Structural studies on solvates of cyclic imide tethered carboxylic acids with pyridine and quinoline

Article abstract of DOI:10.1021/cg900938x

Structures of eight solvates of cyclic imide tethered carboxylic acids and aromatic tetra carboxylic acids with pyridine (solvate I-VI) and quinoline (VII-VIII) are determined. Different types of hydrogen bond motifs (discrete or cyclic) in these solvates are identified. Solvates I and II possess discrete O-H...N interactions, solvates III and VIII possess combinations of cyclic interactions arising from O-H-... -N and C-H- ? -O interactions, solvates IV, V, and VII have both the above namely discrete and cyclic types of interactions, whereas, solvate VI is an exception which possesses discrete O-H...N as well as fl²₂(8) types of interactions and provides a model system for incomplete cleavage of dimeric assembly of carboxylic acid moiety. On the basis of the results of various hydrogen bond motifs, density functional theory calculations (DFT) on similar motifs generated from formic acid and its interaction with pyridine and quinoline are carried out. In the case of a pyridine formic acid system, DFT calculations show that the energy difference between the cyclic R²₂(7) motif and the discrete motif is ～0.6 kcal/mol. Such a small difference accounts for the formation of both types of structural patterns in solvates I-V depending on the steric requirements. The observed motif of VI is established by comparison of theoretical energies between a dimeric carboxylic acid moiety generated from two formic acids interactions and a trimeric moiety that exhibits two formic acids and pyridine interactions. The energy of different types of hydrogen bond motifs formed by the interactions between quinoline and formic acid is also calculated. Calculations based on DFT show that the salt formation between formic acid and pyridine is not a favorable process, but it may occur in the case of quinoline.

Full text of DOI:10.1021/cg900938x

DOI: 10.1021/cg900938x
Structural Studies on Solvates of Cyclic Imide Tethered Carboxylic Acids
with Pyridine and Quinoline
2010, Vol. 10
348–356
Devendra Singh,† Pradip K. Bhattacharyya,‡ and Jubaraj B. Baruah*,†
†Department of Chemistry, Indian Institute of Technology Guwahati, Guwahati 781 039 Assam, India,
and ‡Department of Chemistry, Arya Vidyapeeth College, Guwahati-16, Assam
Received August 8, 2009; Revised Manuscript Received October 3, 2009
ABSTRACT: Structures of eight solvates of cyclic imide tethered carboxylic acids and aromatic tetra carboxylic acids with
pyridine (solvate I-VI) and quinoline (VII-VIII) are determined. Different types of hydrogen bond motifs (discrete or cyclic) in
these solvates are identified. Solvates I and II possess discrete O-H N interactions, solvates III and VIII possess
3 3 3
combinations of cyclic interactions arising from O-H N and C-H O interactions, solvates IV, V, and VII have both
3 3 3
3 3 3
the above namely discrete and cyclic types of interactions, whereas, solvate VI is an exception which possesses discrete
O-H N as well as R2 (8) types of interactions and provides a model system for incomplete cleavage of dimeric assembly of
carboxylic acid moiety. On the basis of the results of various hydrogen bond motifs, density functional theory calculations
2
3 3 3
(DFT) on similar motifs generated from formic acid and its interaction with pyridine and quinoline are carried out. In the case of
a pyridine formic acid system, DFT calculations show that the energy difference between the cyclic R2 (7) motif and the discrete
2
motif is ∼0.6 kcal/mol. Such a small difference accounts for the formation of both types of structural patterns in solvates I-V
depending on the steric requirements. The observed motif of VI is established by comparison of theoretical energies between a
dimeric carboxylic acid moiety generated from two formic acids interactions and a trimeric moiety that exhibits two formic acids
and pyridine interactions. The energy of different types of hydrogen bond motifs formed by the interactions between quinoline
and formic acid is also calculated. Calculations based on DFT show that the salt formation between formic acid and pyridine is
not a favorable process, but it may occur in the case of quinoline.
Introduction
that the two carbonyl groups of the imide would participate in
weak interactions to guide the orientation of the carboxylic
acid groups.
The interactions of carboxylic acids with pyridine and
related nitrogen containing heterocyclic compounds are well
studied.1 The knowledge of these interactions is useful in
pharmceuticals,2 and also in the synthesis of porous materi-
als.3 The hydrogen bondsbetween carboxylic acidsand simple
aromatic amines may be of different types.4 Some possible
hydrogen bond motifs arising from interactions of carboxylic
acid with pyridine and quinoline are shown in Figure 1, and
some of those motifs are already available in the literature.1a,4
Steric factors play an important role in stabilization of these
motifs.5 Depending on the association of parent carboxylic
acids in cyclic hydrogen bonds, it is likely that such hydrogen
bond motifs may originate from cleavage of cyclic dimeric
carboxylic acid by inclusion of a base such as pyridine or
quinoline. The validity of such observations can be checked if
it is possible to identify motifs such as PyA3 as illustrated in
Figure 1. In addition, depending on the packing effect6 as well
as pKa of an acid and a base,1a,7 the hydrogen bonded
assembly of amines with carboxylic acids leads to formation
of either solvates or salts. The effect of pKa on such processes
is reported in detail in the literature.7c The R groups consid-
ered in the present study are either aromatic ring or aromatic
rings attached through a C-N bond to phthalimide or
naphthalimide. It is anticipated that the free rotation of such
phthalimide or naphthalimide aromatic rings around the
C-N bond would provide an environment to adjusthydrogen
bond motifs with geometry guided by the dipolar nature of the
phthalimide or naphthalimide rings.8 Further, it may be noted
Thus, to establish these motifs (as shown in Figure 1) in
solid-state assembly, wehave studied the structures of solvates
of pyridine/quinoline of aromatic tetracarboxylic acid, and
some of the carboxylic acids that are tethered by phthalimide
or naphthalimide. The compounds used in this study for
preparation of solvates are shown in Figure 2. Analogous
motifs derived from interactions of pyridine or quinoline with
formic acid were constructed and their corresponding energies
were calculated by density functional theory (DFT) using
diffuse functions.9
Results and Discussion
The solvates of compounds 1-6 with pyridine (I-VI) were
prepared and characterized (Scheme 1). The structure of all
these pyridine solvates were determined and salt formation
was not observed in any case. The 1:1 (carboxylic acid/
pyridine) stoichiometry of the hydrogen bond donor to
acceptor was found in the solvates and the structure of each
solvate exhibits O-H N interactions. Part of the crystal
3 3 3
structures of pyridine solvates I-V is shown in Figure 3 and
the hydrogen bond parameters are listed in Table 1.
