Preparation and X-ray powder diffraction investigation of some complexes with hydrazone ligands

Abstract

Two hydrazone ligands (L1 and L2)derived from ibuprofenyl hydrazide and benzaldehyde or salicylaldehyde have been synthesized and used in preparing the corresponding Cobalt(II) , Nickel(II) , Copper(II) , Zinc(II) , Cadmium(II) and Calcium(II) complexes. The resulted complexes have been characterized by different physiochemical methods including elemental analyses, infrared and electronic spectroscopy, magnetic moment measurements and molar conductance. The structures of the complexes have been investigated by X-ray powder diffraction and the ligands have been investigated by 1H, 13C-NMR spectra . Infrared spectral data suggest that the ligand L1 behaves , as abidentate ligand with N,O donor atoms towards the metal ions .while the ligand L2 behaves as a tridentate ligand with O,N,O donor atoms sequence towards the metal ions, except with cadium ion it behaves as bidenate ligand. On the basis of the above physicochemical measurements, the complexes have octahedral and tetrahedral geometries .

Full text

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Preparation and X-ray powder diffraction
investigation of some complexes with hydrazone
ligands
Mustafa R. Albayati1, Amira J. Al_Shaheen2, Amal M. Ali3
1Department of Chemistry, College of education for pure science, Kirkuk University, Kirkuk, Iraq
2Department of chemistry, College of Education, Mosul University, Mosul, Iraq
3Department of Chemistry, college of sciences, Mosul University, Mosul, Iraq
ABSTRACT
Two hydrazone ligands (L1 and L2)derived from ibuprofenyl hydrazide and benzaldehyde or salicylaldehyde
have been synthesized and used in preparing the corresponding Cobalt(II) , Nickel(II) , Copper(II) , Zinc(II) ,
Cadmium(II) and Calcium(II) complexes. The resulted complexes have been characterized by different
physiochemical methods including elemental analyses, infrared and electronic spectroscopy, magnetic moment
measurements and molar conductance. The structures of the complexes have been investigated by X-ray powder
diffraction and the ligands have been investigated by 1H, 13C-NMR spectra . Infrared spectral data suggest that
the ligand L1 behaves , as abidentate ligand with N,O donor atoms towards the metal ions .while the ligand L2
behaves as a tridentate ligand with O,N,O donor atoms sequence towards the metal ions, except with cadium ion
it behaves as bidenate ligand. On the basis of the above physicochemical measurements, the complexes have
octahedral and tetrahedral geometries .
Keywords: Hydrazone, (NSAIDs), Metal complexes, X-ray powder diffraction
1. INTRODUCTION
It has been reported that complexes of metallic salts are more potent and less toxic in many cases as compared to the
parent drugs(1) Ibuprofen 2-(4- isobutyl phenyl) propionic acid, is a member of non –steroidal anti-inflammatory drug
(NSAIDs), known to relief symptoms of arthritis, primary dysmenorrhea, fever and also possess mild ant platelet
effect(2). It is useful in sepsis-induced acute phenuomonia, in retarding metastases of mammary carcinoma and in
preventing oxidative lesions of lungs caused by phosgene. High doses of ibuprofen slow down the evolution of lung
disease. it also protects prostaglandin H synthase of human endothelial cells from hydrogen peroxide(3), Hydrazones, a
member of the Schiff base family with triatomic >C=N-N< Linkage , takes the fore front position in the development
of coordination chemistry. Reports on the synthesis, characterization and structural studies on hydrazone ligands
derived from aldehydes (benzaldehyde and salicylaldehyde ) show the importance of hydrazone complexes in various
fields including analytical and biological field(4,5). Hydrazone derivatives possessing anti-inflammatory, analgesic,
antipyretic and antibacterial activities are also reported in the literature (6). These complexes which plays an important
role in reducing the toxicity of the parent drug and acts as apro-drug (7).
2. EXPERIMENTAL
A. Materials and Measurements
All chemicals and solvent used for the syntheses were of analytical grade, the metal salts were commercially available
pure samples and all chemicals used throughout this investigation from Merch ,B.D.H., Aldrich or Fluka and used
without further purification.
B. Analytical and physical measurements
Melting point and decomposition temperature were determined using STUART-SMPIO melting point apparatus ,IR
spectra measurements were recorded using Shimadzo,FTIR-8400, as KBr pellets in the range (400-4000 cm-1). UV-

