyclic R22(7) hydrogen bond motif. The quinoline
molecule further interact to each other via C–Hꢀꢀꢀp
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273
Fig. 2 a Weak interactions between the host and guest bpy molecules in the structure of 1a. b 3D tetrameric channel like assemblies of host
molecules encapsulating bpy molecules (red) along the a-axis. c Space filling model after removal of bpy molecules. (Color figure online)
˚
(dC19ꢀꢀꢀp 3.58 A) interaction which makes a discrete struc-
ture of 27.72 A length (measured from the center of the
differed to each other (Fig. 5). The differences observed in
the position and intensity of the diffraction peaks of these
various crystalline forms are due to the presence of solvent
or other addition molecules in the crystal lattice of host.
The peaks obtained in the PXRD patterns of 1 and its other
forms correlate well with the simulated peaks of single
crystal X-ray structures (Figure S3–S6).
˚
aromatic imide ring to the center of the aromatic imide
ring) involving two host and two quinoline molecules. The
quinoline molecules also interact with the –COOH group
and aromatic imide ring of the host molecule via C–HꢀꢀꢀO
˚
(C22–H22ꢀꢀꢀO3; dDꢀꢀꢀA 3.18 A, \D–HꢀꢀꢀA 131.75°) and
˚
C–Hꢀꢀꢀp (dC26ꢀꢀꢀp 3.62 A) interactions, respectively, making
The crystals of two different solvates of 2, namely 2a
and 2b, in 1:1 host to guest ratio are obtained from DMF
and quinoline solution of 2, respectively, and their struc-
tures are also determined (Scheme 2).
a 1D host–guest structural arrangement. Beside this, the host
molecules also interact to each other via C–HꢀꢀꢀO (C12–
˚
H12ꢀꢀꢀO2; dDꢀꢀꢀA 3.23 A, \D–HꢀꢀꢀA 137.75°) and C–Hꢀꢀꢀp
˚
(dC8ꢀꢀꢀp 3.62 A) interactions which assembles the structure as
Crystal structure analysis revealed that solvate 2a
ꢀ
crystallized in triclinic P1 space group, included one
3D host–guest layered arrangement in which a single layer
of quinoline molecules takes the position between the two
double layer of host molecules as viewed along a-axis.
Thermogravimetric analysis (Figure S1 and S2) of 1b
reveals 18 % weight loss of a three-fourth equivalent of
1,4-dioxane molecule in the temperature range 40–90 °C
(calculated: 18.6 %) whereas 30 % weight loss of one
equivalent of quinoline molecule occurs from 1c in the
temperature range 75–150 °C (calculated: 31 %). Powder
X-ray diffraction (PXRD) patterns for host 1 and its dif-
ferent host–guest crystalline forms, 1a, 1b and 1c are
molecule of 2 and one molecule of solvent water in its
crystallographic asymmetric unit (Fig. 6). In the crystal
lattice, cyclic O–HꢀꢀꢀO interactions between the –COOH
groups of host molecules are absent due to the presence of
water molecules which are engaged in discrete O–HꢀꢀꢀO
hydrogen bonds with host molecules and act as both donor
and acceptor. The oxygen atom of water molecule involves
bifurcated acceptor hydrogen bonding via two different
˚
interactions, namely, O–HꢀꢀꢀO (O1–H1ꢀꢀꢀO5; dDꢀꢀꢀA 2.66 A,
\D–HꢀꢀꢀA 172.57°) and C–HꢀꢀꢀO (C16–H16ꢀꢀꢀO5; dDꢀꢀꢀA
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J Incl Phenom Macrocycl Chem (2013) 76:269–281
Fig. 3 a Weak interactions in
the host–guest assembly of 1b.
