Structural study on few co-crystals and a salt of quinoline derivatives having amide bond

Article abstract of DOI:10.1016/j.molstruc.2009.06.029

The N-[2-(4-Methoxy-phenyl)-ethyl]-2-(quinolin-8-yloxy)-acetamide forms 1:1 co-crystals with aromatic diols namely 1,4-dihydroxybenzene, 1,5-dihydroxynaphthalene. In the later case co-crystal is formed in hydrated form. The hydrated form of co-crystal wit

Full text of DOI:10.1016/j.molstruc.2009.06.029

Journal of Molecular Structure 935 (2009) 47–52
Contents lists available at ScienceDirect
Journal of Molecular Structure
journal homepage: www.elsevier.com/locate/molstruc
Structural study on few co-crystals and a salt of quinoline derivatives having
amide bond
*
Anirban Karmakar, Dipjyoti Kalita, Jubaraj B. Baruah
Department of Chemistry, Indian Institute of Technology Guwahati, Guwahati, 781 039 Assam, India
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 22 May 2009
Received in revised form 18 June 2009
Accepted 18 June 2009
Available online 28 June 2009
The N-[2-(4-Methoxy-phenyl)-ethyl]-2-(quinolin-8-yloxy)-acetamide forms 1:1 co-crystals with aro-
matic diols namely 1,4-dihydroxybenzene, 1,5-dihydroxynaphthalene. In the later case co-crystal is
formed in hydrated form. The hydrated form of co-crystal with 1,5-naphthalenediol has two symmetry
independent host molecules in its unit cell, whereas such phenomenon in the co-crystal 1,4-dihydroxy-
benzene is not observed. The crystal structure of perchloric acid salt of (Quinolin-8-ylamino)-acetic acid
is determined and this salt also shows two symmetry independent parent molecules in unit cell.
Ó 2009 Elsevier B.V. All rights reserved.
Keywords:
Quinoline derivatives
Amides
Dihydroxyaromatics
Co-crystals
Perchlorate salt
Crystal structures
1. Introduction
non-H atoms were refined in the anisotropic approximation
against F2 of all reflections. The H atoms, except those attached
The quinoline derivatives serve as template for guest binding
and have interesting fluorescence properties [1]. The quinoline
derivatives are acid sensitive and the understanding of the binding
ability to guest molecule is of special interest [2]. It is also well
known fact that the heterocyclic aromatic systems interact with
hydroxy aromatics [3, 4] and can in turn effect the fluorescence
emission [4]. Quinoline derivatives are also used as drugs for ma-
laria, arthritis, and lupus [5–8]. Thus, the structural understanding
on quinoline derivative having amide functionality is of impor-
tance. In this study we describe characterisation and structural as-
pects of two co-cystals (2–3) and a perchlorate salt of quinoline
derivative (4) as shown in Fig. 1.
to nitrogen and oxygen atoms were placed at their calculated posi-
tions and refined in the isotropic approximation; some of the H
atoms attached to nitrogen and oxygen were located in the differ-
ence Fourier maps, and refined with isotropic displacement coeffi-
cients, while rest of the H atoms attached to N and O were placed
in their calculated position and refined (Table 1).
2.1. Synthesis of N-[2-(4-Methoxy-phenyl)-ethyl]-2-(quinolin-8-
yloxy)-acetamide (1)
2-(4-Methoxyphenyl)ethylamine (1.51 g, 10 mmol) was dis-
solved in dry dichloromethane (20 ml) and triethylamine (1.01 g,
10 mmol) was added to it. The solution was stirred at 0 °C for
10 min after which bromoacetyl bromide (2.42 g, 12 mmol) was
added dropwise to the stirred solution over a period of 30 min.
