Structural study on solvates of dopamine-based cyclic imide derivatives

Article abstract of DOI:10.1021/cg101316u

A structural study on two dopamine-based imide derivatives, namely, 2-(3,4-dihydroxyphenethyl)isoindole-1,3-dione (1) and 2,6-bis-[2-(3,4- dihydroxyphenyl)ethyl]pyrrolo [3,4-f]isoindole-1,3,5,7-tetrone (2), and their solvates was carried out. The compound 1 (Z′ = 2) was crystallized through a melt crystallization process, whereas its two solvates (Z′ = 1 of each), containing one water molecule (1a) and the other containing two quinoline molecules (1b) in their crystal lattices, respectively, were obtained through solution crystallization. The reasons for Z′ = 2 arising from symmetry nonequivalent molecules in the unit cell of 1 is attributed to the nonparallel arrangement of two layers of self-assembled molecules in crystal lattice, where one layer has C-H???π and another layer has C=O???π interactions. Four different solvates of compound 2 (Z′ = 0.5 of each), containing two DMF molecules (2a), two DMSO molecules (2b), two pyridine molecules (2c), and six quinoline molecules (2d), were also obtained through solution crystallization of 2 in respective solvents. Solvate 2d has channels in its structure which are formed by interaction of 2 with quinoline molecules through O-H???N and C-H???π interactions. Additional quinoline molecules reside in these channels of approximately (11 × 12) A dimension. Structural features of all the compounds and their solvates have been studied by single crystal X-ray structures, powder X-ray diffractions (PXRD), thermogravimetric analyses (TGA), and differential scanning calorimetric (DSC) measurements.

Full text of DOI:10.1021/cg101316u

DOI: 10.1021/cg101316u
Structural Study on Solvates of Dopamine-Based Cyclic Imide
Derivatives
2011, Vol. 11
768–777
Devendra Singh and Jubaraj B. Baruah*
Department of Chemistry, Indian Institute of Technology Guwahati, Guwahati 781 039 Assam, India
Received October 7, 2010; Revised Manuscript Received December 9, 2010
ABSTRACT: A structural study on two dopamine-based imide derivatives, namely, 2-(3,4-dihydroxyphenethyl)isoindole-1,3-
dione (1) and 2,6-bis-[2-(3,4-dihydroxyphenyl)ethyl]pyrrolo [3,4-f]isoindole-1,3,5,7-tetrone (2), and their solvates was carried
out. The compound 1 (Z0 = 2) was crystallized through a melt crystallization process, whereas its two solvates (Z0 = 1 of each),
containing one water molecule (1a) and the other containing two quinoline molecules (1b) in their crystal lattices, respectively,
were obtained through solution crystallization. The reasons for Z0 = 2 arising from symmetry nonequivalent molecules in the
unit cell of 1 is attributed to the nonparallel arrangement of two layers of self-assembled molecules in crystal lattice, where one
layer has C-H π and another layer has CdO π interactions. Four different solvates of compound 2 (Z0 = 0.5 of each),
3 3 3
3 3 3
containing two DMF molecules (2a), two DMSO molecules (2b), two pyridine molecules (2c), and six quinoline molecules (2d),
were also obtained through solution crystallization of 2 in respective solvents. Solvate 2d has channels in its structure which are
formed by interaction of 2 with quinoline molecules through O-H N and C-H π interactions. Additional quinoline
3 3 3
3 3 3
˚
molecules reside in these channels of approximately (11 ꢀ 12) A dimension. Structural features of all the compounds and their
solvates have been studied by single crystal X-ray structures, powder X-ray diffractions (PXRD), thermogravimetric analyses
(TGA), and differential scanning calorimetric (DSC) measurements.
Introduction
Results and Discussion
Solvates are generally known as crystalline materials con-
taininga hostcomponentand molecule/s of thesolvent.1,2 The
intermolecular interactions between organic host and solvent
are responsible for the inclusion of solvent in crystal lattice.3 A
promising method to obtain guest-free crystalline forms of
host is melt crystallization.4 Among the solvates, hydrates are
of special interest in the pharmaceutical industry due to their
different physical properties from corresponding non-
hydrates.5 Weak intermolecular interactions control the sta-
bility of the solvate and also affect their aggregation that may
leadtocrystal structure of particularconformationinthe solid
state.6 Moreover, the inclusion of solvent molecules tunes
geometrical alignment of host molecules, which in turn affects
the Z0 value in crystals.7 Cyclic imide derivatives have versa-
tility in the field of crystal engineering to control the molecular
arrangements by various weak interactions.8 With an objec-
tive to understand the role of weak interactions in stabilizing
various solvates of imide derivative tethered to catecho-
late unit, we describe here a structural study on two dopa-
mine-based mono and diimide derivatives 2-(3,4-dihydroxy-
phenethyl)isoindole-1,3-dione(1) and2,6-bis-[2-(3,4-dihydro-
xyphenyl)ethyl]pyrrolo[3,4-f]-isoindole-1,3,5,7-tetraone (2)
(Chart 1) and their various solvates. Dopamine and its
derivatives have biological applications as a neurotransmit-
ter9 and as drugs for several diseases.10 They are of interest in
theoretical chemistry as a computational study supported by
experimental data has shown the existence of different con-
formers of dopamine derivatives due to C-C bond rotation.11
The other purpose of this study is to understand the
self-assembly of cyclic imide derivatives tethered to electron-
rich catechol unit/s.
The guest-free crystals of 1 were obtained by a melt crystal-
lization process.4 The hydrated form of the crystals, 1a, were
obtained by crystallizing 1 from commercially available sol-
vents such as ethanol, DMF, pyridine, etc., and the crystals of
quinoline solvate 1b were obtained from a quinoline solution
of 1 (Scheme 1).
The compound 1 crystallized in monoclinic P21/c space
group. It possesses two symmetry independent molecules of 1
(X and Y) in its crystallographic asymmetric unit (Figure 1).
