Reduced Schiff-base assisted novel dihydrogenphosphate-water polymer

Article abstract of DOI:10.1039/c2ce25502b

Reduced Schiff bases with a common p-nitro-o-phenylenediamine moiety have been synthesised and their structures have been characterized by single-crystal structural analysis. Schiff bases having self-complementary H-bond donors and H-bond acceptors can form a scissors like structure through intermolecular H-bonding interaction. Reduced Schiff bases interact with biologically important dihydrogenphosphate ion and form stable complexes. Furthermore, dihydrogenphosphate and water form an unprecedented self-assembled dihydrogenphosphate-water [H₂PO₄·H ₂O]_n^n- 1D supramolecular polymer upon complexation with reduced Schiff bases.

Full text of DOI:10.1039/c2ce25502b

View Article Online / Journal Homepage / Table of Contents for this issue
Dynamic Article Links
CrystEngComm
Cite this: CrystEngComm, 2012, 14, 6029–6034
www.rsc.org/crystengcomm
PAPER
Reduced Schiff-base assisted novel dihydrogenphosphate–water polymer{
Sasanka Dalapati,a Md. Akhtarul Alam,*b Sankar Janaa and Nikhil Guchhait*a
Received 5th April 2012, Accepted 29th May 2012
DOI: 10.1039/c2ce25502b
Reduced Schiff bases with a common p-nitro-o-phenylenediamine moiety have been synthesised and
their structures have been characterized by single-crystal structural analysis. Schiff bases having self-
complementary H-bond donors and H-bond acceptors can form a ‘‘scissors’’ like structure through
intermolecular H-bonding interaction. Reduced Schiff bases interact with biologically important
dihydrogenphosphate ion and form stable complexes. Furthermore, dihydrogenphosphate and water
n2
form an unprecedented self-assembled dihydrogenphosphate–water [H2PO4?H2O]n 1D
supramolecular polymer upon complexation with reduced Schiff bases.
their dihydrogenphosphate complexes were structurally char-
Introduction
acterized by X-ray single-crystal diffraction analysis.
Design and syntheses of molecular receptors for recognition and
Interestingly, X-ray crystal analysis shows that compound 1
22
and dihydrogenphosphate ion lead to the [H2PO4?H2O]2
sensing of phosphate ions are of considerable current research
interest due to their biological and environmental importance.1
cluster while compounds
2 and 3 form complexes with
In this respect, development of molecular receptors for recogni-
tion of phosphate ions using amine, amide,2 urea,3 thiourea,4
pyrrole,5 imidazole,6 pyridine moieties and metal assisted
organic frameworks7 bearing multiple binding sites have received
tremendous attention. Recently, several groups reported tripodal
receptors for encapsulation of dihydrogenphosphate ion.8–10
Among these, Kim and co-workers have reported redox-active
ferrocene appended aryl triazole, which can recognize dihydro-
genphosphate ion electrochemically11 and Hossain et al. reported
a cyclic octamer of dihydrogenphosphate.12 In all these cases,
single-crystal X-ray diffraction shows that dihydrogenphosphate
ion or its dimer are surrounded/encapsulated by the ligand and
exhibit beautiful supramolecular structures. However, the water–
dihydrogenphosphate H-bonded ligand is almost unexplored,
although a water–phosphate chain is involved in physiological
processes.13
dihydrogenphosphate and exhibit interesting 1D dihydrogen-
n2
phosphate–water [H2PO4?H2O]n polymer structure, which is
structurally unique compared with the reported dihydrogenpho-
sphate ion containing polymer.
Our designed reduced Schiff bases contain both H-bond donor
(primary amine, –NH2 and secondary amine, –NH–) and
H-bond acceptor sites (pyridine moiety and NO2 group contain-
ing ‘‘O’’ atom, Scheme 2). We expect that they would be ideal
receptors for anions or neutral molecules owing to both H-bond
accepting and H-bond donating capability. Therefore, we have
chosen dihydrogenphosphate as a guest molecule, which has
both H-bond acceptor ‘‘O’’ and ‘‘O2’’ atoms and H-bond donor
–OH groups (Scheme 2).