The reaction mixture was then stirred overnight. Subsequently
the reaction mixture was filtered to remove the hydrobromide salts,
and the filtrate was collected. The filtrate was washed with water
(10 ml), dried over sodium sulphate and then the solvent was re-
moved under reduced pressure. The 2-Bromo-N-[2-(4-methoxy-
phenyl)-ethyl] acetamide was obtained as a brown solid, the crude
product was recrystallised from dichloromethane. The 2-Bromo-N-
[2-(4-methoxy-phenyl)-ethyl] acetamide (2.72 g, 10 mmol), 8-
hydroxyquinoline (1.45 g, 10 mmol) and K2CO3 (2.07 g, 15 mmol)
was added to dry acetone (20 ml) in nitrogen atmosphere and the
reaction mixture was stirred at 60 °C for 10 h. (The reaction
2. Experimental
The X-ray single crystal diffraction data were collected at 296 K
with Mo K
a radiation (k = 0.71073 Å) using a Bruker Nonius
SMART CCD diffractometer equipped with a graphite monochro-
mator. The SMART software was used for data collection and also
for indexing the reflections and determining the unit cell parame-
ters; the collected data were integrated using SAINT software. The
structures were solved by direct methods and refined by full-ma-
trix least-squares calculations using SHELXTL software. All the
* Corresponding author. Tel.: +91 361 2582301; fax: +91 361 2690762.
E-mail address: juba@iitg.ernet.in (J.B. Baruah).
0022-2860/$ - see front matter Ó 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.molstruc.2009.06.029

48
A. Karmakar et al. / Journal of Molecular Structure 935 (2009) 47–52
OH
N
N
NH
O
O
.
NH
O
O
.
H2O
MeO
MeO
OH
1
2
OH
OH
N
ClO4
H
.
N
OH
NH
O
H
MeO
N
O
O
3
4
Fig. 1. Quinoline derivatives, co-crystals and a perchlorate salt.
progress was monitored at regular intervals using TLC). After com-
pletion of the reaction the solvent was removed under reduced
pressure that gave a brown solid. The solids were washed with di-
lute sodium hydroxide solution (5%), and water and then extracted
with dichloromethane. The organic extracts were collected over
anhydrous sodium sulphate. Subsequent removal of the solvent
gave the crude product, which was purified by chromatography
(silica gel; hexane/ethyl acetate 3:2). Isolated yield 46%. IR (KBr,
cmÀ1): 3328(m), 2935(m), 1655(s), 1545(s), 1514(s), 1377(s),
1298(s), 1250(s), 1182(s), 1109(s), 1031(s), 819(s), 785(s), 614(s).
Elemental analysis for C20H20N2O3: calculated C, 71.35; H, 5.95; N,
8.32; found C, 71.51; H, 5.39; N, 8.73. 1H NMR (CDCl3): 8.79(dd,
J = 4 Hz,1.2 Hz, 1H), 8.15(dd, J = 8.4,1.6 Hz, 1H), 7.99(bs, 1H),
7.45(m, 3H), 7.08(dd, J = 6.8,1.6 Hz, 1H), 6.95(d, J = 8.4 Hz, 2H),
6.61(d, J = 8.8 Hz, 2H), 4.76(s, 2H), 3.73(s, 3H), 3.53(q, J = 13.2 Hz,
2H), 2.72(q, J = 13.2 Hz, 2H). 13C NMR (CDCl3): 168.6, 158.2, 153.8,
149.3, 140.0, 136.6, 131.1, 129.7, 127.0, 122.1, 121.5, 113.9, 111.6,
69.60, 55.3, 40.7, 34.8.
2.2. Co-crystal 2
N-[2-(4-Methoxy-phenyl)-ethyl]-2-(quinolin-8-yloxy)-acetam-
ide (1) (0.1 g, 0.3 mmol) and 1,5-Naphthalenediol (0.05 g,
0.3 mmol) were dissolved in 10 ml of methanol. The resultant solu-
tion was then kept for crystallization. After 9 days reddish block
type crystals were appeared. Yield: 61%. IR (KBr, cmÀ1): 3472(bs),
3297(w), 2983(w), 1629(s), 1590(w), 1509(s), 1381(s), 1262(s),
1244(s), 1181(m), 1119(s), 937(w), 823(w), 780(s), 751(m). Ele-
mental analysis for C60H58N4O11: calculated C, 71.21; H, 5.74; N,
5.54; found C, 71.56; H, 5.31; N, 5.36.1H NMR(CDCl3): 9.36(s,
2H), 8.84(d, J = 4.4 Hz, 1H), 8.36(bs, 1H), 8.24(d, J = 8.4 Hz, 1H),
7.71(d, J = 8.4 Hz, 2H) 7.54(m, 3H), 7.21(m, 3H), 6.98(d, J = 7.2 Hz,
2H), 6.88(d, J = 7.2 Hz, 2H), 6.67(d, J = 8.4 Hz, 2H), 4.78(s, 2H),
3.74(s, 3H), 3.53(q, J = 14 Hz, 2H), 2.76(t, J = 7.2 Hz, 2H). 13C NMR
(CDCl3): 168.5, 158.1, 152.7, 148.9, 136.1, 134.2, 130.4, 129.2,
126.5, 126.1, 124.4, 121.6, 121.3, 113.4, 112.9, 111.8, 108.3, 69.6,
54.8, 40.2, 34.3.