Both the symmetry nonequivalent molecules exhibit O-
H
O interactions. These molecules interact with each other
3 3 3
˚
via C-H O (C20-H O1 dD
3.28 A, —D-H
3 3 3
A
A
3 3 3
3 3 3
3 3 3
135.62ꢀ) interaction. Both the symmetry independent sets of
molecules X and Y self-assemble themselves to form two
independent one-dimensional (1D) layers in the lattice. One
of the hydroxyl groups of molecule X involves discrete
˚
O-H O (O4-H4A O4 dD
2.98 A, —D-H
A
A
3 3 3
3 3 3
3 3 3
3 3 3
161.43ꢀ) interaction. The other hydroxyl group engages in a
cyclic R22 (7) hydrogen bond motif formed by the combina-
˚
tion of O-H
O
(O3-H3A O2 dD
2.74 A,
A
3 3 3
3 3 3
3 3 3
—D-H A 166.05ꢀ) and C-H O (C6-H O3 dD
A
3 3 3 3 3 3 3 3 3
3 3 3
˚
3.40 A, —D-H A 146.94ꢀ) interactions, which further
3 3 3
3 3 3
˚
3.55 A) interaction in the
interacts by O-H π (dO3
π
3 3 3
lattice. Similar types of discrete O-H O (O8-H8A O8
3 3 3
3 3 3
˚
dD 3 3 3 2.87 A, —D-H A 161.60ꢀ) interaction and cyclic
A
3 3 3
R22 (7) hydrogen bond motifs formed by the combination of
˚
O-H O (O7-H7A O6 dD
2.72 A, —D-H
3 3 3
A
A
3 3 3
3 3 3
3 3 3
˚
3.31 A,
162.80ꢀ) and C-H O (C22-H O7 dD
A
3 3 3 3 3 3
3 3 3
—D-H A 146.44ꢀ) interactions, along with O-H
π
3 3 3
3 3 3
3.50 A) interaction, are observed among the Y
˚
(dO7
π
3 3 3
molecules in the crystal lattice. Notably, both the hydroxyl
groups of molecule Y involve bifurcated hydrogen bonding
with the hydrogen atom of the phenyl ring of imide functionality
*To whom correspondence should be addressed. E-mail: juba@
iitg.ernet.in.
r
pubs.acs.org/crystal
Published on Web 01/25/2011
2011 American Chemical Society

Article
Crystal Growth & Design, Vol. 11, No. 3, 2011 769
Figure 1. Crystal packing of 1, showing the arrangement of symmetry independent molecules in crystal lattice (X and Y).
Chart 1. Structure of Cyclic Imide Derivatives 1, 2, and Some Solvent Molecules Used for Preparation of Their Solvates
Scheme 1. Structures of Host 1 and Its Two Solvates
via C-H O (C22-H O7 and C22-H O8 dD A 3.34
3 3 3 3 3 3 3 3 3
frame of coordinates to describe them. Thus, the subtle
differences in weak interactions due to slight variations in
orientations of molecules lead to symmetry nonequivalence in
unit cell.12
3 3 3
˚
A, —D-H
A
130.69ꢀ) interactions, which induces
3 3 3
˚
C-H π (dC31 π 3.70 A) interactions among the Y mole-
3 3 3
3 3 3
cules and aggregates them in a one-dimensional (1D) layer
supported by strong π π interactions. These types of
The solvate 1a crystallized in orthorhombic Pna21 space
group. It has one molecule of 1 with a water molecule in
3 3 3
bifurcated as well as C-H π interactions are absent in
the assembly of X molecules. They assemble in a 1D layer
3 3 3
asymmetric unit. In the crystal lattice, the O-H O inter-
3 3 3
structure by CdO π interactions present between the five-
actions between the host molecules are absent due to the
3 3 3
memberimide ringsofX molecules. There is a clear distinction
between the weak interactions in these two layers of X
and Y molecules. Both the layers require an independent
presence of water molecules, which are engaged in O-H
hydrogen bonds with host molecules and act as both donor
O
3 3 3
and acceptor (Figure 2). One of the hydrogen atoms of water

770 Crystal Growth & Design, Vol. 11, No. 3, 2011
Singh and Baruah
Figure 2. (a) Weak interactions in 1a. (b) Edge to face π π interactions between host molecules.
3 3 3
˚
Table 1. Hydrogen Bond Parameters (A, ꢀ) for 1a
d
d
d
D-H
A
(D-H) (H A) —D-H A (D A)
3 3 3
O4-H4A O5
3 3 3
2.15
3 3 3
159.00
3 3 3
2.93 (3)
0.82
3 3 3
[-x þ 2, -y þ 1, z - 1/2]
O4-H4A O3
3 3 3
0.82
0.82
0.78
2.26
1.90
2.25
114.02
163.56
166.32
2.70 (3)
2.69 (3)
3.02 (3)
O3-H3A O5
3 3 3
O5-H5A O4
3 3 3
[x, y, z þ 1]
O5-H5B O1
0.85
0.93
1.94
2.56
176.18
159.25
2.79 (3)
3.44 (4)
3 3 3
[-x þ 3/2, y - 1/2, z þ 1/2]
C16-H16 O2
3 3 3
[x, y, -1 þ z]
Figure 4. PXRD patterns of 1 and its two solvates.
˚
C-H O (C6-H O1 dD
3 3 3 3 3 3
3.33 A, —D-H
A
A
A
A
3 3 3
3 3 3
3 3 3
3 3 3
˚
129.58ꢀ and C16-H O2 dD
3.44 A, —D-H
3.25 A, —D-H
A
3 3 3
3 3 3
˚
159.25ꢀ and C9-H9B O2 dD
A
3 3 3
3 3 3
123.88ꢀ) interactions and edge-to-face π π interactions ex-
3 3 3
perienced between the five-member imide ring and phenyl ring
bearing two hydroxyl groups.
The solvate 1b crystallized in triclinic P1 space group. The
asymmetric unit of this has one molecule of 1 with two
quinoline molecules (Figure 3). Because of the hierarchy of
O-H N interactions over O-H O interactions, O-
3 3 3 3 3 3
Figure 3. A part of crystal packing of 1b showing the weak inter-
actions between the host and quinoline molecules.
