Coordination polymers of N, N'-di-(8-Hydroxyquinolinolyl- 5-methyl)-N, N-diethyl-1, 3-propane diamine (QEPD)

Article abstract of DOI:10.1155/2010/609494

Coordination polymers containing a novel bis(oxine) bidentate ligand, namely N,N'-di(8-hydroxyquinolinolyl-5-methyl)-N,N'-diethyl-1,3- propane diamine (QEPD) have been prepared with the metal ions Zn(II), Cu(II), Ni(II), Co(II) and Mn(II). The novel bis-(bidentate) ligand was synthesized by condensation of 5-chloromethyl-8-hydroxyquinoline hydrochloride with N,N'-diethyl-1,2- propane diamine in the presence of a base catalyses. All of these coordination polymers and the parent ligand were characterized by elemental analyses, IR spectral and diffuse reflectance spectral studies. The thermal stability and number- average molecular weights (Mn) of all of the coordination polymers were determined by thermogravimetric analyses and non-aqueous conductometric titrations, respectively. In addition, all of the coordination polymers have been characterized by their magnetic susceptibilities.

Full text of DOI:10.1155/2010/609494

ISSN: 0973-4945; CODEN ECJHAO
E-Journal of Chemistry
2010, 7(3), 1023-1028
http://www.e-journals.net
Coordination Polymers of N, N’-di-(8-
Hydroxyquinolinolyl- 5-methyl)-N, N-diethyl-1,
3
-propane diamine (QEPD)
*
ASHA D. PATEL, RIGNESH S PATEL and GANPAT R PATEL
§
Department of Chemistry,
M. N. College, Visnagar-384315, Gujarat, India.
§
Department of Chemistry,
M. N. Science College, Patan-384265, Gujarat, India.
dr.rignesh@gmail.com
Received 18 October 2009; Accepted 15 December 2009
Abstract: Coordination polymers containing a novel bis(oxine) bidentate
ligand, namely N,N’-di(8-hydroxyquinolinolyl-5-methyl)-N,N’-diethyl-1,3-
propane diamine (QEPD) have been prepared with the metal ions Zn(II),
Cu(II), Ni(II), Co(II) and Mn(II). The novel bis-(bidentate) ligand was
synthesized by condensation of 5-chloromethyl-8-hydroxyquinoline
hydrochloride with N,N’-diethyl-1,2- propane diamine in the presence of a
base catalyses. All of these coordination polymers and the parent ligand were
characterized by elemental analyses, IR spectral and diffuse reflectance
spectral studies. The thermal stability and number- average molecular weights
(
Mn
)
of all of the coordination polymers were determined by
thermogravimetric analyses and non-aqueous conductometric titrations,
respectively. In addition, all of the coordination polymers have been
characterized by their magnetic susceptibilities.
Keywords: Coordination polymers, Infrared spectra, Diffuse reflectance spectra, Thermogravimetry,
Magnetic susceptibility, Conductometric titrations.
Introduction
The coordination chemistry of bis(oxine), bidentate ligand, has been extensively investigated
1-3
for their chelating properties . In this context bis(oxine) ligand with two oxine units joined
by a bridge of 5,5’- methylene (-CH -), 5,5’-sulfonyl (-SO -), 5,5’-dimethylene sulfide
2
2
4-10
(
synthesis and characterization of coordination polymers based on the bis-oxine ligand joined
-CH -S-CH -) and -CH-O-CH - are reported in literature
Recently, we have reported the
.
2
2
2