In solvate I (1:1 solvate) pyridine molecule is associated
with the carboxylic acid via O-H N interactions as a
3 3 3
discrete hydrogen bond, the molecules of pyridines and the
acids in the lattice also form an assembly through
˚
C5-H O3 (dd-A, 3.18 A, and —A-H D, 132.1ꢀ) and
3 3 3
3 3 3
˚
C18-H O4 (dd-A, 3.38 A, and —A-H D, 137.1ꢀ) inter-
actions. The solvate II is analogous to solvate I, and in this
case also we observed discrete hydrogen bonds between
3 3 3
3 3 3
*To whom correspondence should be addressed. E-mail: juba@iitg.ernet.
in.
r
pubs.acs.org/crystal
Published on Web 10/26/2009
2009 American Chemical Society

Article
Crystal Growth & Design, Vol. 10, No. 1, 2010 349
Table 1. Hydrogen Bond Geometry (A, ꢀ) for the Solvates I-V
˚
compounds
D-H
A
d (D-H)
d (H A)
3 3 3
d (D A)
3 3 3
—D-H
3 3 3
A
3 3 3
I
II
III
IV
O4-H4A N2 [x, -y þ 3/2, z þ 1/2]
0.82
0.82
0.82
0.82
0.82
0.82
0.82
0.82
1.85
1.77
1.82
1.84
1.83
1.75
1.78
1.77
2.66
2.58
2.63
2.65
2.65
2.56
2.57
2.59
174.2
169.7
174.0
175.4
175.0
166.5
161.7
173.6
3 3 3
O4-H4A N2
3 3 3
O2-H2A N2 [-x þ 1/2, y þ 1/2, -z]
3 3 3
O1-H1 N2 [-x þ 1, -y þ 1, -z]
3 3 3
O7-H7 N4 [x - 1, y - 1, z]
3 3 3
O4-H4A N3 [x - 1, y, z]
3 3 3
V
O4-H4 N1 [x, -y þ 3/2, z þ 1/2]
3 3 3
O1-H1 N2
3 3 3
Figure 1. Some hydrogen bonded motifs from interactions of pyr-
idine and quinoline with a carboxylic acid.
pyridine and carboxylic acid group. The pyridine molecules
are further held by C-H O interactions, namely, C29-
3 3 3
˚
H
O2 (dd-A, 3.12 A, and —A-H
D, 109.7ꢀ) and
3 3 3 3
3 3 3
˚
C32-H O2 (dd-A, 3.45 A, and —A-H
D, 140.7ꢀ)
3 3 3 3
3 3 3
3 3 3
˚
and C-H π interactions (dC15 π, 3.59 A) in the assembly.
3 3 3
In solvate III (1:2 solvate), a cyclic R2 (7) type of hydrogen
2
bond pattern is observed between the pyridine molecules and
carboxylic acid groups. Both the pyridine molecules present in
III are involved in cyclic type of hydrogen bonding with the
dicarboxylic acid via O-H N [O2-H2A N2 (dd-A
,
O
3 3 3
3 3 3
˚
2.63 A, and —A-H D, 174.0ꢀ)] as well as C-H
Figure 2. Structure of different compounds studied.
3 3 3
3 3 3
˚
[C11-H11 O3 (dd-A, 3.27 A, and —A-H D, 125.7ꢀ)]
3 3 3 3 3 3
interactions. Moreover, the pyridine molecules are also asso-
ciated in the lattice via C-H O interactions, namely,
nonplanar orientation. Both the discrete and cyclic types of
hydrogen bond patterns are also observed in this solvate. Two
carboxylicacid groups present oneach sideof the naphthalene
ring interact with two pyridine molecules via discrete
3 3 3 3
˚
C12-H12 O1 (dd-A, 3.30 A, and —A-H D, 131.8ꢀ) and
3 3 3 3 3 3
˚
C13-H13 O3 (dd-A, 3.41 A, and —A-H D, 136.3ꢀ)
3 3 3 3 3 3
with dicarboxylic acid molecules.
In solvate IV (1:3 solvate), both cyclic R2 (7) and discrete
O-H N interactions as well as a combination of cyclic
3 3 3
O-H N and C-H O interactions, respectively. Both
2
3 3 3
3 3 3
types of hydrogen bond patterns are observed. Two pyridine
molecules are involved in cyclic type of hydrogen bonding
the discrete and cyclic hydrogen bonded pyridine molecules
are positioned in trans orientation to each other around the
naphthalene ring, and a cyclic hydrogen bond pattern is
with carboxylic acid groups via O-H N [O1-H1 N2
3 3 3 3 3 3
˚
(dd-A, 2.65 A, and —A-H D, 175.4ꢀ) and O7-H7 N4
3 3 3 3 3 3
formed via O4-H4 N1 and C11-H11 O3 interactions.
3 3 3 3 3 3
˚
[(dd-A, 2.65 A, and —A-H D, 175.0ꢀ)] as well as
3 3 3
Since different types of hydrogen bond motifs are observed
in the structures of solvates I-V, we performed DFT calcula-
tions on analogous motifs constructed from formic acid and
pyridine. Optimized structures of pyridine/formic acid motifs
at the B3LYP/6-31þG* level of theory are shown in Figure 4.