H
O interactions are not found between the host molecules
3 3 3
in the crystal lattice. Two symmetry nonequivalent quinoline
molecules interact with host molecules in different ways. One
set of symmetry independent quinoline molecules interacts
with host molecules via discrete O-H N (O3-H3A N3
molecule involves bifurcated donor hydrogen bonding with a
˚
host molecule through O5-H5A O3 (dD
3.01 A,
˚
3.01 A,
A
3 3 3
3 3 3
3 3 3
3 3 3
—D-H A 108.96ꢀ) and O5-H5A O4 (dD
A
3 3 3
3 3 3
3 3 3
˚
dD A 2.93 A, —D-H A 146.30ꢀ) interaction and simul-
3 3 3
3 3 3
taneously involves bifurcated donor hydrogen bonding with
—D-H A 162.76ꢀ) interactions and the oxygen atom
3 3 3
involves bifurcated acceptor hydrogen bonding through
˚
the carbonyl oxygen of the imide ring of the host mole-
˚
O3-H3A O5 (dD
2.69 A, —D-H A 164.88ꢀ) and
3 3 3
A
3 3 3
3 3 3
cule through C-H O (C32-H O2 dD
3.33 A,
˚
3.41 A,
˚
A
3 3 3
3 3 3
O4-H4A O5 (dD A 2.92 A, —D-H A 159.23ꢀ) inter-
3 3 3
3 3 3
3 3 3
3 3 3
actions making a cyclic R3 (6) hydrogen-bonded six-mem-
3
—D-H A 148.18ꢀ and C33-H O2 dD
A
3 3 3
3 3 3
3 3 3
3 3 3
2
bered ring structure (Table 1). Another cyclic R2 (7) hydrogen
—D-H A 136.48ꢀ) interactions and situated inside the
alternate cavities formed between the host molecules via
˚
bond assembly is also formed in the lattice by the donor-accep-
C-H O (C6-H O3 dD
3.31 A, —D-H
3 3 3
A
A
tor O-H O interactions between the host and water mole-
3 3 3
3 3 3
3 3 3
3 3 3
155.96ꢀ) hydrogen bonding interactions. Another set of quino-
cule involving O5-H5A O3 and O4-H4A O5 inter-
3 3 3
3 3 3
line molecules also interact by discrete O-H N (O4-
actions. The other hydrogen atom of the water molecule forms
a hydrogen bond with a carbonyl oxygen atom of the host
˚
3 3 3
˚
H4A N2 dD A 2.82 A, —D-H A 176.91ꢀ) interactions
3 3 3
3 3 3
3 3 3
with host molecules and involve bifurcated acceptor hydro-
molecule via O5-H5B O1 (dD A, 2.79 A, —D-H
A
3 3 3
3 3 3
3 3 3
gen bonding with the hydrogen atom of imide functionality
˚
176.29ꢀ) interaction. This hydrogen atom further interacts to
˚
˚
3.60 A) interaction. Beside
that, the host molecules also assemble in the lattice through
through C-H π (dC4 π 3.69 A and dC4 π 3.70 A) inter-
3 3 3
the host via O-H π (dO5
π
3 3 3
3 3 3
actions. The quinoline molecules further interact with each
3 3 3
3 3 3

Article
Crystal Growth & Design, Vol. 11, No. 3, 2011 771
Figure 5. (a) Weak interactions between the DMF and host molecules in 2a. (b) 1D layer of host supported by π π interactions (along the
3 3 3
a axis). (c) Another 1D layer of host supported by C-H O and CdO π interactions (along the c axis).
3 3 3 3 3 3
Scheme 2. Various Solvates of 2
˚
3.63 A) interaction in the
other via C-H π (dC21
3 3 3
of solvent molecules in this particular temperature range.
Sharp endotherms appear in 1a at 189 ꢀC and in 1b at
185 ꢀC, are due to the melting of the solvates (Support-
ing Information).
Powder X-ray diffraction (PXRD) patterns obtained for 1
and its two solvates, 1a and 1b, show significant differences
(Figure 4). The inclusion of different solvents in the crystal
lattice of the host could easily be distinguished by dissimilar
diffraction patterns obtained for different solvated forms
π
3 3 3
hydrogen-bonded assembly of 1b.
Thermogravimetric analysis of 1a reveals loss of 6% weight
over the temperature range 65-115 ꢀC, which corresponds to
the loss of 1 equiv of water, whereas 45% weight loss
corresponds to 2 equiv of quinoline molecules, occurs from
1b in the temperature range between 75 and 170 ꢀC. The
endothermic peak at 121 ꢀC and a broad endothermic peak at
152 ꢀC in the DSC of 1a and 1b, respectively, confirm the loss

772 Crystal Growth & Design, Vol. 11, No. 3, 2011
Table 2. Hydrogen Bond Parameters (A, ꢀ) for Crystals 2a and 2d
Singh and Baruah
˚
compound
D-H
A
d (D-H)
d (H A)
3 3 3
—D-H
A
d (D A)
3 3 3
3 3 3
3 3 3
154.11
2a
O4-H4A O5 [x þ 1, y - 1, z]
0.82
0.82
0.82
0.97
0.93
0.82
0.82
0.82
1.95
2.30
1.93
2.55
2.41
1.94
2.11
2.33
2.71 (19)
2.73 (19)
2.74 (2)
3.44 (2)
3.07 (3)
2.76 (3)
2.86 (4)
2.74 (3)
3 3 3
O4-H4A O3
113.10
169.70
152.95
128.30
176.31
151.53
111.36
3 3 3
O3-H3A O1 [x þ 1, y - 1, z]
3 3 3
C7-H7A O2 [x - 1, y, z]
3 3 3
C16-H16 O3 [x - 1, y þ 1, z]
3 3 3
2d
O4-H4A N2 [-x þ 2, -y þ 1, -z þ 1]
3 3 3
O3-H3A N3 [x þ 1, y - 1, z]
3 3 3
O3-H3A O4
3 3 3
Figure 6. (a) Weak interactions between the DMSO and host molecules in 2b. (b) 3D tetrameric assemblies of host molecules encapsulating the
DMSO molecules (along the c axis). (c) Space filling model after removal of the DMSO molecules.
1a and 1b which crystallize in different space groups. Com-
parison of PXRD patterns of all three different crystalline
materials with simulated patterns from single crystal X-ray
structures determined at 298 K shows good agreement
(Supporting Information).
The crystal structures of four different solvates of 2
(Scheme 2) were also determined. Each of the solvates has
half of the host molecule (Z0 = 0.5) containing one DMF
molecule (2a), one DMSO molecule (2b), one pyridine mole-
cule (2c), and three quinoline molecules (2d) in the asymmetric
unit of the crystal lattice.