Table 1
The crystallographic parameters of 2, 3 and 4.
Compound code
2
3
4
CCDC No.
727137
727136
727134
Empirical formula
Formula weight
Crystal system
Space group
C60H58N4O11
1011.10
Triclinic
C26H26N2O5
446.49
C11H11ClN2O6
302.67
Monoclinic
P2(1)/c
Orthorhombic
P2(1)2(1)2(1)
a = 5.6277(2) Å
b = 18.3147(6) Å,
c = 22.0626(7) Å,
PÀ1
Unit cell dimension
a = 10.8194(5) Å,
b = 14.2801(7) Å,
c = 17.6702(9) Å,
a = 8.4382(2) Å,
b = 32.4641(10) Å
c = 9.4498(3) Å,
a
= 79.482(4)°,
b = 88.028(3)°,
= 74.127(3)°
a = b = c = 90.00°
a = c = 90.00°,
c
b = 104.458(2)°
2506.68(13)
8
Volume (Å3)
Z
Density (calculated)
Absorption coefficient
F(000)
2581.5(2)
2273.98(13)
4
2
1.301 mg/m3
0.090 mmÀ1
1068
1.304 mg/m3
0.091 mmÀ1
944
1.604 mg/m3
0.334 mmÀ1
1248
Crystal size
Theta range for data collection (°)
Index ranges
0.12 Â 0.24 Â 0.48 mm3
1.73–25.00
À12 6 h 6 12
À16 6 k 6 15
À21 6 l 6 21
23784
0.16 Â 0.21 Â 0.28 mm3
1.45–28.33
À7 6 h 6 7
À23 6 k 6 24
À29 6 l 6 24
25648
0.33 Â 0.27 Â 0.21 mm3
1.25–24.99
À9 6 h 6 10
À35 6 k 6 38
À10 6 l 6 11
19700
Reflections collected
Independent reflections
Completeness to theta
Absorption correction
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I > 2sigma(I)]
R indices (all data)
8740
96.2%
None
8740/0/698
1.030
5630
99.3%
None
5630/0/305
1.040
4387
99.7%
None
4387/0/385
1.260
0.0471
0.0836
0.0487
0.0713
0.0541
0.0756

A. Karmakar et al. / Journal of Molecular Structure 935 (2009) 47–52
49
2.3. Co-crystal 3
TLC). After completion the solvent was removed under reduced
pressure. The product obtained was purified by column chroma-
tography. Yield: 58%. IR (KBr, cmÀ1): 3353(s), 3303(m), 2922(m),
1667(s), 1577(m), 1515(s), 1486(m), 1423(w), 1384(m), 1315(s),
1127(m), 815(m), 782(s). 1H NMR (CDCl3): 10.9(s, 1H), 8.8 (d,
J = 6 Hz, 2H), 8.4(d, J = 4 Hz, 1H), 8.1(d, J = 8.4 Hz,1H), 8.0 (d,
J = 8.4 Hz, 1H), 7.5–7.4 (m, 3H), 7.3–7.2 (m, 2H), 7.1(d, J = 8 Hz,
1H), 7.0 (s, 1H), 6.7 (d, J = 7.6 Hz, 1H), 4.3(s, 2H).