In structure 4a, both the formic acid and pyridine molecules
are coplanar (with a dihedral angle H-O-C-O = 0ꢀ in
˚
C-H O[C21-H21 O8(dd-A, 3.27A, and —A-H D,
3 3 3 3 3 3 3 3 3
˚
126.0ꢀ) and C30-H30 O2 (dd-A, 3.16 A, and —A-
3 3 3
H
D, 126.1ꢀ) interactions, whereas one pyridine molecule
3 3 3 3
is associated with a carboxylic acid group through a discrete
type of O-H N interaction, namely, O4-H4
N3 (dd-A,
3 3 3
3 3 3 3
˚
2.56 A, and —A-H D, 166.5ꢀ) interaction. Moreover,
3 3 3
both types of pyridine molecules involving in cyclic and
discrete hydrogen bondings are also held in the crystal lattice
formic acid), which facilitates the formation of two short-
˚
range interactions viz. O-H N (dH A, 1.73 A) and
3 3 3
3 3 3
˚
via C-H O interactions, namely, C18-H18 O6 (dd-A
,
,
C-H O (dH A, 2.45 A) interactions. However, in the case
3 3 3 3 3 3
3 3 3
3 3 3
˚
3.41 A, and —A-H D, 143.9ꢀ) and C29-H29 O6 (dd-A
of the structure 4b, the two molecules lie at an angle 90ꢀ to
eachother, whichallowsthe formationofonlyoneO-H
(dH 3 3 3 A, 1.78A) interaction, and consequently the structure4b
is found to be less stable than 4a. To obtain a optimized
structure with pyridine/formic acid at an angle 90ꢀ to each
other, asshown in Figure 4b, weuse H-O-C-O =180ꢀ, and
the calculated energy difference between the two conformers
3 3 3 3 3 3
˚
3.36 A, and —A-H D, 143.9ꢀ) interactions respectively
N
3 3 3
3 3 3
˚
and further interact to each other via C-H π interactions
3 3 3
˚
(dC19 π, 3.59 A) in the assembly.
3 3 3
In solvate V (1:4 solvate) the four carboxylic acid groups of
naphthalene-1,4,5,8-tetracarboxylic acid are in a sterically
crowded environment, and they are expected to be in a

350 Crystal Growth & Design, Vol. 10, No. 1, 2010
Scheme 1. Various Solvates of Pyridine
Singh et al.
Table 2. Stability of 4a with Different Basis Sets (in kcal/mol)
II have discrete types of hydrogen bonds, whereas the solvate
III has a cyclic type and the solvates IV-V have both types;
these results combined with the narrow energy differences
between the cyclic and discrete structure suggest that the
interplay of these weak interactions occurs in the packing
pattern and such an effect with steric requirements decide the
formation of different types of hydrogen bond motifs in the
solid-state structures of these systems.
basis sets
relative stability of 4a
6-31þG*
-0.16
-0.13
-0.31
-0.61
6-31þþG*
6-31þþG**
AUG-cc-pVDZ
of the acid molecule (with H-O-C-O = 0ꢀ and with
H-O-C-O = 180ꢀ) and subtracted it from the interaction
energy of 4b to obtain relative stability of 4a (E4a - E4b)
because a stable structure like 4a was obtained only when the
formic acid was used with H-O-C-O = 0ꢀ. Relative stability of
4acalculatedwithdifferentbasisfunctionsisshowninTable2.
It is observed that with lower level basis functions, the relative
stability of 4a is found to be ∼0.15 kcal/mol, whereas highly
polarization and diffuse basis function, 6-31þþG** gives
this value -0.31 kcal/mol. Diffuse double-ζ basis function
AUG-cc-pVDZ shows the highest relative stability, that is,
-0.61 kcal/mol. The importance of such small interaction
energies in crystal lattice is well documented.1f
As mentioned in the introduction, there is a need to under-
stand the origin of these motifs, and one of such model may be
formed from a dimeric carboxylic acid with R2 (8) type
2
hydrogen bond motif as illustrated in Scheme 2. This motif
indicates a path involving dissociation of carboxylic acid
dimer by pyridine molecule to form an assembled structure
between two carboxylic acids and one pyridine molecule.
However, stability of such a motif is governed by a synergic
effect to control the approach of a pyridine molecule to an
optimum distance of dimeric carboxylic acid unit, so that it
does not cross a limiting value to make a monomeric 1:1
solvate. A system that would be appropriate for such process
can be imagined as a system in which the pyridine molecules
Such a small difference in energy1f accounts the probability
of both the structures depicted in Figure 4. The solvates I and
are held by C-H O interactions from the back side of the
3 3 3

Article
Crystal Growth & Design, Vol. 10, No. 1, 2010 351
Figure 3. Part of the crystal structures of solvates (I-V) showing weak interactions among carboxylic acids and pyridine (drawn with 20%
thermal ellipsoid).

352 Crystal Growth & Design, Vol. 10, No. 1, 2010
Table 3. Hydrogen Bond Geometry (A, ꢀ) for the Solvate VI
Singh et al.
˚
D-H
A
d (D-H)
d (H A)
3 3 3
d (D A)
3 3 3
—D-H
3 3 3
A
3 3 3
O2-H2 O4 [x þ 1/2, y þ 1/2, z]
0.82
0.82
1.70
1.88
2.51
2.57
171.0
150.9
3 3 3
O3-H3A N2 [x, y - 1, z]
3 3 3
Scheme 2. Assembly Formation between Two Carboxylic Acid Molecules and a Pyridine Molecule
Table 4. Interaction Energies (Eint) in Acid Dimer (6a) and in the Presence
of Pyridine Molecule (6b) (in kcal/mol)
in acid
dimer
in presence of
pyridine molecule
basis
sets
(Eint,6a
)
(Eint,6b
)
6-31þG*
-15.84
-18.16
-18.09
-18.31
-22.84
6-31þþG*
6-31þþG**
AUG-cc-pVDZ
-25.33
-25.61
-25.40
lower level basis function 6-31þG* is -15.84 kcal/mol,
which increases to ∼ -18.0 kcal/mol with higher level basis
functions. Calculations with different basis function show
that the interaction energy increases by ∼7.0 kcal/mol in
the presence of the pyridine, Figure 6b (Eint,6b = Etrimer
-
Figure 4. (a, b) The optimized structures pyridine/formic acid
motifs at two different orientations.