Experimental
Very recently, we have reported the p-nitro-o-phenylenedia-
mine group and imidazo[1,2-a]pyridine group containing
reduced Schiff base for selective recognition of dihydrogenpho-
sphate ion via an ‘‘unlock–lock’’ mechanism.14 This finding
encouraged us to further investigate whether the pyridyl group is
essential for binding the dihydrogenphosphate ion or not. To
explore this possibility, we have designed and synthesized two
new compounds 2 and 3 (Scheme 1). These two compounds and
Materials and methods
All reagents and solvents were used as received from commercial
sources without further purification. Tetrabutylammonium
aDepartment of Chemistry, University of Calcutta, Kolkata, India.
E-mail: nguchhait@yahoo.com; Fax: 91 33 23519755; Tel: 91 33 23408386
bDepartment of Chemistry, Aliah University, Kolkata, India.
E-mail: alam_iitg@yahoo.com; Fax: 91 33 23671433;
Tel: 91 33 23671434/35
{ CCDC reference numbers CCDC 867103 (2), 867102 (3), 867417
(2?H2PO42) and 867101 (3?H2PO42). For crystallographic data in CIF or
other electronic format see DOI: 10.1039/c2ce25502b
Scheme 1 Compounds used in these studies.
CrystEngComm, 2012, 14, 6029–6034 | 6029
This journal is ß The Royal Society of Chemistry 2012

View Article Online
3170, 1667, 1636, 1598, 1580, 1523, 1492, 1465, 1433, 1386, 1341,
1301, 1252, 1210, 1097, 1000, 841, 766, 744, 641 cm21. ESI-MS (m/z)
calc. for M+ (C12H12N4O2) 244.09, found 245.04 (M + H)+.
1
Compound 3. Yield: 80%, H NMR in CD3CN, 300 MHz, d
(ppm): 4.42 (s,–CH2–), 4.84 (s,–NH2), 6.68 (d, J = 8.4 Hz, 1H),
7.29–7.46 (m, 7H), 7.57 (d, J = 8.7 Hz, 1H). 13C NMR
(75.5 MHz, CD3CN, 20 uC) d (ppm) 47.00, 105.60, 111.85,
115.60, 116.89, 126.78, 127.13, 128.14, 134.46, 138.73, 142.80; IR
(KBr): 3473, 3380, 1638, 1600, 1576, 1522, 1475, 1454, 1429,
1358, 1274, 1149, 1105, 859, 733, 696 cm21. ESI-MS (m/z) calc.
for M+ (C13H13N3O2) 243.10, found 244.00 (M + H)+.
Scheme 2 H-Bond donors and acceptors in dihydrogenphosphate and
receptor 2.
dihydrogenphosphate (Bu4N+H2PO42) was purchased from
Sigma-Aldrich Chemical Company.
IR spectra (KBr pellet, 4000–400 cm21) were recorded on a
1
Parkin Elmer model 883 infrared spectrophotometer. H NMR
Results and discussion
Compounds 2 and 3 were synthesized according to our published
procedure as that of compound 1.14 The purity and character-
ization of the compounds were verified by 1H and 13C NMR, IR
and mass spectrometric analysis. Interestingly, single crystals
suitable for X-ray diffraction for all three compounds were
spectra were recorded on a Bruker, Avance 300 spectrometer,
where chemical shifts (d in ppm) were determined with respect to
tetramethylsilane (TMS) as internal standard.
Suitable single crystals of compounds 2, 3, 2?H2PO4 and
3?H2PO4 were mounted at 293(2) K on a Bruker-AXS SMART
APEX II diffractometer equipped with a graphite monochro-
obtained from methanol–water mixtures. Crystal data and
2
refinement details for compounds 2, 3, 2?H2PO4
2
3?H2PO4 are given in Table 1.