The solvate 2a crystallized in triclinic P1 space group. It has
half of the host molecule lying on the inversion center with one
DMF molecule in the asymmetric unit (Figure 5). The DMF
molecules interact with host molecules via both donor and
acceptor types of interactions in the lattice. The carbonyl
interaction with the oxygen atom of another hydroxyl group
2
of host molecule making a cyclic R2 (8) type of hydrogen
bond motif (Table 2). The methyl hydrogen of DMF also
involves C-H O interaction (C14-H14B O4 dD
A
3 3 3
3 3 3
3 3 3
3 3 3
˚
3.62 A, —D-H A 168.52ꢀ) with the host molecule. The
two carbonyl oxygen atoms of the host molecule involve two
different types of bifurcated acceptor hydrogen bondings.
One such hydrogen atom forms a bifurcated hydrogen bond
via the combination of O-H O (O3-H3A O1 dD
A
3 3 3
3 3 3
3 3 3
˚
2.74 A, —D-H A 169.63ꢀ) and C-H O (C9-H O1
3 3 3
3 3 3
3 3 3
˚
dD 3 3 3 3.32 A, —D-H A 125.18ꢀ) interactions, whereas
A
3 3 3
˚
another via two C-H O (C7-H7A O2 dD
3.44 A,
˚
3.47 A,
A
3 3 3
3 3 3
3 3 3
—D-H A 152.94ꢀ and C13-H O2 dD
A
3 3 3
3 3 3
3 3 3
—D-H A 141.80ꢀ) interactions. The later bifurcated hy-
3 3 3
drogen bonding results in the formation of CdO π interac-
3 3 3
tions between the host molecules making a 1D layered structure
along the c axis. Moreover, the host molecules are also layered
oxygen of DMF molecule acts as an acceptor and involves the
˚
O-H O hydrogen bond (O4-H4A O5 dD
2.71 A,
over each other in the lattice through strong π π interactions
A
3 3 3
3 3 3
3 3 3
3 3 3
—D-H A 154.07ꢀ) with one of the hydroxyl groups of the
host molecule, whereas the hydrogen atom of DMF present
constructing a 1D steplike structure along the c axis. These two
different kinds of layers further grow along the b axis by
interacting with DMF molecules, overall making a 3D host-
guest arrangement in the crystal lattice of 2a.
3 3 3
on carbonyl carbon acts as a donor and involves C-H
O
3 3 3
3.07 A, —D-H A 128.30ꢀ)
˚
(C16-H O3 dD
A
3 3 3
3 3 3
3 3 3

Article
Crystal Growth & Design, Vol. 11, No. 3, 2011 773
Figure 7. (a) Weak interactions between the pyridine and host molecules in 2c. (b) π π interactions between the two layers of host molecules
3 3 3
(red) which holds the pyridine molecules (blue) via O-H N and C-H O interactions.
3 3 3
3 3 3
The solvate 2b crystallized in triclinic P1 space group. The
asymmetric unit of 2b has half of the host molecule that lies on
the inversion center with one DMSO molecule. In the struc-
ture of 2b (Figure 6), the oxygen atom of DMSO molecule is
disordered over two positions having occupancies of 0.86 and
0.14, respectively. The hydroxyl groups of host molecules in
crystal structureof2c is devoid of cyclic hydrogen bondmotifs
and pyridine molecules are held with host molecules through
˚
discrete acceptor O-H N (O4-H4A N2 dD A 2.74 A,
3 3 3
3 3 3
3 3 3
—D-H A 163.01ꢀ) interaction with one of the hydroxyl
3 3 3
groups of the host molecule as well as discrete donor
˚
C-H O (C14-H O1 dD
144.74ꢀ) interaction with one of the carbonyl oxygen atoms
of the host molecule in the lattice (Figure 7). A cyclic R2 (8)
3.45 A, —D-H
3 3 3
A
A
3 3 3
3 3 3
3 3 3
2
the crystal structure of solvate 2b form cyclic R2 (10) hydro-
gen bond motifs interacting with each other via O-H
2
O
3 3 3
˚
(O4-H4A O3 dD A 2.78 A, —D-H A 146.54ꢀ) inter-
hydrogen bond motif forms between the host molecules when
associated together via O-H O (O3-H3A O1 dD
3 3 3 3 3 3
3 3 3
actions, generating a 1D infinite zigzag chain and involve
A
3 3 3
3 3 3
3 3 3
˚
˚
simultaneously O π (O4-C4 = 3.17 A) and π
π
2.80 A, —D-H A 128.25ꢀ) and C-H O (C7-H7B
3 3 3
3 3 3
3 3 3
3 3 3
˚
˚
(C3-C11 = 3.37 A) interactions, which overall construct a
two-dimensional (2D) steplike structure of host molecules.
O3 dD
3 3 3
3.38 A, —D-H A 146.54ꢀ) interactions,
A
3 3 3
3 3 3
generating a repeated tetrameric assembly of host molecules.
These tetramers encapsulate pyridine molecules inside the
assembly in the lattice. No weak interactions among the
pyridine molecules are observed. The pyridine molecules
generally form strong hydrogen bonds with acidic OH func-
tional groups14 and also have tendency to remain in stacked
assemblies in inclusion compounds.8j The host molecules also
The DMSO molecules form hydrogen bonds with host mole-
˚
cules via acceptor O-H O (O3-H3A O5 dD A 2.58 A,
3 3 3
3 3 3
3 3 3
—D-H A 175.25ꢀ) and donor C-H O (C14-H14B-
3 3 3 3 3 3
3 3 3
˚
O2 dD A 3.36 A, —D-H A 162.34ꢀ) interactions and
3 3 3
3 3 3
also interact with each other via C-H O (C15-H15A-
3 3 3
˚
O5dD A 3.30 A, —D-H A 152.75ꢀ) interactioninthe
3 3 3
3 3 3
3 3 3
crystal lattice. All these host-host, host-guest, and guest-
guest interactions result in the construction of repeated three-
dimensional (3D) tetrameric assemblies of host molecules
allow the rectangular voids formation in the lattice filled by
DMSO molecules when viewed along the c axis. The DMSO
molecules generally coordinate to acidic OH groups through
weak interactions,13 but in this case, the DMSO molecules are
held in the interstitial positions.
assemble with each other via another type of C-H
O
3 3 3
3.45 A, —D-H A 147.23ꢀ) CdO
˚
(C9-H O2 dD
A
3 3 3
3 3 3
3 3 3
π interaction. These multiple interactions found among
3 3 3
the host molecules project them in two different directions,
further making a three-dimensional layered arrangements
supported by strong π π interactions which exist between
3 3 3
the five-member imide ring and phenyl ring bearing two
hydroxyl groups. The pyridine molecules adopt a parallel
position between the two sheets of host molecules interacting
The solvate 2c crystallized in monoclinic P21/c space group.