2Eacid
- Epyridine). This increase in interaction
monomer
energy explains the change in orientation of the acid
molecules when pyridine is brought into close contact with
the formic acid dimer and the hydrogen bonding rear-
ranges to that in 6b, which is an energetically favored process.
A similar observation is made in the solvate VI in which the two
carboxylic acid groups along with pyridine adopt a geometry
O-H N interactions so that a pyridine is held by a pull
3 3 3
from the back, as illustrated in Scheme 2.
The structure of a 1:2 solvate of compound 6 with pyridine
(solvate VI) provides a model system for such incomplete
cleavage of dimeric assembly of the carboxylic acid moiety.
Solvate VI is associated with discrete O-H N as well as
stabilized by the O-H N interactions from one side and
3 3 3
3 3 3
R2 (8) type of interactions. Other weak interactions such as
C-H π as well as C-H O interactions from other sides,
2
3 3 3
3 3 3
˚
C23-H O3 (dd-A, 3.18 A, and —A-H D, 122.5ꢀ),
which oppose each other to make an optimized geometry.
The solvates of compound 5 and 7 with quinoline
(VII-VIII) are prepared and characterized (Scheme 3). Part
of the crystal structures of quinoline solvates (VII-VIII) are
shown in Figure 7 and the hydrogen bonding parameters are
listed in Table 5.
3 3 3
3 3 3
˚
C22-H O6 (dd-A, 3.17 A, and —A-H D, 133.7ꢀ), and
3 3 3 3 3 3
˚
C3-H π (dC3 π, 3.79A) interactions and relatively strong
3 3 3
3 3 3
˚
π
containing the carboxylic acids are also present in the part of
π interactions (dC3-C4, 3.39 A) betweenthe aromatic ring
3 3 3
the crystal structure (Table 3, Figure 5).
To follow the feasibility of formation of PyA3 type of motif
as illustrated in Figure 1, which is also the motif seen in solvate
VI, we have calculated the interaction energy of a formic
acid dimer and the effect of presence of one pyridine mole-
cule on acid dimer. The optimized structures of the two
systems at B3LYP/6-31þG* level of theory are shown in
Figure 6.
The quinoline solvate VII (1:4 solvate) is analogous to
pyridine solvate (V) in which quinoline molecules are involved
in both discrete and cyclic R2 (7) types of hydrogen bonds.
2
There are two discrete O-H N interactions involving two
3 3 3
quinoline molecules and two trans carboxylic acid groups of
the parent tetra carboxylic acid. Another two cyclic hydrogen
bonded quinoline molecules show O2-H2 N2 and
3 3 3
In structure 6a, the two acid molecules are coplanar which
facilitate the formation of two short-range O-H O inter-
C17-H17 O1 interactions and are also placed trans to
3 3 3
each other around the naphthalene ring.
In solvate VIII (1:2 solvate) both quinoline molecules
3 3 3
˚
actions (dH 3 3 3 A, 1.71 A). The orientations of the two acid
molecules change in the presence of pyridine molecule and one
interact with parent dicarboxylic acid via O-H
N
3 3 3
˚
˚
short-range O-H O (dH A, 1.72 A) interaction between
[O1-H1 N3 (dd-A, 2.62 A, and —A-H D, 177.0ꢀ) and
3 3 3 3 3 3
3 3 3
3 3 3
˚
the two carboxylic acid molecules and another short-range
˚
O3-H3A N2 (dd-A, 2.70 A, and —A-H D, 177.9ꢀ)] as
3 3 3 3 3 3
˚
O-H N (dH A, 1.68 A) interaction between one acid
well as C-H O [C17-H17 O4 (dd-A, 3.29 A, and
3 3 3
3 3 3 3 3 3
3 3 3
˚
molecule and pyridine is observed in this case (Figure 6b).
Interaction energies of structures 6a and 6b with different
basis sets are shown in Table 4.
—A-H D, 127.3ꢀ) and C26-H26 O2 (dd-A, 3.22 A,
3 3 3
3 3 3
and —A-H D, 121.5ꢀ) interactions exhibiting only a cyclic
3 3 3
type of hydrogen bond pattern. The quinoline molecules
further interact to each other via C-H π interactions
From Table 4 we observed that interaction energy in
acid dimer (Eint,6a = Edimer - 2Eacid monomer) with the
3 3 3
˚
(dC28 π, 3.61 A) and to parent dicarboxylic acid also via
3 3 3

Article
Crystal Growth & Design, Vol. 10, No. 1, 2010 353
Figure 5. Two different views of a part of the crystal structure of VI (drawn with 20%) thermal ellipsoids).
Figure 6. Optimized geometry for (a) formic acid dimer and (b) assembly of pyridine and two formic acids.
Figure 7. Part of crystal structures of the solvates (VII-VIII) showing weak interactions among carboxylic acids and quinolines (drawn with
20% thermal ellipsoid).