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Visible spectral measurements were recorded using Shimaduz 160 spectrophotomer for 10-3 M complexes in DMF
solvent at room temp.using 1cm quarts cell in range (200-900)nm . Elemental analysis were carried out on a CHN
analyzer type Vector, model EA 3000 V.3.0 single Euro .The NMR was recorded on broker shield 300 MHz using
deutrated DMSO-d6 as a solvent . Molar conductance of complexes were measured at room temp. for 10-3 M in DMF
using (BC 3020 professional Bench top conductivity) .
Magnetic susceptibility of the complexes was carried out by (Magnetic Susceptibility Balance of Johnson Mattey
catalytic system division, England) .Via Faradys method at room temperature. Metal contents were estimated spectro
photo metrically using atomic absorption spectrometer NOVAA 350 Scientific Equipments. X-ray powder diffraction
data for complexes ( 1,13 ) were measured at general company for Geological survey and mining-Baghdad by using
Shimadzu x-ray diffraction 7000 model 2009 and the crystal data for complexes , were analyzed by using match
program version 1.6 C .
3. PREPARATION OF THE LIGANDS AND THE COMPLEXES
Synthesis of 2(4-isobutyl phenyl) propionic acid ethyl ester (Ibuprofenyl ethyl ester)
The Ibuprofene was esterified(8)by dissolving( 6.18 g, 0.03 mole) of it in 20ml of ethanol and then to that 2.0 ml of
sulfuric acid was added . The mixture was refluxed for 6-8hrs . After completion of reaction, solvent was removed by
adding 100m of cold water , followed by extracting with sodium bicarbonate and separated in the organic layer . The
yield (80%) , b.p 250-252 oC , empirical formula C15H22O2 .
%N
%H
%C
-
9.40
76.92
Calc.
-
9.50
77.0
Found
Synthesis of 2-(4-isobutylphenyl) propionoic acid hydrazide
The hydrazide was prepared(9)by refluxing (4.68g , 0.02mol) of 2-(4-isobutyl phenyl) ethyl propanate in 15ml ethanol
with an excess of hydrazine hydrate NH2. NH2.H2O(85%) for 24h , the reaction mixture was then left to stand overnight
The compound precipitated on standing over night, filtered and washed with cold distilled water . The pure white solid
hydrazide was obtained by recrystallization from ethanol and dried in an oven at(70-80)C , yield(81%), mp 76-
78oCempirical formula C13H20N2O.
%N
%H
%C
12,72
9.09
70.90
Calc.
12.81
9.22
70.78
Found
Synthesis of hydrazone ligands (L1& L2)
The ligands were synthesized according to the method described in the literature(10 ). by reacting equimolar amount of
Ibuprofenyl hydrazide and benzaldehyde or salicylaldehyde. A hot ethanolic solution of the ligand made by dissolving
( 2.2g, 0.01 mole) of Ibuprofenyl hydazide in 15 ml of ethanol, and has been slowly mixed with a hot ethanolic solution
containing (1.06g , 0.01 mole) of benzaldehyde or (1.22g, 0.01 mole) of salicylaldehyde .The resulting mixture has
been refluxed for about 6 hrs. The mixture has been left to stand for nearly two hours. The precipitated compound was
filtered . recrystallized from ethanol, washed with ether and dried under vacuum.

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The structures of the ligands are shown in Fig. ( 1)
Table 1: physical properties and analytical data of the ligands
Ligands
Empirical formula =
M. wt
Colour
m.p
(C)
Yield
Elemental analysis calcu. (found)
% C
% H
% N
L1
C20H24 N2 O
308
White
180-182
%72
77.92
78.01
7.79
(7.83)
9.09
(8.87)
L2
C20H24 N2O2
324
White
167-169
%79
74.07
(73.87)
7.40
(7.61)
8.64
(8.70)
Synthesis of the complexes
All complexes were obtained according to the following procedure(11) , an ethanolic solution of (0.005mol) metal(II)
chloride or nitrate was mixed with a hot clear ethanolic solution of the ligand L1(3.08 gm , 0.01mol) or L2(3.24gm ,
0.01mol) in the mole ratio 2:1 (L:M) after Mixing, The mixture has been refluxed for 5hrs . Then cooled down to room
temperature. A precipitates were filtered, washed successively with water and ethanol , followed by diethyl ether and
dried in an oven at (70-80)Cº .
Table 2: Weight of metal salts used to prepare complexes.
Table 3: Characterization, analytical, molar conductance and magnetic susceptibility data of the complexes.
Metal salt
Wt(g) metal salt
metal salt
Wt(g) metal salt
CoCl2.6H2O
1.19
CuCl2.2H2O
0.85
Co(NO3)2. 6H2O
1.45
Zn Cl2
0.68
NiCl2. 6H2O
1.18
Cd Cl2
0.91
Ni(NO3)2.6H2O
1.45
Ca Cl2
0.55
NO.
Formula
Molecul
ar
Weight
Colour
Yied
%
m.p
Cº
Meff
B.M
ΛM
DMF
Cm2.
Ohm-
1.mol-
Calculate( Found )%
%C
%H
%N
%M
1
[Co(L1)2Cl2]
746
Brown
69
>300
4.67
18
64.34
(64.22)
6.43
(6.11)
7.50
( 7.23)
7.90
(7.72)
2
[Co(L1)2(H2O)2](NO3)2
835
Green
74
281-
283
4.75
150
57.48
(57.21)
6.22
(6.03)
10.05
(9.92)
7.05
(6.86)