b Channel formation in the
assembly of host and 1,4-
dioxane molecules (along
a axis). c Space filling model
after removal of 1,4-dioxane
molecules residing inside the
channels
Fig. 4 a Weak interactions between the host and quinoline molecules in 1c. b Crystal packing of 1c, showing the arrangement of host and
quinoline molecules in the crystal lattice (along a axis)
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275
solvent quinoline in its crystallographic asymmetric unit
(Fig. 7). Similar to quinoline solvate 1c, the –COOH groups of
the host molecules do not enclose cyclic O–HꢀꢀꢀO hydrogen
bond formation and interact apparently with guest quinoline
molecules via both discrete donor O–HꢀꢀꢀN (O3–H3ꢀꢀꢀN2;
˚
dDꢀꢀꢀA 2.67 A, \D–HꢀꢀꢀA 171.88°) and discrete acceptor
˚
C–HꢀꢀꢀO (C24–H24ꢀꢀꢀO3; dDꢀꢀꢀA 3.46 A, \D–HꢀꢀꢀA 169.82°)
interactions forming cyclic R44(14) hydrogen bond motif in the
lattice which involves two quinoline and two host molecules.
Another cyclic R33(12) hydrogen bond motif is also formed in
the lattice by the combinations of three different interactions,
namely host–guest O3–H3ꢀꢀꢀN2, host–guest C30–H30ꢀꢀꢀO2
˚
(dDꢀꢀꢀA 3.18 A, \D–HꢀꢀꢀA 131.45°) and host–host C8–H8ꢀꢀꢀO4
˚
(dDꢀꢀꢀA 3.33 A, \D–HꢀꢀꢀA 155.09°) interactions, which
involves one quinoline and two host molecules. The host
molecules also assemble in the lattice through C–Hꢀꢀꢀp (dC16ꢀꢀꢀp
˚
3.60 A) interactions experienced between the hydrogen atoms
of cyclohexane ring and aromatic imide ring. No weak inter-
actions among the quinoline molecules are observed in the
lattice of 2b. All these host–host and host–guest interactions
result in the construction of repeated 3D hexameric assemblies
of host molecules allowing the formation of large voids in the
lattice which are filled by quinoline molecules as viewed along
a axis. The quinoline molecules generally form strong cyclic
R22(7) and R22(8) hydrogen bonds with –COOH functional
groups in the lattice [37, 38]. This is valid in the case of solvate
1c. Exception is observed that quinoline molecules are held
with the host molecules through discrete donor–acceptor
interactions in the lattice of 2b.
Fig. 5 PXRD patterns of 1, 1a, 1b and 1c
Thermogravimetric studies on two different solvates of 2
(Figure S3 and S4) show that solvate 2a losses 4.8 % weight
in the temperature range 97–154 °C which corresponds to
the loss of one equivalent of water molecule (calculated:
5.2 %). Another solvate 2b also shows 22 % weight loss of
one equivalent of quinoline molecule in the temperature
range 60–145 °C (calculated: 27.6 %). Significant differ-
ences are observed in the PXRD patterns of guest free
crystalline form of host 2 and its two solvates, 2a and 2b,
which are crystallized in different space groups (Fig. 8).
These differences can be accounted for the inclusion of
different solventsin the crystal lattice of host. PXRD patterns
of all three different crystalline materials are in good corre-
lation with the simulated patterns of single crystal X-ray
structures determined at 298 K.
Scheme 2 Structure of host 2 and its two solvates
˚
3.48 A, \D–HꢀꢀꢀA 144.39°) interactions and both the
hydrogen atoms engage in donor hydrogen bonding with
two carbonyl oxygen atoms of host molecule through
˚
O–HꢀꢀꢀO (O5–H5AꢀꢀꢀO3; dDꢀꢀꢀA 2.83 A, \D–HꢀꢀꢀA 171.43°
˚
and O1–H1ꢀꢀꢀO5; dDꢀꢀꢀA 2.79 A, \D–HꢀꢀꢀA 168.96°) inter-
actions making two different cyclic R44(26) hydrogen bond
motifs in the lattice. The host molecules also interact with
˚
Conclusions
each other via C–HꢀꢀꢀO (C13–H13ꢀꢀꢀO2; dDꢀꢀꢀA 3.23 A,
\D–HꢀꢀꢀA 149.53°) interaction which overall makes a 2D
channel like host–guest network of 2a in the crystal lattice
as viewed along a-axis.