˚
Table 5. Hydrogen Bond Geometry (A, ꢀ) for the Solvates VII-VIII
compounds
D-H
A
d (D-H)
d (H A)
d (D A)
—D-H
3 3 3
A
3 3 3
3 3 3
3 3 3
VII
O3-H3 N1 [-x þ 1, -y þ 2, -z þ 1]
0.82
1.10
0.93
0.82
0.82
1.84
1.80
2.69
1.81
1.88
2.66
2.62
3.29
2.62
2.70
171.0
174.9
123.3
177.0
177.9
3 3 3
O2-H2 N2 [-x, -y þ 1, -z]
3 3 3
C17-H17 O2
3 3 3
VIII
O1-H1 N3 [x þ 2, -y þ 1, -z þ 1]
3 3 3
O3-H3A N2 [x - 1, y, z]
3 3 3
˚
Table 6. Stability of Different Systems (in kcal/mol)
C-H π interactions (dC11 π, 3.78 A). In the case of
3 3 3
3 3 3
quinoline solvates VII and VIII, there may be another type
of cyclic hydrogen bond pattern, namely, QA2 as shown in
Figure 1, but in our case, we observed only the QA3 type of
cyclic pattern. The QA2 pattern is not observed in these cases
possibly due to strong π-π and O-π interactions among the
basis sets
stability of 8b over 8a
stability of 8b over 8c
6-31þG*
-0.57
-0.58
-0.63
-0.54
-13.65
-13.65
-14.87
-14.94
6-31þþG*
6-31þþG**
AUG-cc-pVDZ

354 Crystal Growth & Design, Vol. 10, No. 1, 2010
Singh et al.
Figure 8. Optimized structure of (a, b) solvates and (c) salt of formic acid with quinoline.
Table 7. Crystallographic Parameters of the Solvates I-VIII
compound no.
I
II
III
IV
V
VI
VII
VIII
formulas
formula. wt
C20H14N2O4 C24H16N2O4 C26H19N3O6 C32H24N4O8 C34H28N4O8 C30H21N3O6 C50H36N4O8 C34H23N3O6
346.33
monoclinic
P2(1)/c
296
396.39
triclinic
P1
469.44
monoclinic
C2
592.55
triclinic
P1
620.60
monoclinic
P2(1)/c
296
519.50
monoclinic
C2/c
820.83
monoclinic
P2(1)/n
296
569.55
crystal system
space group
temperature (K)
monoclinic
P2(1)/c
296
296
296
296
296
˚
a/A
17.6509(10)
12.4017(7)
8.1183(5)
90.00
102.295(3)
90.00
1736.35(18)
4
1.325
0.094
720
8.1612(3)
9.2908(3)
13.3668(4)
100.934(2)
96.943(2)
95.880(2)
979.62(6)
2
1.344
0.093
412
8143
23.7837(11)
12.7985(5)
3.8331(2)
90.00
98.111(4)
90.00
1155.11(9)
2
1.350
0.098
488
7.8269(3)
13.0543(5)
15.4327(5)
102.436(2)
100.873(3)
102.566(3)
1456.36(9)
2
1.351
0.099
616
12590
7.5238(7)
20.237(2)
10.1313(9)
90.00
96.131(7)
90.00
1533.8(3)
2
1.344
0.097
648
13.2197(13)
14.1173(13)
27.683(3)
90.00
99.663(8)
90.00
5093.1(8)
8
1.355
0.096
2160
7.4716(3)
20.7861(10)
12.8464(6)
90.00
96.274(2)
90.00
1983.17(15)
2
1.375
0.094
856
13.6989(7)
16.5216(8)
12.8230(7)
90.00
106.265(3)
90.00
2786.0(2)
4
1.358
0.095
1184
˚
b/A
˚
c/A
R/ꢀ
β/ꢀ
γ/ꢀ
3
˚
V/A
Z
density/Mg m-3
abs coeff /mm-1
F(000)
total no. of reflections
reflections, I > 2σ(I)
max 2θ/ꢀ
16803
2406
56.52
5439
1835
50.00
7914
1461
50.00
-8 e h e 8
33859
4554
56.78
20241
2294
50.22
29891
3671
50.00
-16 e h e 16
2056
56.50
3119
50.00
ranges (h, k, l)
-22 e h e 23 -10 e h e 10 -28 e h e 26 -9 e h e 9
-17 e h e 17 -8 e h e 8
-16 e k e 16 -12 e k e 12 -14 e k e 14 -15 e k e 15 -22 e k e 24 -18 e k e 18 -24 e k e 24 -19 e k e 19
-10 e l e 9 -17 e l e 17 -4 e l e 4
-18 e l e 18 -11 e l e 12 -36 e l e 36 -15 e l e 15 -13 e l e 15
complete to 2θ (%)
98.5
data/ restraints/parameters 4248/0/236
96.1
4654/0/272
1.001
0.0516
0.1328
97.1
1968/1/ 161
1.050
0.0310
0.0338
90.8
4669/0/400
1.024
0.0455
0.0746
95.6
2569/0/210
1.006
0.0688
0.1291
98.4
6285/0/354
1.059
0.0509
0.0725
99.5
3518/0/282
1.016
0.0440
0.0799
99.8
4894/0/390
1.064
0.0399
0.0594
GOF (F2)
1.021
0.0472
0.0922
R indices [I > 2σ(I)]
R indices (all data)
Scheme 3. Solvates of Quinoline
quinoline molecules, but such types of interactions are re-
ported in some related systems.5b,c
We have calculated the energy of different hydrogen bond
motifs between formic acid and quinoline arising from the
different orientations of the carboxylic acid molecule with
pyridinium-carboxylate salt are also calculated. Our calcula-
tions show the possibility of formation of quinolinium-car-
boxylate salt only. The optimized structure of quinolinium
carboxylate salt shown in Figure 8c clearly shows that the two
ions are in the same plane. The N-H bond length is found to
˚
respect to the quinoline molecule (Figure 8a,b). It is observed
˚
be 1.06 A, which is much longer than the typical N-H
˚
covalent bond length (0.80 A). The interaction distance
between the H atom of quinolinium cation and the two O
˚
atoms of carboxylate anion are 1.81 and 1.99 A, which shows
that two different short-range O-H N (dH A, 1.76 A in
3 3 3
3 3 3
˚
˚
8a; dH A, 1.73 A in 8b) and C-H O (dH A, 2.35 A in 8a;
3 3 3
3 3 3
3 3 3
˚
dH 3 3 3 A, 2.44 A in 8b) interactions exist in structure 8a and 8b.
The interactions between quinoline and formic acid are
exocyclic in 8a, while these interactions are endocyclic in 8b.