1
024
ASHA D. PATEL et al.
11
with a bridge, -H C-O-Ph-O-CH (Ph = 1,3 phenylene) has been replaced . This work has
2
2
been further extended with the view of investigation of the chelating ability of a bis-8-
quinolinol bis(bidentate) ligand by introducing the bridge of N,N’-diethyl-1,3-proapne
diamine between two 8-hydroxyquinoline moieties. Accordingly, the present work deals with
the synthesis and characterization of a bis(oxine) ligand, namely N,N’-di(8-hydroxyquinoloyl-
5-methyl)-N,N’-diethyl-1,3-propane diamine (QEPD) and its coordination polymers with
Zn(II), Cu(II) Ni(II), Co(II) and Mn(II) metal ions.
Experimental
All chemicals were of analytical grade. The synthesis of N,N’-di(8-hydroxyquinoloy l-5-methyl)-
N,N’-diethyl-1,3-propane diamine (QEPD) was carried out in two steps. 5-Chloromethyl-8-
1
2
hyroxyquinolinolyl hydrochloride was prepared according to a literature method .
Preparation of polymers of N,N’-di(8-hydroxyquinoloyl-5-methyl)-N,N’-diethyl-1,3-
propane diamine (QEPD)
QEPD was prepared as follows; To a suspension of 5-chloromethyl-8-hydroxyquinoline
hydrochloride (23 g, 0.02 mol), N,N’-diethyl-1,3-proapne diamine (17.5 g, 0.1 mol) in an
acetone-water mixture was added. K CO (5.3 g, 0.03 mol) was added as an acid acceptor.
2
3
The resulting mixture was refluxed for 3 h with occasional shaking. The resulting
suspension, which contained a green precipitate, was poured into ice cold (500 mL) water
and then filtered. The solid product was collected and dried to give QEPD (80 % yield).
Analysis for C H N O ; Calculated (%): C, 73.36; H, 7.42; N, 12.23.
28
34
4
2
Preparation of coordination polymers
A solution of copper acetate (1.9 g, 0.001 mol) in aqueous formic acid (50 mL, 50%) was
added drop wise to a solution of QEPD (3.30 g, 0.01 mol) in aqueous formic acid (240 mL,
2
0%) with stirring. The reaction mixture was heated on a water bath for 0.5 h. The reaction
mixture was made alkaline by the addition of dilute aqueous ammonia until the precipitation
was completed. The polymer separated out in the form of a suspension and was digested on
boiling water bath. Finally, the resultant solid brownish yellow precipitates was collected by
filtration and washed with hot water, dimethylformamide (DMF) and then acetone. The
polymer (QEPD-Cu[II]) was air dried. A similar procedure was used to prepare the QEPD-
Co[II], QEPD-Ni(II), QEPD-Mn(II) and QEPD-Zn(II). The yields of all coordination
polymers were almost quantitative.
Measurements
In the co-ordination polymers, metals were analysis by using the EDTA titration and for this
13
process decomposed co-ordination polymers used . The percentage composition. (C, H and
N) for the coordination polymers was determined by a C,H,N Elemental analyzer (Table 1).
The IR spectra of the bis-ligand QEPD and each of the coordination polymers samples were
scanned as KBr pellets using a Perkin Elmer IR spectrophotometer. The solid diffusion,
reflectance spectra of all the coordination polymers were recorded on Shimadzu
spectrophotometer with a solid reflectance attachment MgO was employed as the reference
compound
.
The number average molecular weights ( Mn) of all the coordination polymers were
estimated by end-group analysis. End- group analysis of the hydroxyl group was carried out
by non-aqueous conductometric titration using pyridine as solvent and sodium methoxide as
14,15
titrant base
.

Coordination Polymers of QEPD
1025
Magnetic susceptibility measurements of all the coordination polymers were carried out
at room temperature by the Gouy method. Mercury [tetrathiocynatocobalt] was used for the
18
instrument calibration . Molar susceptibilities were corrected for diamagnetism of the
18
component almost using Pascal’s constant . Thermogravimetry of all these coordination
polymers was carried out using a Dupont thermogravimetric analyzer (TGA). The data are
reported in Table 3.
Results and Discussion
The synthesis QEPD was performed by chloromethylation of the oxine followed by
condensation with N,N’-diethyl-1,3-proapne diamine (Scheme 1).
CH Cl
2
Dry HCl(g)
+
HCHO
N
Formaldehyde
N
+
-
OH
quinolin-8-ol
H Cl
OH
-(chloromethyl)quinolin-8-ol
5
+
NH - CH - CH - CH - NH
2
2
2
CH - CH2
CH
2
-CH
3
3
N,N-diethyl-1,3-proapne diamine
K CO
2
3
HO
CH - N - CH - CH - CH - N - CH
OH
2
2
2
2
2
CH - CH2
CH -CH3
2
3
N
N
M
O
CH - N - CH - CH - CH - N - CH
O
2
2
2
2
2
M
M
CH - CH2
CH -CH3
2
3
N
N
Coordination polymers, QEPD-Mt, Where Mt= Cu, Ni,Co, Mn, Zn
Scheme 1
-
1
-1
The important IR spectral features are (i) a broad band from 3550 cm to 3200 cm that
17
-1
is attributed to the hydrogen-bonded OH group . (ii) The weak bands near 1220 cm and
-
020 cm that are due to asymmetric and symmetric stretching vibrations of methylene
1
1
groups (CH ) of the –CH –NH–CH – bridge. (iii) The weak band at 1110 cm that confirms
the presence of a dialkyl amine function. and (iv) the bands near 1610, 1508, 1470 and 1420
-1
2
2
2
-
cm that are the characteristic frequencies of the 8-hydroxyquinoline nucleus . The weak
1
12
-1
band around 1085 and 1118 cm may also be attributed to the amine group bridge. It was also