It includes half of the host molecule that lies on inversion
center and one pyridine molecule in the asymmetric unit. The
via discrete O-H N and C-H O interactions in the
3 3 3 3 3 3
lattice of 2c.

774 Crystal Growth & Design, Vol. 11, No. 3, 2011
Singh and Baruah
Figure 9. PXRD patterns of 2 and its solvates.
quinoline molecules belong to the first and second set also
interact with each other via C-H π (dC16
˚
3.70 A and
π
3 3 3
3 3 3
3.52 A) interaction. This creates tetrameric assem-
˚
dC27
blies of quinoline molecules which adopts a chairlike geome-
π
Figure 8. (a) A part of the crystal structure of 2d showing different
types of weak interactions between the host and three symmetry
independent quinoline molecules. (b) Channel formation in assem-
bly of host and quinoline molecules (along the a axis). (c) Space
filling model after removal of one set of quinoline molecules residing
inside the channels.
3 3 3
try. Assemblies of pyridine derivatives held by C-H
π
π
3 3 3
3 3 3
interactions are reported in the literature.14 The C-H
interactions present between the host molecules and quinoline
molecules aggregate them in a 1D layer, which further results
in the formation of a 3D channel-like structure by the inter-
actions present between host and quinoline molecules. A third
set of quinoline molecules do not participate in the channel
formation. However, the channels created along the a axis
accommodate these quinoline molecules (Figure 8). When the
The solvate 2d crystallized in triclinic P1 space group. The
asymmetric unit of this structure has half of the host molecule
lying on the inversion center with three symmetry nonequiva-
lent quinoline molecules. Unlike the other solvates, the
O-H O and C-H O interactions found between the
3 3 3
3 3 3
˚
solventmolecules are omitted, thesechannelshave (11ꢀ 12) A
host molecules are absent in the crystal structure of 2d
(Figure 8). Apparently, the host molecules aggregate with
˚
dimension (Figure 8c). It may be noted that the C-H bond
next to the nitrogen atom of pyridine and quinoline partici-
pates in weak hydrogen bonding with carboxylic acid or
related functional groups.8k,l We have attempted to remove
the quinoline molecules by pyridines but it was not possible.
However, the reverse was possible; that is, the pyridine solvate
(2c) led to quinoline solvate (2d) on crystallization from
quinoline but not vice versa.
eachother via only weak C-H π (dC7 π 3.53 A) hydrogen
3 3 3
3 3 3
bonding interactionsappearing between the methylene hydro-
gen of flexible arms and the five-member imide ring of host
molecules. All the three symmetry independent quinoline
molecules have different types of interactions with host
molecules. The first set of quinoline molecules have three
different types of interactions withhost moleculesinthe lattice
˚
Thermogravimetric studies on these solvates show that
solvate 2a loses 2 equiv of DMF (21% weight loss) over the
temperature range 60-102 ꢀC, solvate 2b loses 2 equiv of
DMSO (17% weight loss) over the temperature range 95-
138 ꢀC, solvate 2c loses 2 equiv of pyridine (23% weight loss)
over the temperature range 65-118 ꢀC, while solvate 2d loses
6 equiv of quinoline molecules (56% weight loss) over the
temperature range 75-150 ꢀC. The results obtained from
TGA are further confirmed by DSC analyses. The endother-
mic peaks at 100, 140, 120, and 130 ꢀCappearduetothe loss of
solvent molecules in DSC profile of solvates 2a, 2b, 2c, and 2d,
respectively (Supporting Information).
The PXRD patterns obtained for solvent-free host 2 and
its different solvated forms 2a, 2b, 2c and 2d are shown in
Figure 9. The differences in the position and intensity of
diffraction peaks of the various solvates are due to the
inclusion of different solvent molecules in the crystal lattice
of host. The peaks obtained in the PXRD patterns of different
(i) discrete O-H N (O3-H3A N3 dD
2.86 A,
A
3 3 3
3 3 3
3 3 3
—D-H A 151.48ꢀ) interaction with one of the hydroxy
3 3 3
groups of the host; (ii) C-H O (C30-H O2 dD
A
3 3 3
3 3 3
3 3 3
˚
3.36 A, —D-H A 134.50ꢀ) interaction with one of the
carbonyl oxygens, in the combination of acceptor C-H
(dC6 π 3.76 A) interaction with methylene hydrogen of host;
3 3 3
π
3 3 3
˚
3 3 3
˚
(iii) bifurcated donor C-H π (dC24 π 3.68 A and dC24
π
3 3 3
3 3 3
3.72 A) interactions withthe phenyl ringbearing twohydroxyl
3 3 3
˚
groups of the host molecules. Asecond set of quinoline
1
molecules form a cyclic R2 (6) hydrogen bond motif by the
˚
combination of O-H N (O4-H4A N2 dD A 2.76 A,
3 3 3
3 3 3
3 3 3
—D-H A 176.31ꢀ) and C-H N (C12-H N2 dD
A
3 3 3 3 3 3 3 3 3
3 3 3
˚
3.34 A, —D-H A 130.69ꢀ) interactions (Table 2). A third
3 3 3
set of quinoline molecules do not facilitate by O-H
interactions but form a cyclic R2 (8) hydrogen bond motif by
N
3 3 3
2
˚
the combination of C-H N (C3-H N4 dD A 3.51 A,
3 3 3 3 3 3
3 3 3
—D-H A 158.29ꢀ) and C-H O (C32-H O1 dD
A
3 3 3 3 3 3 3 3 3
3 3 3
˚
3.53 A, —D-H A 150.96ꢀ) interactions in the lattice. The
3 3 3

Article
Crystal Growth & Design, Vol. 11, No. 3, 2011 775
Table 3. Crystallographic Parameters of 1, 1a, 1b, 2a, 2b, 2c, and 2d
compound no.