and
˚
mator and Mo-Ka (l = 0.71073 A) radiation. The crystal was
Compound 2 was crystallized in space group C2/c. Crystal
analysis shows that the N atom of the pyridine molecule and N
atoms of the o-phenylenediamino moiety are at a relative twist
angle of 62.54u (Fig. 1). The crystal lattice shows that compound
2 forms a ‘‘scissors’’ like dimer and is connected by four
intermolecular H-bonding interactions. In such cases one
molecular unit containing primary amine (N1H1B) and second-
ary amine (N2H2A) act as H-bond donors and the other
molecular unit containing the pyridine N4 atom acts as a
positioned at 60 mm from the CCD. 360 frames were measured
with a counting time of 5 s. The structure was solved using the
Patterson method by using SHELXS97. Subsequent difference
Fourier synthesis and least-squares refinement revealed the
positions of the remaining non-hydrogen atoms. Non-hydrogen
atoms were refined with independent anisotropic displacement
parameters. Hydrogen atoms were placed in idealized positions
and their displacement parameters were fixed to be 1.2 times
larger than those of the attached non-hydrogen atom. Successful
convergence was indicated by the maximum shift/error of 0.001
for the last cycle of the least squares refinement. Absorption
corrections were carried out using the SADABS program.15 All
calculations were carried out using SHELXS97, SHELXL97,
PLATON99, ORTEP-32 and WinGX system Ver-1.64.16
˚
H-bond acceptor and vice versa (distances 3.206 and 3.217 A
respectively, Fig. 1, Table 2). Due to these intermolecular
H-bonding interactions, two molecular units come close
together, and two pyridine rings are further connected by p–p
˚
interaction (3.790 A). Furthermore, the N1H1A atom of the
primary amine is connected with another molecular unit
containing O1 and O2 atoms of the –NO2 group through
Syntheses
˚
H-bonds (distances 3.364 and 3.265 A, respectively) and forms a
Compounds 2 and 3 were prepared by following the synthetic
procedure14 of compound 1 and are presented in the following
synthetic scheme 3.
1D supramolecular polymer (Fig. 2).
Interestingly, a similar type of ‘‘scissors’’ like structure has
been reported in case of compound 1 (Fig. 1).14 However, in such
cases the twist angle between o-phenylenediamine and imi-
dazo[1,2-a]pyridine moieties is about y76.38u, which is slightly
higher than in case of compound 2 (y62.54u). As a result an
increase in intermolecular donor–acceptor distances were
observed and hence, a solvent (water) molecule is required as
an intermediate H-bond donor–acceptor during the crystal-
lization of compound 1. The water molecule O1w acts as H-bond
acceptor and forms an H-bond with H-bond donor N2H2,
N3H3C of o-phenylenediamine. On the other hand, the N5 atom
of the imidazo[1,2-a]pyridine moiety acts as H-bond acceptor
and O1wH1 (water) acts as H-bond donor. Because of these
intermolecular H-bonding interactions two imidazole[1,2-a]pyr-
idine moieties come close together and are connected by strong
p–p interaction. Interestingly, these p–p interactions facilitate to
form a further p–p interaction between two nitrobenzene
moieties (in compound 1, Fig. 3). However, such type of p–p
interaction is absent in the case of compound 2 (Fig. 1).
1
Compound 2. Yield: 85%, H NMR in CD3CN, 300 MHz, d
(ppm): 4.50 (s,–CH2–), 4.85 (s,–NH2), 6.70 (d, J = 8.7 Hz, 1H), 7.23–
7.76 (m, 5H), 8.57 (d, J = 4.8 Hz, 1H). 13C NMR (75.5 MHz,
CD3CN, 20 uC) d (ppm) 48.52, 105.68, 112.01, 115.69, 116.92,
121.31, 121.96, 134.57, 136.42, 142.89, 148.74; IR (KBr): 3419, 3350,
Scheme 3 Synthetic scheme of compounds.
6030 | CrystEngComm, 2012, 14, 6029–6034
This journal is ß The Royal Society of Chemistry 2012

View Article Online
2
Table 1 Crystal data and refinement details for compounds 2, 3, 2?H2PO4 and 3?H2PO4
2
2
2
Parameters
2
3
2?H2PO4
3?H2PO4
Formula
Mr
C12H12N4O2
244.26
C13H13N3O2
243.27
C28H52N5O7P
601.72
C29H53N4O7P
600.72
Crystal system
Space group
Monoclinic
C2/c
Monoclinic
P21/c
Triclinic
P-1
Monoclinic
P21/n
˚
a/A
15.007(13)
10.891(9)
16.137(14)
90
114.279(10)
90
2404(4)
8
1.350
0.1012
2289
13.1110(4)
5.9151(2)
16.3090(5)
90
110.012(1)
90
1188.44(7)
4
1.365
0.0457
2431
9.602(5)
13.194(5)
15.104(5)
113.014(5)
94.332(5)
105.702(5)
1659.6(12)
2
1.204
0.0678
6579
5090
9.7398(15)
14.884(2)
23.545(4)
90
98.880(2)
90
3372.4(9)
4
1.181
0.1177
6400
˚
b/A
˚
c/A
a/u
b/u
c/u
3
˚
V/A
Z
Dc/g cm23
Rint
No. unique data
No. data with I . 2s(I)
R1, wR2
1235
0.0469, 0.1347
0.959
1958
0.0358, 0.1124
1.031
3731
0.0676, 0.2101
1.004
0.0532, 0.1670
1.045
GOF on F2
Fig. 2 1D polymer through intermolecular H-bonding/p interactions in
compound 2.