The energy for the formation of quinolinium-carboxylate and
the formation of the moderately strong hydrogen bond
˚
between them. Two C-H O interactions with dH A (A)
3 3 3
3 3 3 3
2.18 and 2.45 are also exist there. Among the three structures,

Article
Crystal Growth & Design, Vol. 10, No. 1, 2010 355
8b is found to be the most stable. Stability of 8b over 8a and 8c
is shown in Table 6. Different levels of calculations show that
the stability of 8b compared to 8a lies in the range -0.57 kcal/
compounds have CCDC numbers 739794, 739795, 739796,
739797, 739798, 739799, 739312 and 739315.
Synthesis and Characterization of Compounds and Their Solvates.
The compound naphthalene-1,4,5,8-tetracarboxylic acid was ob-
tained from Sigma Aldrich (USA) and used as received. 2-(1,3-Dio-
xo-1,3-dihydro-isoindol-2-yl)-benzoic acid: A solution of phthalic
anhydride (0.740 g, 5 mmol) and anthranilic acid (0.685 g, 5 mmol)
in acetic acid (25 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 brown colored precipitate of the product
was obtained. This was filtered, air-dried. Yield: 85%; IR (KBr,
cm-1): 3180 (m), 1725 (s), 1704 (s), 1602 (m), 1493 (w), 1466 (w),
1455 (w), 1384 (m), 1291 (w), 1236 (m), 1218 (m), 1172 (w), 1118 (m),
mol to -0.63 kcal/mol, which also affects the order of N
H
3 3 3
˚
bond distances in structures 8a and 8b (8a, 1.76 A > 8b,
˚
1.73 A). The formation of quinolinium carboxyltae salt (8c) is
possible, but it is quite unstable compared to 8a or 8b. The
range of stability of 8b compared to 8c with different basis sets
is found to be -13.65 kcal/mol to -14.94 kcal/mol. This
theoretical data suggest that there are geometrical require-
ments, which are over and above the conventional pKa values
of an acid under consideration to make solvates or deproto-
nated species in solid-state assembly.1a
1
1084(w), 895 (m), 857 (w), 790 (w), 704 (m), 644 (w), 578 (w). H
NMR (400 MHz, CDCl3): 8.15 (d, 1H, J = 7.6 Hz), 7.90 (dd, 2H,
J = 3.2 Hz), 7.75 (dd, 2H, J = 3.2 Hz), 7.69 (t, 1H, J = 7.6 Hz), 7.53
(t, 1H, J = 7.6 Hz), 7.37 (d, 1H, J = 8.0 Hz). Solvate I: The solvate
of 2-(1,3-dioxo-1,3-dihydro-isoindol-2-yl)-benzoic acid with pyri-
dine was obtained by crystallizing it from pyridine solution as
colorless blocks. IR (KBr, cm-1): 3445 (m), 2928 (w), 1736 (s),
1709 (s), 1606 (w), 1486 (m), 1472 (m), 1385 (s), 1291 (w), 1238 (w),
1176 (w), 1119 (m), 1098 (w), 1006 (w), 883 (w), 811 (m), 793 (w), 718
(m), 531 (w). 1H NMR (400 MHz, CDCl3): 8.67 (d, 2H, J = 4.4 Hz),
8.15 (d, 1H, J = 7.6 Hz), 7.90 (dd, 2H, J = 3.2 Hz), 7.75 (dd, 2H,
J = 3.2 Hz), 7.69 (t, 1H, J = 7.6 Hz), 7.53 (t,1H, J = 7.6 Hz), 7.49 (t,
1H, J = 7.2 Hz)7.37 (d,1H, J = 8.0 Hz), 6.43 (bs, 2H). 2-(1,3-dioxo-
1H,3H-benzo[de]isoquinolin-2-yl)-benzoic acid: Compound 2-(1,3-
dioxo-1H,3H-benzo[de]isoquinolin-2-yl)-benzoic acid was synthe-
sized by refluxing a solution of 1,8-naphthalic anhydride (0.990 g,
5 mmol) with anthralinic acid (0.685 g, 5 mmol) in acetic acid for 3 h.
On cooling, pure crystalline product was obtained. Yield: 82%; IR
(KBr, cm-1): 3445 (m), 2858 (w), 1772 (w), 1705 (s), 1679 (s), 1663
(s), 1601 (w), 1588 (m), 1411 (w), 1374 (m), 1356 (m), 1304 (m), 1270
(m), 1237 (s), 1197 (m), 953 (w), 775 (m), 710 (w). 1H NMR
(400 MHz, CDCl3): 8.57 (d, 2H, J = 6.8 Hz), 8.23 (d, 2H, J =
8.0 Hz), 8.16 (d, 1H, J = 8.0 Hz), 7.72 (m, 3H), 7.52 (t, 1H, J =
8.0 Hz), 7.32 (d, 1H, J = 8.0 Hz).
Conclusions
A series of structures of pyridine and quinoline solvates of
aromatic tetracarboxylic acid and some of the imide tethered
carboxylic acids is studied. It is observed that the discrete as
well as cyclic types hydrogen bonds are involved with the
O-H N interactions. The presence of different hydrogen
3 3 3
bond patterns is governed by the substrates. DFT calculations
on energy of different formic acid/pyridine and formic acid/
quinoline motifs suggest that the energy differences between
these motifs are very small and within the limit of very weak
hydrogen bonds. Thus, their formation is controlled by the
other weak interactions present in the motifs. These observa-
tions are revealed in the experimental structural data, and
based on them we could obtain an assembly arising from 1:2
composition of a carboxylic acid with pyridine. This assembly
is stabilized by the opposing effect of the weak interactions
such as C-H O to the stronger O-H N interactions in
3 3 3 3 3 3
the crystal structure.