1
1a
1b
2a
2b
2c
2d
formulas
C16H13NO4
283.27
monoclinic
P21/c
23.4842(15)
5.0207(4)
25.7292(16)
90.00
115.859(4)
90.00
2729.9(3)
8
1.378
0.100
1184
27295
2721
50.00
C16H15NO5
301.29
orthorhombic triclinic
C34H27N3 O4 C32H34N4 O10 C30H32N2O10S2 C36H30N4 O8
C80H62N8O8
1263.38
triclinic
P1
8.790(3)
12.746(4)
15.130(5)
101.030(13)
91.205(14)
99.449(12)
1638.7(10)
1
1.280
0.084
662
16165
2455
50.00
formulawt
crystal system
space group
541.59
634.63
triclinic
P1
644.72
triclinic
P1
646.64
monoclinic
P21/c
Pna21
26.316(11)
7.329(4)
7.737(3)
90.00
90.00
90.00
1492.2(12)
4
1.341
0.101
632
9114
2273
50.00
P1
˚
a /A
8.6650(17)
12.644(2)
12.964(2)
77.925(9)
86.183(8)
87.733(9)
1385.4(5)
2
1.298
0.086
568
8789
6.3217(2)
8.5303(3)
15.5713(6)
80.929(2)
89.670(2)
69.818(2)
777.21(5)
1
1.356
0.102
334
7315
9.4527(5)
9.4740(4)
9.7186(4)
104.394(3)
101.121(3)
106.048(3)
777.52(6)
1
1.377
0.231
338
9245
14.9497(5)
8.8863(3)
12.1128(4)
90.00
98.096(2)
90.00
1593.12(9)
2
1.348
0.097
676
˚
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/ꢀ
17442
1989
50.00
3147
50.00
2190
50.00
1970
50.00
ranges (h, k, l)
-26 e h e 27 -31 e h e 31 -10 e h e 9
-7 e h e 7
-10 e k e 9
-11 e h e 11
-11 e k e 11
-11 e l e 11
98.2
4212/0/264
1.025
0.0809
-17 e h e 17 -10 e h e 10
-10 e k e 10 -14 e k e 15
-5 e k e 5
-30 e l e 30
100.0
-8 e k e 8
-8 e l e 9
98.7
2525/1/209
1.073
0.0476
-15 e k e 6
-15 e l e 13 -18 e l e 18
-14 e l e 13
99.5
-17 e l e 16
92.9
5355/0/435
1.016
0.0585
complete to 2θ (%)
data/restraints/parameters 4781/0/379
GOF (F2)
R indices [I > 2σ(I)]
R indices (all data)
98.0
4778/0/372
1.050
0.0673
0.0907
95.8
2691/0/212
1.068
0.0465
0.0532
2796/0/217
0.997
0.0400
0.925
0.0452
0.0860
0.0529
0.1029
0.0603
0.1664
solvates correlate well with the simulated peaks of X-ray
structures (Supporting Information).
Synthesis and Characterization of Compounds 1, 2, and Their
Solvates. 2-(3,4-Dihydroxyphenethyl)isoindole-1,3-dione (1).
A
solution of phthalic anhydride (0.740 g, 5 mmol) and dopamine
hydrochloride (0.945 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 brown-colored
crystalline material of the product was obtained. This was filtered and
dried in open air. Yield: 85%; IR (KBr, cm-1): 3373 (m), 3273 (m),
2929 (w), 1759 (m), 1693 (s), 1615 (m), 1531 (w), 1446 (s), 1435 (s), 1402
(s), 1357 (m), 1266 (m), 1242 (m), 1117 (w), 1090 (w), 1001 (w), 952 (w),
724 (m). 1H NMR (400 MHz, DMSO-d6): 8.79 (s, 1H), 8.68 (s, 1H),
7.82 (s, 4H), 6.56 (d, 2H, J = 7.6 Hz), 6.39 (d, 1H, J = 8.0 Hz), 3.70 (t,
2H, J = 7.2 Hz), 2.71 (t, 2H, J = 7.2 Hz). 13C NMR (DMSO-d6):
167.8, 145.2, 143.8, 134.4, 131.6, 129.0, 132.1, 119.3, 116.0, 115.6, 33.2.
ESI-MS: 284.115 [M þ Hþ]. The compound 1 was heated up to 200 ꢀC
in a test tube using oil bath and the resulting neat liquid phase was
cooled rapidly, putting the test tube in ice cubes. Crystals of 1 were
obtained immediately.
1a: The crystals of the solvate 1a were obtained as colorless
blocks from the corresponding solution of compound 1 in a variety
of ordinary solvents such as ethanol, isopropanol, t-butanol, 1,4
dioxane, tetrahydrofurane, N,N-dimethylformamide, dimethylsulf-
oxide, and pyridine. The hydrated form (1a) was obtained from each
solvent which was also confirmed by unit cell parameters. IR (KBr,
cm-1): 3340 (s), 3226 (s), 2948 (m), 1768 (m), 1692 (s), 1614 (m), 1529
(w), 1432 (s), 1403 (s), 1367 (s), 1263 (m), 1242 (m), 1199 (m), 1089
(w), 1002 (w), 952 (w), 861 (w), 720 (m). 1H NMR (400 MHz,
DMSO-d6): 8.79 (s, 1H), 8.68 (s, 1H), 7.82 (s, 4H), 6.57 (d, 2H, J =
7.6 Hz), 6.39 (d, 1H, J = 8.0 Hz), 3.70 (t, 2H, J = 7.2 Hz), 3.55 (s,
2H), 2.71 (t, 2H, J = 7.2 Hz).
Conclusions
The role of weak interactions of solvents with host mole-
cules,namely, 2-(3,4-dihydroxyphenethyl)isoindole-1,3-dione
(1) and 2,6-bis-[2-(3,4-dihydroxyphenyl)ethyl]pyrrolo [3,4-
f]isoindole-1,3,5,7-tetraone (2), in changing their packing
patterns are studied. The weak interactions play crucial roles
in changing the packing patterns and a subtle difference in
weak interactions such as C-H π and CdO π interac-
3 3 3 3 3 3
tions distinguishes the symmetry nonequivalent molecules in
the crystal lattice of 1. Hydrogen bonding interactions are
responsible for forming a porous structure to accommodate
DMSO molecules in the interstitial sites in the structure of 2b.