Fig. 1 ‘‘Scissors’’ like molecular dimers of compounds 1 and 2 and
molecular structure of compound 3.
receptor or ligand. Our designed molecular systems have self-
complementary H-bond donors and acceptors, which is suitable
to interact with the dihydrogenphosphate molecule.
In compound 3, the phenyl ring and o-phenylenediamine
containing the benzyl ring are approximately perpendicular to
each other by an angle of 82.31u. It is noteworthy to mention
that due to the absence of H-bond acceptor moieties (present in 1
and 2), compound 3 does not exhibit any ‘‘scissors’’ like dimer
(Fig. 1). However, an interesting intermolecular H-bonding
polymer was observed. The primary amine (N1H1B) and
secondary amine (N2H2A) were H-bonded with the next
molecular unit containing O2 of nitro group (distances 3.127
Compounds 2 and 3 interact with tetrabutylammonium
2
dihydrogenphosphate to form complexes 2?H2PO4
2
3?H2PO4 , respectively. Single crystals suitable for X-ray
and
diffraction were grown by vapour diffusion of diethyl ether
into a mixture of an acetonitrile solution of each compound
and tetrabutylammonium dihydrogenphosphate salt at room
temperature.
˚
and 3.212 A, respectively, Table 3) and forms a 1D polymer
The crystal analysis shows that mixture of compound 2 and
dihydrogenphosphate (n-Bu4N?H2PO4) was crystallized in space
group P-1 with molecular formula [2?H2PO4?(n-Bu4N)?H2O]
(Fig. 5, middle). In the presence of dihydrogenphosphate ion,
H-bond donors N1 and N2 atoms of the o-phenylenediamine
(Fig. 4, top). The other N1H1A atom of the primary amine also
forms an H-bond with another molecular unit nitro group
˚
containing O1 atom within the distance of 3.173 A and leads to a
2D supramolecular network (Fig. 4, bottom).
According to the previous reported literature,17 generally the
dihydrogenphosphate ion can form a dimer through self-
complementary (–OH and O2 ion) H-bonding interaction. The
remaining ‘‘–OH’’ group and ‘‘LO’’ atom are available as
H-bond donor and H-bond acceptor, respectively, with the
Table 2 Different types of H-bonding interactions in 2
a
…
…
…
˚
A/A
…
D–H A/u
˚
D–H/A
˚
A/A
D–H
A
H
D
…
N1–H1A O2
N1–H1B N4
N2–H2A N4
0.82(2)
0.99(3)
0.78(2)
2.49(2)
2.22(3)
2.45(2)
3.265(4)
3.206(4)
3.217(4)
160(2)
175(2)
165(2)
…
…
a
D is donor and A is acceptor.
Fig. 3 Polymeric chain of ‘‘scissor’’ like structure of compound 1.
CrystEngComm, 2012, 14, 6029–6034 | 6031
This journal is ß The Royal Society of Chemistry 2012

View Article Online
Table 3 Different types of H-bonding interactions in 3
a
…
…
˚
A/A
…
˚
A/A
…
D–H A/u
˚
D–H/A
D–H
A
H
D
…
N1–H1A O1
0.90(2)
0.86(3)
0.78(2)
2.51(2)
2.31(3)
2.50(2)
3.173(2)
3.127(19)
3.212(2)
131.0(16)
159(2)
152.6(17)
…
N1–H1B O2
…
N2–H2A O1
a
D is donor and A is acceptor.