N-[2-(4-methoxy-phenyl)-ethyl]-2-(quinolin-8-yloxy) acetam-
ide (1) (0.1 g, 0.3 mmol) and 1,4-dihydroxybenzene (0.03 g,
0.3 mmol) were dissolved in methanol (5 ml). The resultant solu-
tion was kept for crystallization. After 5 days colourless block type
crystals were appeared. Yield: 54%. IR (KBr, cmÀ1): 3309(bs),
2930(w), 1651(s), 1563(m), 1506(s), 1472(m), 1377(m), 1317(m),
1246(s), 1212(s), 1118(s), 1032(m), 824(s), 759(s), 515(w). Ele-
mental analysis for C26H26N2O5: calculated C, 69.88; H, 5.82; N,
6.27; found C, 69.61; H, 5.61; N, 5.93. 1H NMR(CDCl3): 8.79(d,
J = 4.4 Hz, 1H), 8.33(bs, 1H), 8.20(d, J = 9.6 Hz, 1H), 7.48(m, 3H),
7.10(dd, J = 3.2, 5.6 Hz, 1H), 6.98(d, J = 8.8 Hz, 2H), 6.72(s, 1H),
6.67(d, J = 8.4 Hz, 2H), 4.73(s, 2H), 3.72(s, 3H), 3.51(q, J = 14 Hz,
2H), 2.73(t, J = 7.6 Hz, 2H). 13C NMR (CDCl3): 167.8, 159.0, 153.8,
149.7, 148.4, 135.8, 132.2, 129.5, 127.0, 122.4, 121.5, 113.5,
116.7, 110.5, 68.8, 54.8, 40.3, 35.1.
2.5. Synthesis of perchloric acid salt of (Quinolin-8-ylamino)-acetic
acid (4)
Compound 4a was dissolved in dilute HClO4 solution (3 M) and
the reaction mixture was warmed for 30 min to obtain a homoge-
neous solution. The solution was kept undisturbed and brown col-
ored crystal appeared after14 days. Yield: 52%; IR (KBr, cmÀ1):
3401(b), 3323(m), 2926(m), 2800(m), 1747(s), 1626(s), 1591(m),
1569(m), 1473(m),1378(m), 1341(m), 1217(m), 1180(m), 1147
(s), 1120(s), 1080(s), 808(s), 753(s), 625(s). 1H NMR (CDCl3): 8.9
(d, J = 4.8, 1H), 8.5(d, J = 8, 1H), 7.7 (m, 1H), 7.5 (t, J = 7.6, 1H),
7.2(m, 1H), 6.8(d, J = 7.6), 5.1(bs, 1H), 4.0(s, 2H).
2.4. Synthesis of (Quinolin-8-ylamino)-acetic acid (4a)
8-Aminoquinoline (0.72 g, 5 mmol) was dissolved in dry dichlo-
romethane (20 mL) and triethylamine (0.69 mL, 5 mmol) was
added to it. The solution was stirred at 0 °C for 15 min and then
bromoacetylbromide (0.43 mL, 5 mmol) was added drop wise to
the stirred solution. The reaction mixture was then stirred over-
night at room temperature. It is them filtered to remove the hydro-
bromide salts, and the filtrate was removed under reduced
pressure. The product obtained was further purified by recrystalli-
zation from dichloromethane. In the next step, the amide obtained
(1.4 g, 5 mmol), 8-aminoquinoline (0.72 g, 5 mmol) and K2CO3
(1.03 g, 7.5 mmol) were added to dry acetone (20 mL) in nitrogen
atmosphere and the reaction mixture was stirred at 60 °C for 9 h
(progress of the reaction was monitored at regular intervals using
3. Results and discussion
The
N-[2-(4-methoxy-phenyl)-ethyl]-2-(quinolin-8-yloxy)
acetamide forms 1:1 co-crystal (2) with 1,5-dihydroxynaphthalene
which is isolated as colorless crystals and characterized by
spectroscopic techniques (Scheme 1). A relatively strong absorp-
tion in 3472 cmÀ1 in the IR spectra of co-crystal 2 is attributed to
the hydrogen bonded phenolic –OH groups of 1,5-dihydroxy
naphthalene.
The carbonyl stretching of amide appears at 1629 cmÀ1 1H
.
NMR spectrum of the 1 shows the N–H proton as broad singlet
OH
OH
N
N
Methanol/water
.
NH
O
O
.
H2O
+
2
NH
O
MeO
MeO
OH
OH
O
1
2
Scheme 1.
Fig. 2. 1H NMR spectra of compound 1 and the co-crystal 2 (The peak due to guest molecule are indicated by G).