The role of weak interactions between the hosts and guests
(solvents or other additional molecules) in the formation of
different cyclic hydrogen bond motifs in different structures of
hosts 1 and 2 is discussed. The structural features of 1 and 1b
reveals the formation of cyclic R22(8) motifs by intermolecular
The solvate 2b crystallized in monoclinic P21/c space
group, included one molecule of 2 and one molecule of
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Fig. 6 a A part of crystal structure showing host–guest weak interactions in 2a. b Crystal packing arrangement showing the channel like
structure of 2a
acidꢀꢀꢀacid interactions whereas the structures of 1a and 1c are
devoid of these R22(8) interactions and are governed by discrete
O–HꢀꢀꢀN interactionsor cyclic R22(7) interactions. Formation of
repeated 3D tetrameric assemblies of host molecules occurs in
1a which encapsulate the additional bpy molecules inside
were recorded using a Varian Mercury plus 400 MHz
instrument. Chemical shifts were reported in parts per mil-
lion (ppm) relative to internal TMS (0 ppm). Electrospray
ionization mass (ESI–MS) spectra were recorded on a
Waters (Micromass MS Technologies) Q-Tof Premier mass
spectrometer. PXRD data were collected on a Bruker D2
diffractometer in Bragg–Brentano h–h geometry with Cu Ka
˚
themselves whereas 3D channels of approximate 14 9 11 A
dimension accommodate the guest 1,4-dioxane molecules in
the crystal lattice of 1b. In the structure of 1b, two symmetry
nonequivalent molecules of host are also responsible for the
formation of three types of cyclic hydrogen bond motifs,
namely, R22(8), R22(10) and R22(14), through different weak
interactions. The discrete O–HꢀꢀꢀO interactions observed
between the water and host molecules are sufficient enable to
cleave the dimeric assembly of carboxylic acid moiety in the
structure of 2a and these water molecules occupy the positions
inside the 2D channels like network of host molecules. Instead
of making conventionally observed cyclic R22(7) or R22(8)
hydrogen bond motifs, the quinoline molecules are held in the
repeated hexameric assemblies by discrete O–HꢀꢀꢀN and
C–HꢀꢀꢀO interactions in the structure of 2b, which allows the
creation of large solvent voids.
˚
radiation (k = 1.5418 A) on a glass surface of an air-dried
sample using a secondary curved graphite monochromator.
Diffraction patterns were collected over a 2h range of 5–50°
at a scan rate of 2° min-1. Thermogravimetric analyses
(TGA) were performed on a Mettler Toledo TGA/SDTA
851e module. Samples were placed in open alumina pans in
the temperature range 25–300 °C and were purged with a
stream of dry N2 flowing at 100 mL min-1
.
Structure determination
The X-ray single crystal diffraction data were collected at
˚
296 K with MoKa radiation (k = 0.71073 A) using a Bru-
ker Nonius SMART CCD diffractometer equipped with a
graphite monochromator. The SMART software was used
for data collection and also for indexing the reflections and
determining the unit cell parameters; the collected data
were integrated using SAINT software. The structures were
solved by direct methods and refined by full-matrix least-
squares calculations using SHELXTL software [68]. All
the non-H atoms were refined in the anisotropic approxi-
mation against F2 of all reflections. The H-atoms, except
those attached to nitrogen and oxygen atoms were placed at
their calculated positions and refined in the isotropic
Experimental section
General
All reagents and solvents were obtained from commercial
sources. The IR spectra were recorded on a Perkin-Elmer-
Spectrum One FT-IR spectrometer with KBr disks in the
range 4,000–400 cm-1. The 1HNMR and 13CNMR spectra
123

J Incl Phenom Macrocycl Chem (2013) 76:269–281
277
Fig. 7 a Host–guest weak
interactions in a part of crystal
structure of 2b. b 3D hexameric
assemblies of host molecules
(red) encapsulating quinoline
molecules (blue) along the
a axis. c Space filling model
after removal of the quinoline
molecules inside the voids.