The quinoline molecules along with 2 act as a constituent for
building a secondary host system to encapsulate additional
molecules of quinoline. While forming such a structure, the
quinoline molecules occupy positions in the crystal lattice
which requires three independent sets of coordinates to de-
scribe their positions in the lattice.
Experimental Section
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 displacement coefficients. Crystallographic data collec-
tion was done at room temperature and the data are tabulated in
Table 3. In structure 2b, the DMSO molecule is disordered and
modeled by splitting occupancies of the oxygen atom.
1b: The solvate 1b was crystallized as brown-colored blocks from
the quinoline solution of compound 1. IR (KBr, cm-1): 3477 (m),
3067 (m), 2944 (m), 1767 (w), 1707 (s), 1617 (m), 1503 (w), 1465 (w),
1434 (m), 1393 (s), 1353 (m), 1298 (w), 1186 (m), 1112 (w), 1087 (w),
1
955 (w), 944 (w), 805 (m), 787 (m), 721 (m). H NMR (400 MHz,
CDCl3): 8.90 (m, 4H), 8.18 (d, 2H, J = 8.0 Hz), 8.11 (d, 2H, J = 8.4
Hz), 7.82 (d, 2H, J = 8.0 Hz), 7.77 (dd, 2H, J = 3.2 Hz), 7.72 (t, 2H,
J = 7.2 Hz), 7.65 (dd, 2H, J = 3.2 Hz), 7.55 (t, 2H, J = 7.2 Hz), 7.42
(dd, 2H, J = 4.0 Hz), 6.79 (d, 2H, J = 8.0 Hz), 6.62 (d, 1H, J = 8.0
Hz), 3.83 (t, 2H, J = 7.6 Hz), 2.82 (t, 2H, J = 7.6 Hz).
2,6-Bis-[2-(3,4-dihydroxyphenyl)ethyl]pyrrolo[3,4-f]isoindole-1,3,-
5,7-tetrone (2). A solution of pyromellitic dianhydride (1.09 g,
5 mmol) and dopamine hydrochloride (1.89 g, 10 mmol) in acetic
acid (35 mL) was refluxed for 4 h. The reaction mixture was cooled
to room temperature, poured into ice-cooled water (100 mL), and

776 Crystal Growth & Design, Vol. 11, No. 3, 2011
Singh and Baruah
stirred for 15 min. A yellow-colored precipitate of the product was
filtered and air-dried. Yield: 90%. IR (KBr, cm-1): 3461 (s), 3410
(s), 2949 (w), 1763 (m), 1702 (s), 1614 (m), 1518 (m), 1433 (m), 1396
(s), 1354 (s), 1302 (m), 1284 (w), 1234 (w), 1192 (m), 1179 (m), 1120
(w), 1096 (w), 1007 (w), 812 (w), 730 (w). 1H NMR (400 MHz,
DMSO-d6): 8.77 (s, 2H), 8.67 (s, 2H), 8.15 (s, 2H), 6.57 (s, 4H), 6.40
(s, 2H), 3.75 (s, 4H), 2.74 (s, 4H). 13C NMR (DMSO-d6): 166.1,
145.2, 143.8, 136.9, 128.8, 119.3, 117.3, 116.0, 115.6, 33.0. ESI-MS:
489.201 [M þ Hþ].
Hughes, D. S.; Hursthouse, M. B.; Lancaster, R. W.; Tavener, S.;
Threlfall, T. L. Chem. Commun. 2001, 603. (g) Nangia, A.; Desiraju,
G. R. Chem. Commun. 1999, 605. (h) Ma, B.-Q.; Coppens, P. Cryst.
Growth Des. 2004, 4, 1377. (i) Moorthy, J. N.; Natarajan, N. Cryst.
Growth Des. 2008, 8, 3360.
(3) (a) Sarma, J. A. R. P.; Desiraju, G. R. Polymorphism and Pseudo-
polymorphism in Organic Crystals:
A Cambridge Structural
Database Study; In Crystal Engineering; Seddon, K. R., Zaworotko,
M., Eds.; Kluwer: Norwell, MA, 1999; p 325. (b) Jetti, R. K. R.; Boese,
R.; Thallapally, P. K.; Desiraju, G. R. Cryst. Growth Des. 2003, 3,
1033.
2a: Solvate 2a was crystallized from a solution of DMF as red
block. IR (KBr, cm-1): 3461 (s), 3408 (s), 2924 (w), 1763 (m), 1703
(s), 1661 (m), 1518 (w), 1434 (m), 1395 (s), 1354 (s), 1302 (w), 1283
(w), 1192 (w), 1152 (w), 1120 (m), 1095 (m), 1006 (w), 812 (w), 729
(w). 1H NMR (400 MHz, DMSO-d6): 8.80 (s, 2H), 8.70 (s, 2H), 8.16
(s, 2H), 7.94 (s, 2H), 6.57 (dd, 4H, J = 4.4 Hz), 6.40 (d, 2H, J = 8.0
Hz), 3.74 (t, 4H, J = 7.6 Hz), 2.88 (s, 12H), 2.73 (t, 4H, J = 7.6 Hz).
2b: The crystals of solvate 2b were obtained as yellow blocks from
a solution of compound 2 in DMSO. IR (KBr, cm-1): 3461 (s), 3410
(s), 2935 (w), 1763 (m), 1702 (s), 1656 (w), 1620 (m), 1524 (m), 1435
(m), 1396 (s), 1354 (s), 1302 (m), 1284 (w), 1234 (w), 1192 (m), 1179
(4) (a) Sarma, B.; Roy, S.; Nangia, A. Chem. Commun. 2006, 4918.
(b) Saha, B. K.; Nangia, A. CrystEngComm 2006, 8, 440.
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Desiraju, G. R. Angew. Chem., Int. Ed. 2003, 42, 1963. (d) Yu, L.
ꢀ
ꢀ
ꢀ ꢀ
J. Am. Chem. Soc. 2003, 125, 6380–6381. (e) Kalman, A.; Fabian, L.;
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Argay, G.; Bernath, G.; Gyarmati, Z. J. Am. Chem. Soc. 2003, 125,
34. (f) Duntiz, J. D.; Bernstein, J. Acc. Chem. Res. 1995, 28, 193.