50
A. Karmakar et al. / Journal of Molecular Structure 935 (2009) 47–52
at 8.0 ppm in CDCl3. After formation of co-crystals with 1,5-naph-
thalenediol the N–H peak gets shifted to 8.3 ppm, which indicates
that the N–H proton participate in a strong hydrogen bonding
interaction (Fig. 2).
decided by weak interactions between 1,5-dihydroxynaphthalene
molecule and amide derivatives in which the diols are in two dif-
ferent environments. A chain like structure is formed, in which
water along with diol molecules act as bridges between the amides
on one side and diols as bridges on the other side. This makes two
different environments around the diols and enables one to distin-
guish two amide hosts in terms of their symmetry. The dihydroxy
molecules are held by the receptor through N1ÀHÁ Á ÁO8 [dN1Á Á ÁO8
3.05 Å,<D–HÁ Á ÁA 147.3°], N3ÀHÁ Á ÁO7 [dN3Á Á ÁO7 2.96 Å,<D–HÁ Á ÁA
151.5°], O7ÀHÁ Á ÁN4 [dO7Á Á ÁN4 2.67 Å,<D–HÁ Á ÁA 173.2°] and
O8ÀHÁ Á ÁN2 [dO8Á Á ÁN2 2.70 Å,<D–HÁ Á ÁA 171.2°] hydrogen bonding
interactions, where the N-H protons of amide behave as hydrogen
bond donor but the phenolic -OH group serve as donor as well as
acceptor atom. It was earlier showed that the N-(2,6-dimethyl-
phenyl)-2-(quinolin-8-yloxy)acetamide forms 1:1 co-crystal with
1,5-dihydroxynaphthalene in that case there were no water of
crystallisation [9]. It has a chain like structure where symmetry
non-equivalent molecules of the same compounds were not ob-
served. This indicates clearly the role of water molecule in this
crystal on generating symmetry non-equivalent molecules. It is
worth noting that the crystal structure of hydrated and anhydrous
form of the receptor 1 is already determined [9]; which does not
show symmetry non-equivalence. This result also suggests the ori-
gin of symmetry non-equivalent molecules in the case of 2, to a
combined role of all the three components by formation of
assemblies.
The phenolic –OH proton is not observed in the 1H NMR spectra
of the co-crystal 2 in CDCl3 at room temperature. This probably oc-
curs due to proton exchange with water present in the solvent.
Moreover, no appreciable changes in the chemical shift of the pro-
tons of the host molecule are observed upon co-crystal formation.
On the other hand the co-crystal 3 is prepared by mixing 1 and
1,4-dihydroxybenzene in stoichiometric amounts in methanol as
colorless plates (Scheme 2). Elemental analysis shows that 3 show
it to have 1:1 ratio between host and guest.
In the co-crystal 3, the OÀH stretching appears as broad absorp-
tion at 3309 cmÀ1 and the amide carbonyl stretching frequency ap-
pears at 1651 cmÀ1. A broad singlet appears at 2930 cmÀ1 due to
the NÀH stretching frequency. The N–H proton of the host is
shifted from 8.0 ppm to 8.3 ppm after the formation of co-crystal.
A singlet appears at 6.7 ppm due to the aromatic protons of 1,4-
dihydroxybenzene. The other aromatic protons are not affected
significantly upon formation of co-crystal.
The 1:1 co-crystal of N-[2-(4-methoxy-phenyl)-ethyl]-2-(quin-
olin-8-yloxy) acetamide with 1,5-dihydroxynaphthalene and it
crystallizes in the triclinic P-1 space group. From the crystal
structure it is observed that two units of N-[2-(4-methoxy-phe-
nyl)-ethyl]-2-(quinolin-8-yloxy) acetamide co-crystal with 1,5-
dihydroxynaphthalene molecule forms assembly with one
molecule of water of crystallization (Fig. 3A). The structure is
The water molecule with the host molecule in a bridging fash-
ion is held by the oxygen atoms of two symmetry non-equivalent
OH
N
OH
N
Methanol
.
NH
O
O
+
NH
O
MeO
MeO
OH
OH
O
1
3
Scheme 2.
Fig. 3. (A) Crystal structure of co-crystal 2, (B) Structure of compound 3.

A. Karmakar et al. / Journal of Molecular Structure 935 (2009) 47–52
51
Table 3
Hydrogen bond geometry (Å,°) for co-crystal 3.