(Color figure online)
approximation; those attached to nitrogen and oxygen were
located in the difference Fourier maps, and refined with
isotropic displacement coefficients. Crystallographic data
collection was done at room temperature and the data are
tabulated in Table 1. The CCDC numbers of the com-
pounds 1, 1a, 1b, 1c, 2a and 2b are 826469–826474.
dried in open air. The crystals of solvent free host 1 were
obtained by recrystallizing it from dry ethanol in a sealed test
tube. Yield: 85 %; IR (KBr, cm-1): 3406 (w), 2915 (m), 2854
(m), 2528 (w), 1769 (w), 1712 (s), 1596 (s), 1538 (w), 1433
(m), 1399 (s), 1360 (m), 1331 (m), 1304 (m), 1249 (m), 1223
(m), 1197 (s), 1158 (m), 1061 (m), 983 (w), 805 (m), 772 (m).
1H NMR (400 MHz, CDCl3):7.82(dd, 2H, J = 2.8 Hz), 7.69
(dd, 2H, J = 3.2 Hz), 3.52 (d, 2H, J = 6.8 Hz), 2.24 (t, 1H,
J = 12.0 Hz), 2.00 (d, 2H, J = 10.8 Hz), 1.78 (d, 3H,
J = 6.8 Hz), 1.37 (q, 2H, J = 8.4 Hz), 1.07 (q, 2H,
J = 10.4 Hz). 13C NMR (CDCl3): 168.9, 150.4, 145.9, 134.1,
132.2, 123.4, 121.8, 43.9, 43.2, 36.6, 30.0, 28.5. ESI–MS:
288.156 [M ? H?].
Synthesis and characterization of compounds
and their solvates
Compound 1
A solution of phthalic anhydride (0.740 g, 5 mmol) and trans-
4-(aminomethyl)cyclohexanecarboxylic acid (0.785 g,
5 mmol) in acetic acid (20 mL) was refluxed for 3 h. The
reaction mixture was cooled to room temperature, poured into
ice cooled water (50 mL) and stirred for 15 min. A white
coloredcrystallineproductwasobtained. Thiswasfilteredand
Compound 1a
The solvent free crystals of 1 (0.287 g, 1 mmol) were
dissolved again in dry ethanol and a pre prepared solution
123

278
J Incl Phenom Macrocycl Chem (2013) 76:269–281
cm-1): 3459 (w), 2932 (m), 2849 (m), 2528 (w), 1925 (w),
1770 (w), 1713 (s), 1431 (w), 1396 (m), 1357 (m), 1329
(m), 1305 (m), 1251 (m), 1222 (w), 1209 (m), 1058 (m),
1
984 (w), 950 (w), 927(w), 816 (m), 788 (w), 722 (m). H
NMR (400 MHz, CDCl3): 8.92 (d, 2H, J = 3.2 Hz), 8.16
(dd, 2H, J = 8.0 Hz), 7.81 (m, 2H), 7.70 (m, 2H), 7.54 (t,
1H, J = 7.6 Hz), 7.40 (dd, 2H, J = 4.0 Hz), 3.52 (d, 2H,
J = 6.4 Hz), 2.26 (t, 1H, J = 12.0 Hz), 2.04 (d, 2H,
J = 12.4 Hz), 1.78 (d, 3H, J = 10.8 Hz), 1.40 (q, 2H,
J = 12.0 Hz), 1.06 (q, 2H, J = 12.4 Hz).
Compound 2
A solution of 1,8-naphthalic anhydride (0.990 g, 5 mmol)
and trans-4-(aminomethyl)cyclohexanecarboxylic acid
(0.785 g, 5 mmol) in N,N-dimethylformamide (15 mL)
was refluxed for 5 h. The reaction mixture was cooled to
room temperature, poured into ice cooled water (30 mL)
and stirred for 15 min. A brown colored precipitate of the
product was formed, which was filtered and air dried.