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Zaworotko, M. J. Angew. Chem., Int. Ed. 1997, 36, 972.
1
(m), 1120 (w), 1096 (w), 1075 (m), 1007 (w), 812 (w), 730 (w). H
(6) (a) Steiner, T. Angew. Chem., Int. Ed. 2002, 41, 48. (b) Nangia, A.
Acc. Chem. Res. 2008, 41, 595. (c) Jeffrey, G. A.; Saenger, W.
Hydrogen Bonding in Biological Structures; Springer Verlag: Berlin,
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University Press: New York, 1997. (e) Desiraju, G. R. Acc. Chem. Res.
2002, 35, 565. (f) Desiraju, G. R.; Steiner, T. The Weak Hydrogen
Bond in Structural Chemistry and Biology; Oxford University Press:
Oxford, U.K., 1999. (g) Bernstein, J. In Organic Solid State Chem-
istry; Desiraju, G. R., Ed.; Elsevier: Amsterdam, 1987; p 471. (h)
Blagden, R.; Davey, R. J.; Lieberman, H. F.; Williams, L.; Payne, R.;
Roberts, R.; Rowe, R.; Docherty, R. J. Chem Soc. Faraday Trans.
1998, 94, 1035. (i) Buttar, D.; Charlton, M. H.; Dochetry, R.; Starbuck,
J. J. Chem. Soc. Perkin Trans. 2 1998, 763. (j) Starbuck, J.; Docherty,
R.; Charlton, M. H.; Buttar, D. J. Chem. Soc. Perkin Trans. 2 1999,
677. (k) Kumar, V. S. S.; Addlagatta, A.; Nangia, A.; Robinson, W. T.;
Broder, C. K.; Mondal, R.; Evans, I. R.; Howard, J. A. K.; Allen, F. H.
NMR (400 MHz, DMSO-d6): 8.81 (s, 2H), 8.72 (s, 2H), 8.20 (s, 2H),
6.61 (dd, 4H, J = 4.0 Hz), 6.47 (d, 2H, J = 8.0 Hz), 3.75 (t, 4H, J =
7.6 Hz), 2.75 (t, 4H, J = 7.6 Hz).
2c: The solvate 2c was obtained by crystallization of compound 2
from pyridine solution as yellow blocks. IR (KBr, cm-1): 3460 (s),
3410 (s), 2945 (w), 1761 (m), 1707 (s), 1610 (m), 1517 (m), 1432 (m),
1395 (s), 1353 (m), 1297 (w), 1281 (w), 1178 (s), 1119 (s), 1094 (m),
1006 (m), 957 (w), 812 (w), 727 (w). 1H NMR (400 MHz, DMSO-
d6): 8.80 (s, 2H), 8.70 (s, 2H), 8.57 (d, 4H, J = 5.6 Hz), 8.16 (s, 2H),
7.84 (t, 4H, J = 7.6 Hz), 7.38 (t, 4H, J = 6.4 Hz), 6.57 (dd, 4H, J =
4.0 Hz), 6.41 (d, 2H, J = 8.0 Hz), 3.76 (t, 4H, J = 7.6 Hz), 2.76
(t, 4H, J = 7.6 Hz).
2d: A solution of compound 2 in pyridine and quinoline resulted
in the formation of crystals of solvate 2d as red blocks. IR (KBr,
cm-1): 3460 (s), 3412 (s), 2924 (w), 1763 (m), 1714 (s), 1597 (w), 1503
(w), 1434 (w), 1392 (s), 1353 (s), 1281 (w), 1194 (m), 1121 (m), 1094
€
Angew. Chem., Int. Ed. 2002, 41, 3848. (l) Aakeroy, C. B.; Desper, J.;
1
Urbina, J. F. Chem. Commun. 2005, 2820.
(m),, 957 (w), 801 (w), 729 (w). H NMR (400 MHz, DMSO-d6):
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8.89 (m, 4H), 8.77 (s, 6H), 8.36 (d, 6H, J = 8.0 Hz), 8.13 (s, 2H),
8.00 (dd, 12H, J = 8.0 Hz), 7.76 (t, 6H, J = 6.8 Hz), 7.61 (t, 6H,
J = 6.8 Hz), 7.53 (dd, 6H, J = 4.4 Hz), 6.58 (dd, 4H, J = 4.0 Hz),
6.40 (d, 2H, J = 8.4 Hz), 3.74 (t,4H, J = 7.2 Hz), 2.74 (t, 4H, J =
7.2 Hz).
(8) (a) Kishikawa, K.; Tsubokura, S.; Kohmoto, S.; Yamamoto, M.;
Yamaguchi, K. J. Org. Chem. 1999, 64, 7568. (b) Kishikawa, K.;
Iwashima, C.; Kohmoto, S.; Yamaguchi, K.; Yamamoto, M. J. Chem.
Soc. Perkin Trans. 1 2000, 2217. (c) Degenhardt, C., III; Shortell,
D. B.; Adams, R. D.; Shimizu, K. D. Chem.Commun. 2000, 929. (d)
Degenhardt, C. F.; Lavin, J. M.; Smith, M. D.; Shimizu, K. D. Org.
Lett. 2005, 7, 4079. (e) Rasberry, R. D.; Smith, M. D.; Shimizu, K. D.
Org. Lett. 2008, 13, 2889. (f) Colquhoun, H. M.; Williams, D. J.; Zhu,
Z. J. Am. Chem. Soc. 2002, 124, 13346. (g) Cheney, M. L.; McManus,
G. J.; Perman, J. A.; Wang, Z.; Zaworotko, M. J. Cryst. Growth Des.
2007, 7, 616. (h) Barooah, N.; Sarma, R. J.; Baruah, J. B. Cryst. Growth
Des. 2003, 3, 639. (i) Baruah, J. B.; Karmakar, A.; Barooah, N.
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Acknowledgment. The authors thank Department of
Science and Technology, New Delhi (India), for financial
support. D.S. is thankful to Council of Scientific and Industrial
Research, New Delhi (India), for Senior Research Fellowship.
Supporting Information Available: The CIF of the structures are
deposited to the Cambridge Crystallographic Database UK and has
the CCDC nos. 793834-793840. The PXRD, TG, DSC of the
compounds, and hydrogen bond table for 1 and 1b. This material
is available free of charge via the Internet at http://pubs.acs.org.
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