DÀHÁ Á ÁA
d(DÀH)
d(HÁ Á ÁA)
d(DÁ Á ÁA)
<DÀHÁ Á ÁA
N(1)ÀH(1 N)Á Á ÁO(5) [1Àx, À1/2 + y,
1/2Àz]
0.92(3)
2.12(3)
2.99(3)
159.1(2)
O(4)ÀH(4A)Á Á ÁO(2) [1 + x, y, z]
O(5)ÀH(5)Á Á ÁN(2) [1Àx, 1/2 + y,
1/2Àz]
0.82
0.82
1.90
1.91
2.71(3)
2.72(2)
169.8
166.8
159.1°] hydrogen bonding (Fig. 5). The phenolic –OH group of
1,4-dihydroxybenzene molecule is also hydrogen bonded with
quinolinic nitrogen through O5ÀHÁ Á ÁN2 [dO5Á Á ÁN2 2.72 Å,<D–HÁ Á ÁA
166.8°] interaction. The carbonyl of amide group is involved in
O4ÀHÁ Á ÁO2 [dO4Á Á ÁO2 2.71 Å,<D–HÁ Á ÁA 169.8°] hydrogen bonding
interaction with the hydroxyl group of 1,4-dihydroxybenzene (Ta-
Fig. 4. Hydrogen bonded one dimensional assembly in co-crystal 2.
ble 3). The aromatic ring protons participate in weak C13ÀHÁ Á Á
p
Table 2
Hydrogen bond geometry (Å,°) for co-crystal 2.
[dC13Á Á Á 3.77 Å] and C18ÀHÁ Á Á [dC18Á Á Á 3.70 Å] hydrogen bonding
p
p
p
interactions with quinoline rings. Absence of water of crystallisa-
tion makes the system symmetric in terms of the 1,4-dihydroxy-
benzene bridges and the co-crystals are placed symmetrically in
the lattice with respect to each other. The structure has similarity
to the reported structure of co-crystal of 1,4-dihydroxybenzene
with N-(2,6-dimethylphenyl)-2-(quinolin-8-yloxy) acetamide [9].
The above example shows the occurrence of symmetry non-
equivalent molecules in lattice is by a combined effect of binding
of a host to water molecules through a guest molecule. However,
symmetry equivalence may arise in system without a solvent
molecule but by self assembling process [10]. The crystal structure
DÀHÁ Á ÁA
d(DÀH) d(HÁ Á ÁA) d(DÁ Á ÁA) <DÀHÁ Á ÁA
N(1)ÀH(1 N)Á Á ÁO(8)
0.98(3)
2.18(3)
2.15(3)
1.86
3.05(3)
2.96(3)
2.67(2)
2.70(2)
2.74(2)
2.89(3)
2.81(3)
2.69(3)
147.3(2)
151.5(2)
173.2
N(3)ÀH(2 N)Á Á ÁO(7) [ 1Àx, 1Ày, 1Àz ] 0.89(3)
O(7)ÀH(7A)Á Á ÁN(4) [1Àx, 1Ày, 1Àz]
O(8)ÀH(8)Á Á ÁN(2)
0.82
0.82
0.82
1.89
1.92
171.2
178.8
O(9)ÀH(9)Á Á ÁO(2) [1Àx, 1Ày, Àz]
O(11)ÀH(11O)Á Á ÁO(2) [1Àx, 1Ày, Àz] 0.86(5)
2.04(5)
1.94(4)
1.87
175.9(1)
170.0(3)
174.2
O(11)ÀH(12O)Á Á ÁO(5)
0.87(4)
0.82
O(10)ÀH(10)Á Á ÁO(11) [À1 + x, y, z]
of the salt
4 (Scheme 3) shows symmetry non-equivalent
receptors through O11ÀHÁ Á ÁO2 [dO11Á Á ÁO2 2.89 Å,<D–HÁ Á ÁA 175.9°]
and O11ÀHÁ Á ÁO5 [dO11Á Á ÁO5 2.81 Å,<D–HÁ Á ÁA 170.0°] intermolecular
hydrogen bonding interactions (Fig. 4).
cations in the lattice. The perchlorate salt of quinoline containing
carboxylic acid 4 is formed from a hydrolytic reaction as shown
in Scheme 3.
The water molecule is also hydrogen bonded with 1,5-naphtha-
lenediol by intermolecular O10ÀHÁ Á ÁO11 [dO1OÁ Á ÁO11 2.69 Å,<D–
HÁ Á ÁA 174.2°] interaction, where the oxygen atom of water acts
as acceptor and the –OH group as donor. One of the dihydroxy mol-
ecules is held by the receptor through O9ÀHÁ Á ÁO2 [dO9Á Á ÁO2
2.74 Å,<D–HÁ Á ÁA 178.8°] interaction and the amide carbonyl act
as a bifurcated acceptor (Table 2). A two dimensional hydrogen
bonded molecular assembly is formed in the lattice.