Yield: 78 %; IR (KBr, cm-1): 3501 (s), 2946 (s), 2855 (m),
1725 (s), 1695 (s), 1651 (s), 1590 (m), 1442 (w), 1389 (w),
1354 (m), 1316 (w), 1255 (m), 1237 (m), 1198 (m), 1176
(m), 1074 (w), 1030 (w), 973 (w), 935 (w), 776 (m).
1HNMR (400 MHz, CDCl3): 8.57 (d, 2H, J = 7.2 Hz),
8.19 (d, 2H, J = 8.0 Hz), 7.73 (d, 2H, J = 7.2 Hz), 4.05
(d, 2H, J = 6.8 Hz), 2.26 (t, 1H, J = 9.2 Hz), 2.00 (d, 2H,
J = 13.2 Hz), 1.82 (d, 3H, J = 14.0 Hz), 1.34 (q, 2H,
J = 12.0 Hz), 1.18 (q, 2H, J = 11.2 Hz). 13CNMR
(CDCl3): 164.8, 134.2, 131.6, 127.2, 122.8, 45.9, 43.01,
36.2, 30.1, 28.4. ESI–MS: 338.185 [M ? H?].
Fig. 8 PXRD patterns of 2, 2a, and 2b
of bpy (0.078 g, 0.5 mmol) in dry chloroform was layered
over the ethanol solution in a sealed test tube. Colorless
needle shape crystals of 1a were obtained after five days.
IR (KBr, cm-1): 3463 (w), 2932(m), 2856 (m), 1773 (w),
1705 (s), 1400 (m), 1366 (m), 1336 (m), 1263 (m), 1211
(m), 1189 (w), 1153 (w), 1054 (m), 951 (w), 933 (w), 719
1
(m), 713 (m). H NMR (400 MHz, CDCl3): 8.72 (d, 2H,
J = 4.8 Hz), 7.82 (dd, 2H, J = 3.2 Hz), 7.68 (dd, 2H,
J = 4.0 Hz), 7.52 (d, 2H, J = 6.0 Hz), 3.52 (d, 2H,
J = 6.8 Hz), 2.26 (t, 1H, J = 12.8 Hz), 2.02 (d, 2H,
J = 11.6 Hz), 1.80 (d, 3H, J = 10.0 Hz), 1.40 (q, 2H,
J = 10.4 Hz), 1.08 (q, 2H, J = 8.8 Hz).
Compound 2a
The crystals of the solvate 2a were obtained from a solu-
tion of compound 2 from any of the solvents like ethanol,
isopropanol, t-butanol, N,N-dimethylformamide, dimeth-
ylsulphoxide and pyridine as brown colored blocks. IR
(KBr, cm-1): 3504 (s), 2946 (s), 2855 (m), 1724 (s), 1695
(s), 1650 (s), 1621 (s), 1589 (s), 1441 (w), 1346 (m), 1316
(m), 1254 (m), 1237 (m), 1198 (m), 1176 (m), 1074 (w),
917 (w), 776 (w). 1HNMR (400 MHz, CDCl3): 8.57
(d, 2H, J = 7.6 Hz), 8.19 (d, 2H, J = 8.4 Hz), 7.73 (d, 2H,
J = 8.0 Hz), 4.05 (d, 2H, J = 7.2 Hz), 2.26 (t, 1H, J =
12.4 Hz), 2.00 (d, 2H, J = 11.2 Hz), 1.82 (d, 3H,
J = 12.8 Hz), 1.34 (q, 2H, J = 10.4 Hz), 1.18 (q, 2H,
J = 11.2 Hz).