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4. RESULTS AND DISCUSSION
The two ligands and their metal complexes are solid and most of them are coloured, insoluble in water but soluble in
organic solvents such as DMF at 10-3 M. The molar conductance values of all complexes are in the range (12-28)
ohm -1 cm2 mol-1indicating non electrolytic nature . While the molar conductance values of the complexes 2,4 & 7
are in the range ( 133-150) ohm -1 cm2 mol-1 indicating a ( 1: 2) electrolytic nature of these complexes. The molar
conductance values are in a good agreement with given formulations(12). the metal percentage in the complexes
and physical data of complexes are given in table (3).
Electronic Spectra and magnetic moment
The ultraviolet spectra for the ligands exhibited two bands in the UV intervals at (27173-29069 ) cm-1 and
(30487- 38461) cm-1, assigned to n  π* , and π π* transitions respectively .All these transitions were also found
in the spectra of the complexes but they were shifited to lower frequencies confirming the coordination of the
ligand to the metal ions( 13) (table 4 ).
The electronic spectra of Co(II) complexes 1,2and 9 exhibt bands at (11157-12820) cm-1 due to ν1 and (14947-15625)
cm-1 due to ν2 , and (16366-20533) cm-1due to ν 3, which are assigned to following transitions:
4T1g (F)4T2g (F)ν1 7500-11000
4T1g (F)4A2g (F)ν2 11000-16000
4T1g (F)4T1g (P)ν3 17000-22000
and these values agreed with high spin octahedral configuration. The value of magnetic moment obtained for these
complexes are (4.65-4.75)B.M. and this value greater than the the ortical value (3.87) B.M due to orbital
contribution(14).
While Ni(II) complexes 3,4 and10 exhibit electronic spectrum bands at (11100 – 12468)cm-1 , (14513 – 20449) cm-1
and (20533 – 24752) cm-1 respectively , and assigned to transitions :
3 A2g (F) 3 T2g (F) ν1 7000-11000
3 A2g (F)3 T1g (F) ν212000-20000
3 A2g (F)3 T1g (P) ν321000-28000
The octahedral geometry of Ni(II) ion in the complexes is confirmed with the measured magnetic moment values(2.92–
3.31)B.M( 15) .
3
[Ni(L1)2Cl2]
745
Brown
68
239-
241
3.28
17
64.42
(64.11)
6.44
(6.17)
7.51
(7.24)
7.78
(7.63)
4
[Ni(L1)2 (H2O)2](NO3)2
834
Olive
61
257*
2.92
143
57.55
(57.21)
6.23
( 6.11)
10.07
(9.78)
6.95
(6.76)
5
[Cu(L1)2Cl2]
750
Black
69
254*
2.15
22
64.00
(63.85)
6.40
(6.23)
7.46
(7.35)
8.40
(8.33)
6
[Zn(L1)2Cl2]
752
White
81
>300
Dia
25
63.82
(63.45)
6.38
( 6.10)
7.44
( 7.21)
8.64
(8.46)
7
[Cd(L1)2 (H2O)2 ]Cl2
835
White
72
295*
Dia
133
57.48
(57.31)
6.22
( 6.01)
6.70
(6.44)
13.41
(13.32)
8
[Ca(L1)2Cl2]
727
White
Yellowi
sh
85
275-
277
Dia
16
66.02
(65.88)
6.60
( 6.45)
7.70
(7.65)
-
9
[Co(L2)2]
706
Red
69
292-
294
4.65
13
67.98
( 67.87)
6.65
(6.47)
7.93
( 7.69)
8.35
(8.22)
10
[Ni(L2)2]
705
green
66
206-
208
3.31
15
68.08
( 67.77)
6.66
(6.76)
7.94
( 7.71)
8.22
(8.03)
11
[Cu(L2)2]
710
Brown
78
290*
1.99
27
67.60
(67.40)
6.61
(6.34)
7.88
(7.94)
8.87
(8.67)
12
[Zn(L2)2]
712
Pale
Yellow
65
270-
272
Dia
18
67.41
(67.22)
6.60
(6.40)
7.86
(7.40)
9.12
(8.88)
13
[Cd(L2)2]
759
White
69
>300
Dia
12
63.24
(62.89)
6.19
(5.81)
7.37
(6.91)
14.75
(14.43)
14
[Ca(L2)2]
687
White
80
285-
287
Dia
28
69.86
(69.66)
6.84
(6.62)
8.15
(7.64)
-