Solvate II. The solvate II was obtained by crystallization of
2-(1,3-dioxo-1H,3H-benzo[de] isoquinolin-2-yl)-benzoic acid in
pyridine as colorless blocks. IR (KBr, cm-1): 3476 (m), 2930 (w),
1722 (s), 1698 (s), 1661 (s), 1645 (s), 1622 (m), 1589 (m), 1491 (w),
1438 (w), 1380 (m), 1361 (m), 1244 (s), 1201 (m), 1140 (w), 1079 (w),
847 (w), 780 (m), 710 (w), 515 (w). 1H NMR (400 MHz, CDCl3): 8.60
(d, 2H, J = 7.2 Hz), 8.50 (d, 2H, J = 7.6 Hz), 8.23 (m, 3H), 7.70 (m,
3H), 7.53 (t, 1H, J = 7.6 Hz), 7.34 (d, 1H, J = 7.6 Hz), 7.25 (m, 3H).
5-(1,3-Dioxo-1,3dihydro-isoindol-2-yl)-isophthalic Acid. The com-
pound 5-(1,3-dioxo-1,3dihydro-isoindol-2-yl)-isophthalic acid was
synthesized by refluxing a solution of phthalic anhydride (0.740 g,
5 mmol) and 1-amino 3,5-benzenedicarboxylic acid (0.905 g, 5 mmol)
in N,N-dimethylformamide for 3 h. On cooling pure crystalline
product was obtained. IR(KBr, cm-1): 3445 (m), 2925 (w), 1728
(s), 1605 (w), 1416 (m), 1382 (s), 1281 (s), 1226 (m), 1112 (w), 1081
(w), 875 (w), 759 (m), 711 (s), 641 (w), 530 (w). 1H NMR (400 MHz,
DMSO-d6): 8.49 (s, 1H), 8.28 (s, 2H), 7.99 (dd, 2H J = 3.2 Hz), 7.91
(dd, 2H J = 3.2 Hz). Solvate III: The solvate III was obtained by
crystallization of 5-(1,3 dioxo-1,3dihydro-isoindol-2-yl)-isophthalic
acid in pyridine as colorless blocks. IR (KBr cm-1): 3451 (m), 3083
(w), 2854 (w), 1716 (s), 1605 (m), 1427 (m), 1382 (s), 1283 (s), 1226
(m), 1114 (m), 921 (w), 758 (w), 712 (w), 691 (w), 642 (w), 530 (w).
1HNMR (400 MHz, DMSO-d6): 8.52 (bs, 4H), 8.49 (s, 1H), 8.28 (s,
2H), 7.99 (dd, 2H J = 3.2 Hz), 7.91 (dd, 2H J = 3.2 Hz) 7.89 (t, 2H,
J = 6.8 Hz), 7.39 (bs, 4H). 2-(5-carboxy-1,3-dioxo-1,3-dihydro-
isoindol-2-yl)-terephthalic acid: This compound was synthesized by
refluxing a solution of 1,3-dioxo-1,3-dihydro-isobenzofuran-5-car-
boxylic acid (0.960 g, 5 mmol) and 1-amino 2,4-benzene dicarboxylic
acid (0.905 g, 5 mmol) in acetic acid for 4 h. On cooling, pure
crystalline product was obtained. Yield: 84%; IR (KBr, cm-1):
3425 (m), 2899 (m), 2661 (m), 1786 (w), 1709 (s), 1572 (w), 1498
(w), 1445 (m), 1416 (m), 1298 (s), 1274 (s), 1220 (m), 1111 (m), 866
(w), 753 (w), 727 (w), 608 (w), 529 (w). 1HNMR (400 MHz, DMSO-
d6): 8.44 (d, 1H, J = 7.6 Hz), 8.33 (s, 1H), 8.15 (s, 2H), 8.12 (d,
1H, J = 4.0 Hz), 8.11 (s, 1H). Solvate IV: Solvate IV was obtained
as colorless blocks from the pyridine solution of the compound
2-(5-carboxy-1,3-dioxo-1,3-dihydro-isoindol-2-yl)-terephthalic acid.
Experimental Section
Computational Details. We have considered motifs derived from
formic acid with pyridine or quinoline as model system for calcula-
tion of energy. The geometries of the models have been calculated
with DFT9 using the combined Becke’s three-parameter exchange
functional and the gradient-corrected functional of Lee, Yang and
Parr (B3-LYP functional)10 at 6-31þG* levels. This functional has
been demonstrated to predict reliable geometries for hydrogen-
bonded systems.11 Single point calculations at the 6-31þG*,
6-31þþG** and B3LYP/AUG-cc-pVDZ12 level were performed
on the fully optimized geometries using B3LYP/6-31þG*. All cal-
culations are performed using the Gaussian03 program.13 The
choice of this basis set is based on the consideration to obtain
reliable properties for hydrogen-bonded systems, and it is essential
to employ basis sets that possess sufficient diffuseness and angular
flexibility.14 This basis set 6-31þþG** is sufficient to predict
reliable properties for hydrogen-bonded systems.11 All calculations
are carried out in the gas phase.
Structure Determination. The X-ray single crystal diffraction data
˚
were collected at 296 K with MoKR radiation (λ = 0.71073 A) using
a Bruker 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.15 All the non-H atoms were refined in the
anisotropic approximation 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
approximation; those attached to nitrogen and oxygen were located
in the difference Fourier maps, and refined with isotropic displace-
ment coefficients. The Crystallographic data collection was done at
room temperature and the data are tabulated in Table 7. The

356 Crystal Growth & Design, Vol. 10, No. 1, 2010
Singh et al.
IR (KBr cm-1): 3445 (m), 3064 (w), 2461(w), 1778 (m), 1716 (s), 1599
(m), 1489 (w), 1423(m), 1373 (m), 1286 (s), 1251(s), 1209 (s), 1121(m),
1101 (m), 1061(m), 1007 (w), 758 (m), 729 (w), 636 (w), 573(w).