Compound 1b
The crystals of solvate 1b were obtained as white blocks from a
solution of compound 1 in 1,4-dioxane. IR (KBr, cm-1): 3456
(w), 2924 (m), 2859 (m), 1770 (w), 1709 (s), 1415 (m), 1390
(m), 1366 (m), 1336 (m), 1255 (m), 1211 (m), 1196 (w), 1173
(w), 1054 (m), 986 (w), 950 (w), 930 (w), 770 (m), 722 (m). 1H
NMR (400 MHz, CDCl3): 8.71 (d, 6H, J = 4.4 Hz), 7.81 (m,
2H), 7.67 (m, 2H), 7.53 (d, 6H, J = 4.4 Hz), 3.51 (d, 2H,
J = 6.8 Hz), 2.25 (t, 1H, J = 12.0 Hz), 2.00 (d, 2H,
J = 10.8 Hz), 1.78 (d, 3H, J = 10.8 Hz), 1.37 (q, 2H,
J = 12.4 Hz), 1.07 (q, 2H, J = 11.2 Hz).
Compound 2b
Compound 1c
The solvate 2b was obtained by crystallization of com-
pound 2 from quinoline solution as brown block crystals.
IR (KBr, cm-1): 3503 (w), 2925 (m), 2851 (m), 2485 (w),
The solvate 1c was crystallized as brown colored blocks
from the quinoline solution of compound 1. IR (KBr,
123

J Incl Phenom Macrocycl Chem (2013) 76:269–281
279
Table 1 Crystallographic parameters of 1, 1a, 1b, 1c, 2a and 2b
Compound No.
1
1a
1b
1c
2a
2b
Formulae
C16 H17 N O4
287.31
C21 H21 N2 O4
365.40
C38 H46 N2 O11
706.77
C25 H24 N2 O4
416.46
C20 H21 N O5
355.38
C29 H26 N2 O4
466.52
Formula. wt.
Crystal system
Space group
Monoclinic
P21/c
Monoclinic
P21/n
Triclinic
Orthorhombic
P212121
5.4464(4)
11.6278(8)
33.471(2)
90.00
Triclinic
Monoclinic
P21/c
ꢀ
P1
ꢀ
P1
˚
a (A)
5.5389(9)
26.406(4)
10.8187(15)
90.00
5.3895(3)
11.4669(6)
29.4655(16)
90.00
6.9998(7)
13.6084(14)
19.931(2)
74.897(7)
84.667(7)
80.376(7)
1804.8(3)
2
7.0784(4)
9.0908(6)
14.4330(8)
101.630(4)
99.886(4)
103.335(4)
861.64(9)
2
5.12940(10)
18.4728(4)
25.1209(5)
90.00
˚
b (A)
˚
c (A)
a (°)
b (°)
c (°)
116.329(9)
90.00
93.998(3)
90.00
90.00
91.5870(10)
90.00
90.00
3
˚
V (A )
1418.2(4)
4
1816.56(17)
4
2119.7(3)
4
1593.12(9)
4
Z
Density (Mg-3
Abs. Coeff. (mm-1
F(000)
)
1.346
1.336
1.301
1.305
1.370
1.302
)
0.097
0.093
0.096
0.089
0.099
0.087
608
772
752
880
376
984
Total no. of reflections
Reflections, I [ 2r(I)
Max. 2h (°)
7,729
24,847
16,749
16,715
10,403
18,030
1,428
2,986
3,339
2,473
1,794
1,860
50.00
56.76
45.06
49.98
50.00
44.12
Ranges (h, k, l)
-6 B h B 6
-31 B k B 27
-11 B l B 11
81.9
-7 B h B 7
-12 B k B 15
-39 B l B 32
99.5
-7 B h B 7
-14 B k B 14
-21 B l B 21
98.9
-6 B h B 6
-13 B k B 13
-39 B l B 35
99.2
-8 B h B 8
-10 B k B 10
-17 B l B 17
99.5
-5 B h B 5
-19 B k B 19
-26 B l B 26
99.5
Completeness to 2h (%)
Data/restraints/parameters
Goof (F2)
2,048/0/190
1.045
4,525/1/245
1.058
4,694/0/462
1.078
3,677/0/281
1.047
3,019/0/244
1.081
2,943/0/317
0.891
R indices [I [ 2r(I)]
R indices (all data)
0.0663
0.0543
0.0689
0.0524
0.0589
0.0466
0.0831
0.0867
0.0930
0.0854
0.0960
0.0718
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