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The Cu(II) complexes 5& 11 show one broad band peaking at 16780 or 18845 cm–1. This band may arise from
the 2Eg →2T2g transition of 2D state .This band has been comparable both in position and width with the earlier
reported octahedral complexes .Because the eg state has been highly affected by Jahn tellar effect , therefore,
copper complex had distorted octahedral geometry. The magnetic moment value obtained for Copper (II)complexes(
2.15,1.99) B.M respectively (16).which may suggest an distorted octahedral structure .
Table 4: Electronic spectra data of the complexes
CT = Charge transfer band
Infrared Spectra
The coordination sites of the ligand involved in the bonding with metal ions had determined by careful comparsion of
the infrared spectra of these complexes with that of the parent ligand. The ligand basically composed of different
groups of potent ability to coordinate with the metal ion . The IR spectra of the ligands (L1 and L2) show band at (3182
, 3120) cm-1 due to NH stretching vibration(17) respectively, and a new absorption bands appeared at (1672 , 1662)cm-
1 which has been attributed to frequency of C=O amide group . The IR spectra of the ligands L1 and L2 show a strong
band in the region (1608 , 1614)cm-1 , which is a characteristic of the azomethine (stretching vibration of C=N) group
and, these bands in complexes are shifted to lower frequency indicating coordination of carbonyl oxygen atom and
azomethine nitrogen atom to the metal(18) .
In the spectra of the ligands L1 and L2 showed , a weak band at (2952 , 2950)cm-1 due to sym & asym . C-H aliphatic
of CH2 group and this band remains unaltered on complexation. Also the spectra of L1 and L2 showed abroad band at
(1066,1050 ) cm-1 due to N-N group shifted towards lower frequency (954-1033)cm-1 on complexation(19). The aqua
complexes contain a weak to medium abroad band at (3450 – 3464) cm-1 due to OH stretching vibration of H2O .
water molecules are coordinated , confirmed by occurrence of additional strong band at (846 – 875) cm-1 due to OH
rocking vibration . The spectra of the complexes showed bands in the region (514 – 591) cm-1 and (420 – 500) cm-1 are
assigned to M-O and M-N stretching bands of the metal complexes.
In addition the coordination of chloride could not be inferred from infrared spectra of the complexes, because
the band due to these group occurred beyond the range of our instrument, whereas for Cl- ligand has been
checked by AgNO3 .The chloride complex 7 shows a band at 570 cm-1 has been attributed to ionic Cl (Table 5). The
band located at 1380, cm-1 in nitrate complexes, were attributed to ionic nitrate group(20,21).
1HNMR&13CNMR Spectra
The coordination of the ligands have been further substantiated by 1HNMR &13CNMR spectra of the ligands and some
of their complexes in DMSO- d6 as a solvent.
1HNMRdata
The ligands exhibit a sharp singlet at δ 8.2 ppm due to the proton azomethine group were shifted down filed in the
spectra of the complexes( δ 8.5,8.7) ppm .This deshielding is possibly due to the donation of the lone pair of electrons
by the azomethine nitrogen to the metal atom resulting in the formation of a coordination .
The spectrum of the L1&L2 showed singlet broad signals at (δ=11.2,11.1) ppm due to amide proton NH-CO- and, this
signal remained unaltered in the complexation which indicates non participates of NH -in coordination to metal ion,
also there is no conversion of the ligand to enolic form and confirmed the bonding through the C=O group. The OH
proton of L2exhibits singlet signals at δ 11.8 ppm, this signal in the spectra of complex disappeared due to the
deprotonation that takes place and to the coordination between oxygen and the metal atom. The aromatic ring proton
show a multi signals at (δ=7.1- 8.0) for L1, (δ=6.9-7.6) for L2, while the aliphatic protons show signals at 0.8-2.4 ppm
Complex. No.
Electronic transition of d-d cm-1
CT
ν1
ν2
ν3
1
12820
15337
16366
35714
2
12297
15625
20533
24154
3
12468
14513
24752
28169
4
11100
20449
22935
37764
9
11157
14947
18103
33557
10
12468
14517
26638
28169