1
026
ASHA D. PATEL et al.
observed that H L has numerous IR spectral features in common with those of 5,5-
2
1
methylene bis(8-hydroxyquinoline) . These features support the proposed structure of H L.
2
The coordination polymers derived from H L are insoluble in common organic solvents. All
2
o
these coordination polymers decomposed at approximately 250 C. The molecular mass was
estimated by evaluating the number of terminal OH groups using non-aqueous
conductometric titration. Perusal of the literature revealed that there are few reports
regarding the determination of the number average molecular weight ( Mn ) of coordination
1
8-21
polymers.
However, efforts are made by the present authors to estimate ( Mn ) of the H L
2
coordination polymers by utilizing the non-aqueous conductometrie titration method under
22
controlled experimental conditions . For the sake of convenience, the required amount of
coordination polymer was suspended in pyridine for 24 h. It was observed that the properties
of polymers did not change in the presence of pyridine.
Assuming that the only end-groups in the polymers are OH, the titration was carried out
by addition of controlled volume of NaOMe, since more volume of NaOMe may cause de-
coordination of polymers. A discernible break was observed in the titration curve and the
molecular weights were calculated as shown in Table 1. Examination of the metal content in
the polymers (Table 2) reveals a 1:1 metal: ligand (M/L) stoichiometry for all the polymers.
Table 1. Analytical data for coordination polymer of QEPD.
Elemental analysis, %
Coordination
polymers
Colour
N
M
Mn
Cal
Found
10.2
10.3
10.3
10.3
10.2
Cal
Found
11.55 5415
10.8 5367
10.85 5369
QEPD-Cu(II)
QEPD-Ni(II)
QEPD-Co(II)
QEPD-Mn(II)
QEPD-Zn(II)
Green
Green
Brown
10.34
10.43
10.42
10.5
11.73
10.93
10.92
10.3
Light green
Pale yellow
10.1
11.9
5329
5437
10.3
12.03
Table 2. Thermogravimetry Analysis (TGA) of the coordination polymer of QEPD.
Coordination
polymers
% Weight loss at temperature
o
o
o
o
o
100 C 200 C 250 C 300 C 400 C 500 C
o
QEPD-Cu(II)
QEPD-Ni(II)
QEPD-Co(II)
QEPD-Mn(II)
QEPD-Zn(II)
8.05
7.51
7.49
6.0
64.9
10.22
10.22
9.0
68.4
12.1
12.4
15.3
45.9
79.53
14.71
14.31
20.5
-
-
-
71.44
71.44
64.0
80.0
-
85.0
82.0
8.0
14.0
65.25
Comparison of the IR spectrum of the ligand H L and those of the coordination polymers
2
-1
reveal certain characteristic difference. Thus, the broad band in the region from 3550 to 3200 cm
for H L is absent in the spectra of the polymers. This is consistent with the involvement of OH
2
-1
groups in a coordinate interacting with the polymers. However, the weak band near 3400 cm for
11
H L-Mn indicates that water molecules might be strongly absorbed by the polymer sample. The
2
-1
band in H L due to C = N stretching at 1600 cm is shifted towards lower frequency (ca 1558
2
-1
cm ) in the coordination polymers. The red shift suggests coordination of metal ion through the
-1
nitrogen of 8-hydroxyquinoline. In addition, a weak band at 1100 cm is attributed to the C-O-M
-1
stretching frequency . The band at 1430 cm in QEPD is assigned to the in-plane OH
16
16
-1
deformation . This band is shifted toward higher frequency (1468 cm ) in the spectra of the
polymers and supports the formation of a metal-oxygen bond.