1HNMR (400 MHz, DMSO-d6): 8.58 (d, 6H, J = 4.0 Hz), 8.45 (d,
1H, J = 7.6 Hz), 8.35 (s, 1H), 8.16 (s, 2H), 8.13 (d, 1H, J = 3.6 Hz),
8.11 (s, 1H), 7.83 (t, 3H), 7.38 (t, 6H). Solvate V: Solvate V was
obtained as colorless blocks from the pyridine solution of naphtha-
lene-1,4,5,8-tetracarboxylicacid. IR(KBr, cm-1): 3416(m), 2928(w),
2772 (w), 2381(m), 1706 (s), 1599 (w), 1501(m), 1385(m), 1284 (s),
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1
1196 (s), 872 (w), 805 (m), 778 (m), 670 (w). HNMR (400 MHz,
DMSO-d6): 8.56 (d, 8H, J = 8.0 Hz), 8.05 (s, 4H), 7.76 (m, 8H), 7.38
(t, 4H, 6.4 Hz). 2-(1,3-Dioxo-1H,3H-benzo[de]isoquinolin-2-yl)-tere-
phthalic acid: This compound was synthesized by refluxing a
solution of 1,8-naphthalic anhydride (0.990 g, 5 mmol) and 1-amino
2,4-benzenedicarboxylic acid (0.905 g, 5 mmol) in N,N-dimethylfor-
mamide. IR (KBr cm-1): 3436 (s), 2923 (w), 1710 (s), 1659 (s), 1591
(m), 1498 (w), 1438 (w), 1406 (w), 1380 (m), 1281 (s), 1248 (s), 1204
(m), 1120 (w), 1069 (w), 1017 (m), 952 (w), 886 (w), 850 (w), 780 (m),
769 (m), 709 (w), 535 (w). 1H NMR (400 MHz, DMSO-d6): 8.53 (dd,
4H, J = 7.2 Hz), 8.19 (d, 1H, J = 8.4 Hz), 8.13 (d, 1H, J = 8.0 Hz),
8.08 (s, 1H), 7.92 (t, 2H, J = 8.0 Hz). Solvate VI: The solvate VI was
obtained as colorless blocks from the pyridine solution of compound
2-(1,3-dioxo-1H,3H-benzo[de]isoquinolin-2-yl)-terephthalic acid. IR
(KBr, cm-1): 3446 (m), 3074 (w), 2474 (w), 1702 (s), 1661(s), 1588
(m), 1491(w), 1374 (m), 1245 (s), 1162 (m), 949 (w), 892 (w), 774 (m),
703 (w), 591(w). 1HNMR (400 MHz, DMSO-d6): 8.57 (d, 4H, J =
3.2 Hz), 8.52 (dd, 4H, J = 6.0 Hz), 8.21 (d, 1H, J = 8.4 Hz), 8.15 (d,
1H, J= 8.4Hz), 8.10(s,1H), 7.91(t, 2H, J= 8.0Hz), 7.78(t, 2H, J=
7.6 Hz), 7.37 (m, 2H). Solvate VII: Solvate VII was obtained from a
solution of naphthalene-1,4,5,8-tetracarboxylic acid in quinoline as
colorless blocks. IR (KBr, cm-1): 3432 (m), 2381(m), 1926 (w), 1704
(s), 1597 (m), 1504 (m), 1396 (m), 1274 (s), 1188 (s), 872 (w), 805 (m),
775 (m), 670 (w). 1H NMR (400 MHz, DMSO-d6): 8.91 (d, 4H, J =
4.0 Hz), 8.37 (d, 4H, J = 8.0 Hz), 8.01 (m, 12H), 7.77 (t, 4H, J =
6.8 Hz), 7.61 (t, 4H, J = 6.8 Hz), 7.53 (dd, 4H, J = 4.0 Hz).
2-(1,3dioxo-1,3-dihydro-isoindol-2-yl)-terephthalic acid: Compound
2-(1,3dioxo-1,3-dihydro-isoindol-2-yl)-terephthalic acid was synthe-
sized by refluxing a solution of phthalic anhydride (0.740 g, 5 mmol)
and 1-amino 2,4-benzene dicaboxylic acid (0.905 g, 5 mmol) in acetic
acidfor 3 h. Yield:87%;IR(KBr, cm-1): 3082(m), 2644(w), 1694(s),
1444 (s), 1376 (m), 1292 (m), 1250 (s), 1175 (w), 1140 (w), 1118 (m),
946 (w), 883 (w), 792 (w), 759 (m), 725 (w), 529 (w). 1H NMR
(400 MHz, DMSO-d6): 8.13 (s, 2H), 8.10 (s,1H), 7.99 (dd,2H, J =
3.2 Hz), 7.93 (dd, 2H, J = 3.2 Hz). Solvate VIII: Solvate VIII was
obtained as colorless blocks from the quinoline solution of com-
pound 2-(1,3 dioxo-1,3-dihydro-isoindol-2-yl)-terephthalic acid. IR
(KBr, cm-1): 3463 (m), 2788 (w), 2449 (m), 1774 (w), 1715 (s), 1496
(m), 1473 (w), 1459 (w), 1421 (m), 1376 (m), 1282 (s), 1234 (m), 1216
(m), 1141 (w), 1120 (m), 881(w), 809 (m), 785 (m), 720 (w), 636 (w),
528 (w). 1HNMR (400 MHz, DMSO-d6): 8.90 (dd, 2H, J = 3.2 Hz),
8.37(d, 2H, J = 7.6 Hz), 8.14 (s, 2H), 8.11 (s, 1H), 8.00 (m, 6H), 7.92
(dd, 2H, J = 3.2 Hz), 7.75 (t, 2H, J = 7.2 Hz), 7.61 (t, 2H, J =
6.8 Hz), 7.53 (dd, 2H, J = 4.0 Hz).
Acknowledgment. The authors thank Department of
Science and Technology (New Delhi, India) for financial
support. One of the authors D.S. is thankful to Council of
Scientific and Industrial Research, New Delhi (India) for a
fellowship.
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Supporting Information Available: Crystallographic information
files are available free of charge via the Internet at http://pubs.
acs.org.
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