The compound 1 and 1,4-dihydroxybenezene form a 1:1 co-
crystal (3) of host and guest and it crystallizes in the orthorhombic
P212121 space group. The crystal structure of the co-crystal is
shown in Fig. 3. The N–H proton of the host molecule binds the
guest molecule through N1ÀHÁ Á ÁO5 [dN1Á Á ÁO5 2.99 Å,<D–HÁ Á ÁA
The crystal structure of 5 (Fig. 6a) has two symmetry non-
equivalent cations and anions in each asymmetric unit (Z’ = 2). Re-
cently, we have shown that in the crystal structure of carbamates
and urea derivatives of amino or hydroxy-quinolines have symme-
try non-equivalent molecules in lattice on formation of perchlorate
salts [11]. However, in those cases water of crystallisation had also
a role on the symmetry non-equivalence. In the present case the
perchlorate salt without water of crystallisation leads to assembly
formation, in which pairs of symmetry non-equivalent carboxylic
acids are placed in head to tail orientations. The packing pattern
of the molecule is governed by C–HÁ Á ÁO and N–HÁ Á ÁO interactions
(Table 4). The structure does not posses direct O–HÁ Á ÁO hydrogen
Fig. 5. One dimensional hydrogen bonded assembly of host and guest in co-crystal 3.

52
A. Karmakar et al. / Journal of Molecular Structure 935 (2009) 47–52
ClO4
N
H
NH2
H
N
N
OH
N
NH
H
N
H
N
Aqeous HClO4
ClO4
O
+
O
4a
4
Scheme 3.
Fig. 6. (a) Crystal structure of salt 4, (b) the weak interactions in its crystal lattice.
structures are further held by intervening perchlorate anions. The
packing pattern is such that the parent compounds in each layer
along c-axis are not symmetrically equivalent.
Table 4
Hydrogen bonds in the salt 4.
DÀHÁÁÁÁA
DÀH
HÁÁÁÁA
DÁÁÁÁA
DÀHÁÁÁÁA
N(1)ÀH(1 N)ÁÁÁÁO(3) [x, 1/2Ày, 1/2 + z]
O(2)ÀH(2C)ÁÁÁÁO(7) [À1 + x, 1/2Ày,
À1/2 + z]
0.80(4)
0.82
2.04(4)
2.22
2.781(4)
2.981(5)
154.2(4)
154.6
Acknowledgements
The authors thank Department of Science and Technology, New
Delhi, India for financial support.
O(2)ÀH(2C)ÁÁÁÁO(8) [À1 + x, 1/2Ày,
À1/2 + z]
0.82
2.38
3.030(5)
137.2
N(3)ÀH(3 N)ÁÁÁÁO(9) [x, y, À1 + z]
O(4)ÀH(4)ÁÁÁÁO(1) [x, 1/2Ày, À1/2 + z]
N(4)ÀH(4A)ÁÁÁÁO(9) [x, y, À1 + z]
C(1)ÀH(1)ÁÁÁÁO(7) [x, 1/2Ày, 1/2 + z]
C(2)ÀH(2)ÁÁÁÁO(2) [1 + x, y, 1 + z]
C(7)ÀH(7)ÁÁÁÁO(11) [À1 + x, y, À1 + z]
C(14)ÀH(14)ÁÁÁÁO(8) [2Àx, Ày, 1Àz]
0.81(3)
0.82
0.86
0.93
0.93
0.93
0.93
2.17(3)
1.87
2.57
2.37
2.59
2.60
2.908(4)
2.624(4)
3.371(4)
3.283(5)
3.352(5)
3.525(5)
3.494(5)
152.5(3)
151.6
154.8
168.4
149.8
174.2
167.5
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bonding interactions among the carboxylic acid group but they
form cyclic hydrogen bonded network with the NH+ and C@O of
the quinolinium and carboxylic acid functional group of the parent
compound. The dimeric units formed, are associated with a per-
chlorate anion through N–HÁ Á ÁO interactions and leads to a chain
like structure along crystallographic c-axis (Fig. 6b). The chain like