Coordination Polymers of QEPD
1027
The magnetic moments (µ ) of the polymeric chelates are given in Table 3. The diffuse
eft
electronic spectrum of QEPD-Cu(II) coordination polymer shows two broad bands near
1
-1
1
5.625 cm- and 22.222 cm . The first band may be due to 2T → 2E transition while the
g g
second may be due to charge transfer. The first band shows some structural characteristics
that suggest a distorted octahedral geometry. The higher theoretical value of µeff of the
QEPD-Cu(II) polymer supports this view. The QEPD-Ni(II) and QEPD-Co(II) polymers
-
1
exhibit two absorption bands at 16,000 and 23,809 cm respectively. These bands are
4
2
4
2
22
assigned to the T1g → T . T → T (P) transitions, respectively both the absorption
2g
1g
2g
bands and the values of µeff lower than required for a spin value only state.
Table 3. Reflectance spectral and magnetic moment data of the QEPD coordination
polymers.
Coordination
polymers
Absorption
Magnetic moment,
-1
Transitions
band, cm
(µeff)BM
2
1
2
1
2
3,470
5,626
2,471
5,601
2,989
Charge transfer
2
QEPD-Cu(II)
QEPD-Ni(II)
2
1.93
3.5
B ---- A
1g
1
g
3
3
A ----- T (P)
2
g
1g
3
3
A ---- T (F)
2
g
1g
4
4
4
T (F)---- T (F)
1
g
2g
4
4
QEPD-Co(II)
QEPD-Mn(II)
16,530
,051
4,051
19,651
6,226
QEPD-Zn(II) is diamagnetic
T (F)--- T
4.4
5.7
1
g
2g
4
9
T (F)---- T (P)
1
g
2g
6
6
6
4
4
2
A ---- A . E
1g 1g g
4
A --- T (4G)
1
g
2g
4
1
A --- T (4G)
1g 1g
The TGA data of all the coordination polymers are summarized in Table 4. The
coordination polymers are as thermally stable as bis(8-hydroxy-5-quinolymethylene) sulfide
2
3
(
BHQS) and 5,5’-methylene bis(oxine) (MBQ) .
-1
Table 4. Infrared frequencies (cm ) of QEPD coordination polymers.
Coordination
polymers
γ(OH)
γ C=N)
δ(C-N-C) δ (C-O) δ (M-N) δ (M-O)
QEPD-Cu(II)
QEPD-Ni(II)
QEPD-Co(II)
QEPD-Mn(II)
QEPD-Zn(II)
3540
3600
3520
3500
3510
1602
1602
1595
1602
1595
1105
1100
1105
1105
1100
1353
1367
1353
1353
1353
776
769
776
762
762
500
500
500
500
500
All the polymers decomposed in a single step. They start their degradation at around
o
00 C. The rapid degradation after this temperature may be due to catalytic oxidation by
1
metal oxide which forms in situ during decomposition of the polymer. The relative order of
thermal stability of the coordination polymers is Cu<Co<Ni<Mn.
References
1
2
.
.
Horowitz E and Perros T P, J Inorg Nucl Chem., 1964, 26, 139.
Bailer Jr J C, Judd M L and Mclean M J, WADC Technical Reports, 1969, 58- 61
Part-II, 116.
3
.
Patel R D, Patel H S and Patel S R, Eur Polym J., 1987, 23, 229.