Fig. 6 Dimers of 1?H2PO4?H2O, 2?H2PO4?H2O and 3?H2PO4?H2O
(tetrabutylammonium cations, Bu4N+) omitted for clarity.
Table 4 Different types of H-bonding interactions in 2?H2PO4
a
…
…
˚
A/A
…
˚
A/A
…
˚
D–H/A
D–H
A
H
D
D–H A/u
…
O3(w)–H3A N1
0.84(5)
0.85(3)
0.85(4)
0.89(5)
0.87(4)
0.83(3)
0.83(3)
2.44(5)
1.86(3)
1.81(4)
1.64(5)
2.19(4)
2.23(3)
2.15(3)
3.162(4)
2.707(3)
2.663(4)
2.527(3)
3.008(4)
3.043(4)
2.975(3)
145(4)
176(4)
173(3)
177(5)
157(4)
166(3)
171(3)
…
O3(w)–H3B O7
…
O4–H4A O3(w)
…
O5–H5A O6
…
…
N1–H1A O6
Fig. 4 1D polymer through intermolecular H-bonding (top) and 2D
polymer through intermolecular H-bonding (bottom) of compound 3.
N1–H1B O7
…
N2–H2A O7
a
D is donor and A is acceptor.
moiety and the H-bond acceptor N4 atom of pyridine molecule
are twisted by an angle of 90.18u and are pointing to opposite
directions. As a result, the N4 atom of the pyridine moiety does
not take part in H-bond formation but facilitates the incoming
dihydrogenphosphate ion for dimerization with the other
dihydrogenphosphate unit (Fig. 6, middle). Crystal structure
analysis shows that primary amine (N1H1B) and secondary
amine (N2H2A) forms a hydrogen bond with O7 of the
2
However, the crystal packing of 2?H2PO4 shows that the O6
atom of dihydrogenphosphate ion is H-bonded with the next
molecular unit containing the N1H1A atom and thus constructs
a dihydrogenphosphate bridge dimer. The water O3 atom acts as
H-bond acceptor and O4H4A atom of dihydrogenphosphate
˚
acts as H-bond donor (distance 2.663 A) and water molecules act
˚
dihydrogenphosphate ion (distances 3.043 and 2.976 A respec-
as a bridging agent between two dihydrogenphosphate dimers.
Interestingly, the water molecule (O3H3A) is also H-bonded
˚
with the N1 atom of a primary amine (Table 4, 3.162 A).
tively). Interestingly, one water molecule O3H3B is also
˚
H-bonded with the O7 atom (distance 2.662 A) (Fig. 5 middle,
Table 4).
Furthermore, the O5H5A atom of one dihydrogenphosphate
acts as a H-bond donor and the other dihydrogenphosphate O6
atom acts as an H-bond acceptor and vice versa and forms a 1D
polymer (Fig. 7). The 1D polymer is further connected by C–H –p
interaction between two layers and forms a 2D supramolecular
architecture (Fig. 8). Such type of dihydrogenphosphate–water
polymer is hardly reported in the literature.18
2
In contrast, for the 1?H2PO4 complex,14 dihydrogenpho-
sphate ion reinforces the N3 atom of imidazo[1,2-a]pyridine
moiety pointing unidirectionally with respect to the N1 and N2
atoms of the amine group. As a result, O3 and O5 of H2PO42 ion
form H-bonds with N3, N1 and N2 atoms of 1. These types
of H-bonding interactions ‘‘locked’’ the free rotation of
imidazo[1,2-a]pyridine moiety of compound 1 (Fig. 5, left).14
Thus, the water molecule in 1?H2PO4 (Fig. 6, left) and in
2?H2PO4 (Fig. 6, middle) are H-bonded with dihydrogenphosphate
Fig. 5 Molecular structures of 1?H2PO4, 2?H2PO4 and 3?H2PO4
(tetrabutylammonium cations, Bu4N+) omitted for clarity
Fig. 7 1D framework through intermolecular H-bonding interactions in
2
2?H2PO4 with 1D dihydrogenphosphate–water polymer.
6032 | CrystEngComm, 2012, 14, 6029–6034
This journal is ß The Royal Society of Chemistry 2012

View Article Online
Fig. 9 Discrete dihydrogenphosphate–water cluster through intermole-
2
cular H-bonding interactions in 1?H2PO4
.