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in a free ligand, the spectra show none change in these signal values for the prepared complexes which indicate non-
participation in the coordination (22,23).
13CNMR data
The13CNMR was recorded in d6-(DMSO) solution. The two ligands show signals at (18-44), ppm due to the carbon
atom of the aliphatic L1 and L2 respectively, and signals in range (126-147) ,( 116-157) ppm due to the aromatic ring
No change appeared in these signals in complexes formation. And this refers to uncoordinated aliphatic and aromatic
carbons in the metal complexes .While the signals due to azomethine carbon and carbonyl carbon were appeared at 169
ppm and 174 ppm and these signals were altered in coordination(24,25) (table 5).
Table 5: Selected I.R. bands of the ligands and its complexes (in cm)-1
X-ray Powder Diffraction Analysis
The XRD patterns indicate a crystalline nature for complexes . Indexing of the diffraction patterns was
performed using High Score Plus software Match(26) program, and their Miller indices (hkl) along with observed
and calculated 2Ø angle , d values, and relative intensities , From the indexed data the unit cell parameters
were also calculated . The Powder XRD patterns of the compounds are completely different from those of the
starting materials, demonstrating the formation of coordination compounds. It is found that complexes have
orthorhombic and tetragonal structure As shown in Tables (6) .Moreover, using diffraction data, the mean
crystallite sizes of the complexes, ,were determined according Scherrer equation (D = 0.9 λ / (β cos θ), where λ X-
ray wavelength (1.5406 A-˚), θ is Bragg diffraction angle, and β is the full width at half maximum of the diffraction
peak(27).
Table 6: Crystal data and structure refinement for complex 1&13Table 6
No
Complex
1
1
Molecular Formula
C40H48Cl2O2N4Co
2
Molecular weight
746
Comp
No.

(OH)

(N-H)

(C=O)

(N-N)

(C=N)

(C-O)

(M-N)

(M-O)
Other
L1
--
3182
1672
1066
1608
--
--
--

(C-H)2952
L2
3197
3120
1662
1060
1614
1274
--
--

(C-H)2950
1
--
3178
1636
1030
1555
--
420
560
2
--
3187
1640
1022
1570
--
455
550

(OH2)3450 , 875

(NO3)1383 , 750
3
--
3185
1643
995
1578
--
478
586
4
--
3184
1620
1022
1556
--
422
530

(OH2)3464 , 850

(NO3)1389 , 777
5
--
3180
1653
1022
1557
--
421
533
6
--
3177
1612
1043
1564
--
467
514
7
--
3180
1653
1022
1557
--
421
533
ionicCl 625

(OH2)3421 , 846
8
--
3185
1655
1005
1583
--
447
567
9
--
3115
1600
1000
1539
1298
426
590
10
--
3118
1613
1021
1591
1251
500
567
11
--
3122
1630
1010
1584
1240
500
569
12
--
3124
1610
1002
1539
1238
551
588
13
--
3117
1660
946
1550
1247
447
567
14
--
3123
1646
1009
1543
1260
491
551

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3
Crystal system
Orthorhombic
4
Space group
P2|2|2|
5
Unit cell parameters (Ao)
a-9.1440(1) A, b = 12.0110(1) A,
c = 33.5670 (4) A
6
Cell Volume (Ao3)
726.62 (6) A3
7
Z
8
8
θ range , deg
2.50– 31.7
9
Index ranges
27  h  30, 12  k 6,15  L  3
No
Complex
13
1
Molecular Formula
C40 H46N4O4Cd
2
Molecular weight
759
3
Crystal system
Pi Tetragonal
4
Space group
P-4(85)
5
Unit cell parameters (Ao)
a= 20.1 Ao , c= 5.33 Ao
6
Cell Volume (Ao3)
784.37 Ao3
7
Z
4
8
θ range , deg
25.14 – 46.13
9
Index ranges
16  h  20
16  k  4
13  L  2
5. CONCLUSION
From the above discussion of various physicochemical, spectral and according to the measurements of XRD analysis,
the crystal geometries of some complexes has been established, and we concluded that the metal ions are hexa
coordinate with most probable octahedral structure has been suggested for most complexes. Whereas cadium complex
has tetrahedral geometriy. The analytical and spectroscopic data showed that ligand L1 act's as bidentate coordinated
to the metal ions through oxygen carbonyl and azomethine nitrogen atoms while, L2 act's as tridentate ligand with
O,N,O donor atoms sequence towards the metal ions, except with cadium ion it behaves as bidenate ligand .

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Fig. (2): The structure of the prepared complexess
Fig. 3: The structures of complexes 1&13 Cheme Office. Version. Ultra 8.0. 3D
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