1
028
ASHA D. PATEL et al.
4
5
6
7
.
.
.
.
Shah T B, Patel H S and Dixit R B, Oriontal J Chem., 1999, 15, 107.
Manolova N, Ignatova M and Rashkov I, Eur Polym J., 1998, 34, 1133.
Raj L M, Raj M M, Patel H S and Shah T B, Eur Polym J., 1999, 35, 1537.
GaralehM,LahciniM,KricheldorfHRandWeidnerSM, J Polym Sci Part A: Polym Chem.,
2
009, 47, 170-177.
Tsai Y-H, Lin C-H , Lin C-C and Ko B-T, J Polym Sci Part A: Polym Chem., 2009,
7, 4927-4936.
Noro S I, Kitangawa S, Yamashita M and Wada T, Cryst Eng Comm., 2002, 4(29),
62-164.
8
9
.
.
4
1
1
1
1
1
1
1
1
1
0. Shah T B, Patel H S and Dixit R B, Synth React Inorg Met Org Chem., 2001, 31, 649-659.
1. Patel K D and Pachani S C, J Ultra Scientist of Physical Sciences, 2003, 15(2), 195.
2. Burkhalter J H and Laib R I, J Org Chem., 1961, 26, 4078.
3. Vogel A I, Inorganic Quantitative Analysis, ELBS, London, 1978.
4. Chatterjee S K and Gupta N D, J Poly Sci., Part A-I., 1973, 11, 1261.
5. Mitra R P and Chatterjee S K, Indian J Chem., 1963, 1, 62.
6. Figgis B N and Lewis J, Modern Coordination Chemistry, Wiley Interscience, 1964.
7. Figgis R G, Freiser H F, Priedel R, Hilliand L E and Johnston R D, Spectrochem
Acta, 8, 1 1958.
1
1
8. Patel K D and Panchani S C, E Journal of Chemistry, 2004, 1(3), 158-163.
9. Nierengarten H, Rojo J, Leize E, Lehn J and Dorsselaer A, Eur J Inorg Chem., 2002,
2
002(3), 573-579.
2
2
2
2
0. Paulusse and Sijbesma R P, Chem Comm., 2003, 13, 1494-1495.
1. Cho Y S, Lee H K and Lee J S,Macromolec Chem Phys., 2002, 203(17), 2495-2500.
2. Patel R N and Patel S R, Angew Makromol Chem., 1981, 96, 85.
nd
3. Lever A B P, Inorganic Electronic Spectroscopy 2 Ed. Elsevier, Amsterdam, 1984.

International Journal of
International Journal of
Organic Chemistry
International
International Journal of
Advances in
Photoenergy
Medicinal Chemistry
Analytical Chemistry
Physical Chemistry
Hindawi Publishing Corporation
Hindawi Publishing Corporation
http://www.hindawi.com
Hindawi Publishing Corporation
http://www.hindawi.com
Hindawi Publishing Corporation
Hindawi Publishing Corporation
http://www.hindawi.com
Volume 2014
Volume 2014
Volume 2014
http://www.hindawi.com
Volume 2014
http://www.hindawi.com
Volume 2014
International Journal of
Carbohydrate
Chemistry
Journal of
Quantum Chemistry
Hindawi Publishing Corporation
http://www.hindawi.com
Hindawi Publishing Corporation
http://www.hindawi.com
Volume 2014
Volume 2014
Submit your manuscripts at
http://www.hindawi.com
Journal of
The Scientific
Analytical Methods
in Chemistry
World Journal
Hindawi Publishing Corporation
Hindawi Publishing Corporation
http://www.hindawi.com
http://www.hindawi.com
Volume 2014
Volume 2014
Journal of
International Journal of
International Journal of
Journal of
Bioinorganic Chemistry
Spectroscopy
Inorganic Chemistry
Electrochemistry
Applied Chemistry
and Applications
Hindawi Publishing Corporation
http://www.hindawi.com
Hindawi Publishing Corporation
Hindawi Publishing Corporation
Hindawi Publishing Corporation
Hindawi Publishing Corporation
Volume 2014
http://www.hindawi.com
Volume 2014
http://www.hindawi.com
Volume 2014
http://www.hindawi.com
Volume 2014
http://www.hindawi.com
Volume 2014
Journal of
Chromatography
Journal of
International Journal of
Journal of
Theoretical Chemistry
Catalysts
Research International
Chemistry
Spectroscopy
Hindawi Publishing Corporation
http://www.hindawi.com
Hindawi Publishing Corporation
http://www.hindawi.com
Hindawi Publishing Corporation
http://www.hindawi.com
Hindawi Publishing Corporation
http://www.hindawi.com
Hindawi Publishing Corporation
http://www.hindawi.com
Volume 2014
Volume 2014
Volume 2014
Volume 2014
Volume 2014