In the complex 3?H2PO42, primary amine (N1H1B), and
secondary amine (N2H2A) act as H-bond donors and form
hydrogen bond with O7 of dihydrogenphosphate ion (distances
˚
3.074 and 2.998 A, respectively, Fig. 6, right and Table 5).
Interestingly, one water molecule (O1wH1) is also H-bonded
˚
with the O4 atom of dihydrogenphosphate ion (distance 2.584 A,
Fig. 8 2D architecture through intermolecular H-bonding/p interac-
2
tions in 2?H2PO4 with 1D dihydrogenphosphate–water polymer.
Table 5).
The lattice diagram shows that the N1H1A atom is further
H-bonded with another dihydrogenphosphate ion containing O5
˚
atom (distance 3.253 A). The O7H7 atom of dihydrogenpho-
in two different ways. In 1?H2PO4 the water molecule acts as a
H-bond donor with two dihydrogenphosphate ions but in
2?H2PO4 the water molecule acts as an H-bond donor with one
dihydrogenphosphate ion and an H-bond acceptor with the other
dihydrogenphosphate ion. Furthermore, in 1?H2PO4 a dihydro-
genphosphate–water cluster (Fig. 9 and 10) is formed through the
water molecule, where the water O1 acts as a H-bond acceptor
from the primary amine of N1 but in 2?H2PO4 a dihydrogenpho-
sphate–water polymer is formed through a dihydrogenphosphate
bridge, where the O5H acts as H-bond donor and O6
atom of another molecule acts as H-bond acceptor and vice versa
(Fig. 7).
sphate acts as H-bond donor and O1w (water molecule) acts as
H-bond acceptor. Importantly, here the water molecule
(O1wH2) forms an H-bond with the primary amine (N1,
˚
distance 3.072 A). Furthermore, dihydrogenphosphate ions form
dimers through intermolecular H-bonding interactions, where
the O5H5A atom of one dihydrogenphosphate ion acts as an
H-bond donor and O6 atom of another dihydrogenphosphate
˚
ion acts as H-bond acceptor and vice versa (distance 2.496 A)
and forms a 1D dihydrogenphosphate–water polymer (Fig. 11).
In summery, we have structurally characterized reduced Schiff
bases having a common nitro-o-phenylenediamine moiety, which
form interesting supramolecular architectures. Among these,
Schiff bases containing pyridyl/imidazole moieties form mole-
cular ‘‘scissors’’. Moreover, these compounds act as efficient
hosts to interact with biologically important dihydrogenpho-
sphate guest, therefore, in all compounds (1, 2 and 3) the p-nitro-
o-phenylenediamine moiety plays an important role for the
To examine the necessity of a pyridine/imidazo[1,2-a]pyridine]
moiety as an H-bond acceptor for the formation of
a
dihydrogenphosphate complex we have designed and synthesized
compound 3, where one H-bond acceptor is absent compared to
1 and 2. Interestingly, we also obtained single crystals from a
1 : 1 mixture of 3 and dihydrogenphosphate ion. The crystal
structure analysis shows that complex crystallized in space group
P21/n with molecular formula [3?H2PO4(n-Bu4N)?H2O]. The
crystal structure shows that the o-phenylenediamine and benzyl
moieties were deviated by an angle of y83.96u from one another
and form a stable conformer (Fig. 5, right). Additionally, the
H-bonding interactions between compound 3 and dihydrogen-
phosphate ion are also similar with that of the H-bonding
interactions between compound 2 and dihydrogenphosphate ion.
Table 5 Different types of H-bonding interactions in 3?H2PO4
a
…
…
˚
A/A
…
˚
A/A
…
˚
D–H/A
D–H
A
H
D
D–H A/u
…
O1w–H1w1 O4
0.8500
0.8500
0.8200
0.93(3)
0.77(4)
0.92(4)
0.73(4)
1.8300
2.2900
1.9200
1.57(3)
2.58(4)
2.19(4)
2.28(4)
2.584(5)
3.072(5)
2.633(4)
2.496(4)
3.253(5)
3.074(5)
2.998(5)
147.00
153.00
145.00
178(3)
147(3)
161(3)
171(4)
…
O1w–H2w1 N1
…
O7–H7 O1w
…
O5–H5A O6
…
N1–H1A O5
…
…
N1–H1B O7
N2–H2A O7
Fig. 10 2D architecture through intermolecular H-bonding/p interac-
2
tions in 1?H2PO4 with discrete dihydrogenphosphate–water cluster.
a
D is donor and A is acceptor.
This journal is ß The Royal Society of Chemistry 2012
CrystEngComm, 2012, 14, 6029–6034 | 6033

View Article Online
2011, 17, 2272; (d) H. Xie, S. Yi, X. Yang and S. Wu, New J. Chem.,
1999, 23, 1105.
4 (a) S. Sasaki, M. Mizuno, K. Naemura and Y. Tobe, J. Org. Chem.,
2000, 65, 275; (b) P. Buhlmann, S. Nishizawa, K. P. Xiao and Y.
Umezawa, Tetrahedron, 1997, 53, 1647.
5 (a) J. Yoo, M. S. Kim, S. J. Hong, J. L. Sessler and C. H. Lee, J. Org.
Chem., 2009, 74, 1065; (b) P. Anzenbacher, K. Jursikova and J. L.
Sessler, J. Am. Chem. Soc., 2000, 122, 9350; (c) C. B. Black, B.
Andrioletti, A. C. Try, C. Ruiperez and J. L. Sessler, J. Am. Chem.
Soc., 1999, 121, 10438.
6 (a) Z. Xu, S. K. Kim and J. Yoon, Chem. Soc. Rev., 2010, 39, 1457;
(b) H. N. Lee, N. J. Singh, S. K. Kim, J. Y. Kwon, Y. Y. Kim, K. S.
Kim and J. Yoon, Tetrahedron Lett., 2007, 48, 169; (c) J. Yoon, S. K.
Kim, N. J. Singh, J. W. Lee, Y. J. Yang, K. Chellappan and S. K.
Kim, J. Org. Chem., 2004, 69, 581.
7 (a) H. Z. Lin, J. S. Ou, Y. C. Duan, G. B. Zhang and P. Z. Bai, Chem.
Commun., 2006, 624; (b) P. Plitt, D. E. Gross, V. M. Lynch and J. L.
Sessler, Chem.–Eur. J., 2007, 13, 1374; (c) H. Z. Lin, G. Y. Zhao,
Y. C. Duan, G. B. Zhang and P. Z. Bai, Dalton Trans., 2006, 3678; (d)
R. Custelcean, J. Bosano, P. V. Bonnesen, V. Kertesz and B. P. Hay,
Angew. Chem., Int. Ed., 2009, 48, 4025; (e) C. R. Bondy, P. A. Gale
and S. J. Loeb, J. Am. Chem. Soc., 2004, 126, 5030.
8 S. K. Dey and G. Das, Dalton Trans., 2011, 40, 12048.
9 P. S. Lakshminarayanan, I. Ravikumar, E. Suresh and P. Ghosh,
Chem. Commun., 2007, 5214.
10 J. L. Sessler, D.-G. Cho and V. Lynch, J. Am. Chem. Soc., 2006, 128,
16518.
Fig. 11 1D framework through intermolecular H-bonding interactions
2
in 3?H2PO4 with 1D dihydrogenphosphate–water polymer.
formation of water–dihydrogenphosphate self-assemblies.
Importantly, ‘host–guest’ complexation occurs through inter-
molecular H-bonding interaction and results in an unprece-
dented 1D dihydrogenphosphate–water polymer (H2PO4?
H2O)nn2. In the present studies we try to explore how to
construct an efficient host for the recognition of dihydrogenpho-
sphate guest and the results clearly shows that p-nitro-o-
phenylenediamine moiety is an effective recognizing unit in
crystal engineering for preparing dihydrogenphosphate–water
hybrid supramolecular polymers.
11 Q. -Y. Cao, T. Pradhan, S. Kim and J. S. Kim, Org. Lett., 2011, 13,
4386.
12 M. A. Hossain, M. Isiklan, A. Pramanik, M. A. Saeed and F. R.
Fronczek, Cryst. Growth Des., 2012, 12, 567.
Acknowledgements
This work is supported by grants from DST, India (Project No.
SR/S1/PC/16/1008) and CSIR, India (Project No. 01(1161)07/
EMR-II) to NG. We thank to the Department of Chemistry,
University of Calcutta for instrumentals facilities through FIST
programme. SD and SJ would like to acknowledge UGC for
Fellowship. MAA thanks to the VC and Registrar of AU for
their encouragement and allowing him to work at CU. We also
thanks to Rajat Saha for helping in crystal structure determina-
tion at the initial stage.
13 (a) A. K. H. Hirsch, F. R. Fischer and F. Diederich, Angew. Chem.,
Int. Ed., 2007, 46, 338; (b) H. Xie, S. Yi, X. Yang and S. Wu, New J.
Chem., 1999, 23, 1105; (c) V. Amendola, M. Boiocchi, D. Esteban-
Gomez, L. Fabbrizzi and E. Monzani, Org. Biomol. Chem., 2005, 3,
2632; (d) V. Kral, H. Furuta, K. Shreder, V. Lynch and J. L. Sessler,
J. Am. Chem. Soc., 1996, 118, 1595; (e) J. L. Sessler, D.-G. Cho and
V. Lynch, J. Am. Chem. Soc., 2006, 128, 16518; (f) S. Sambasivan,
S.-G. Kim, S. M. Choi, Y. M. Rhee and K. H. Ahn, Org. Lett., 2010,
12, 4228; (g) C. Bazzicalupi, A. Bencini, C. Giorgi, B. Valtancoli, V.
Lippolis and A. Perra, Inorg. Chem., 2011, 50, 7202; (h) Q. -Y. Cao,
T. Pradhan, S. Kim and J. S. Kim, Org. Lett., 2011, 13, 4386.
14 S. Dalapati, M. A. Alam, S. Jana, R. Saha, S. Biswas and N.
Guchhait, ChemPlusChem, 2012, 77, 93.
References
15 SAINT, version 6.02; SADABS, version 2.03; Bruker AXS, Inc.,
Madison, WI, 2002.
1 A. K. H. Hirsch, F. R. Fischer and F. Diederich, Angew. Chem., Int.
Ed., 2007, 46, 338.
16 (a) G. M. Sheldrick, SHELXS 97, Program for Structure Solution,
University of Go¨ttingen, Germany, 1997; (b) G. M. Sheldrick,
SHELXL 97, Program for Crystal Structure Refinement, University
of Go¨ttingen, Germany, 1997; (c) A. L. Spek, PLATON, Molecular
Geometry Program, J. Appl. Crystallogr., 2003, 36, 7; (d) L. J. J.
Farrugia, J. Appl. Crystallogr., 1997, 30, 565; (e) L. J. Farrugia, J.
Appl. Crystallogr., 1999, 32, 837.
17 C. A. Ilioudis, D. G. Georganopoulou and J. W. Steed, J. Mater.
Chem., 2002, 4, 26.
18 I. R. Evans, J. A. K. Howard and J. S. O. Evans, Cryst. Growth Des.,
2008, 8, 1635.
2 (a) P. D. Beer, Acc. Chem. Res., 1998, 31, 71; (b) M. A. Hossain, J. M.
Llinares, D. Powell and K. Bowman-James, Inorg. Chem., 2001, 40,
2936; (c) J. B. Cooper, M. G. B. Drew and P. D. Beer, J. Chem. Soc.,
Dalton Trans., 2000, 2721; (d) P. D. Beer, V. Timoshenko, M.
Maestri, P. Passaniti and V. Balzani, Chem. Commun., 1999, 1755.
3 (a) T. Gunnlaugsson, M. Glynn, G. M. Tocci, P. E. Kruger and F. M.
Pfeffer, Coord. Chem. Rev., 2006, 250, 3094; (b) B. H. M. Snellink-
Ruel, M. M. G. Antonisse, J. F. J. Engbersen, P. Timmerman and
D. N. Reinhoudt, Eur. J. Org. Chem., 2000, 165; (c) M. Li, B. Wu, C.
Jia, X. Huang, Q. Zhao, S. Shao and X.-J. Yang, Chem.–Eur. J.,
6034 | CrystEngComm, 2012, 14, 6029–6034
This journal is ß The Royal Society of Chemistry 2012