Green Chemistry Letters and Reviews

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Solid–solid synthesis, characterization, thermal

decomposition and antibacterial activities of
zinc(II) and nickel(II) complexes of glycine–vanillin
Schiff base ligand

Guo-Qing Zhong & Qin Zhong

To cite this article: Guo-Qing Zhong & Qin Zhong (2014) Solid–solid synthesis, characterization,
thermal decomposition and antibacterial activities of zinc(II) and nickel(II) complexes of
glycine–vanillin Schiff base ligand, Green Chemistry Letters and Reviews, 7:3, 236-242, DOI:
10.1080/17518253.2014.927008

To link to this article: https://doi.org/10.1080/17518253.2014.927008

© 2014 The Author(s). Published by Taylor & Published online: 20 Jun 2014.
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Green Chemistry Letters and Reviews, 2014
Vol. 7, No. 3, 236–242, http://dx.doi.org/10.1080/17518253.2014.927008

RESEARCH LETTER
Solid–solid synthesis, characterization, thermal decomposition and antibacterial activities of
zinc(II) and nickel(II) complexes of glycine–vanillin Schiff base ligand
Guo-Qing Zhong* and Qin Zhong

State Key Laboratory Cultivation Base for Nonmetal Composite and Functional Materials, School of Material Science and
Engineering, Southwest University of Science and Technology, Mianyang, China
(Received 15 November 2013; final version received 19 May 2014)

The zinc(II) and nickel(II) complexes of glycine–vanillin Schiff base were synthesized by one-step solid–solid reaction
at room temperature. The composition and structure of the complexes were characterized by elemental analyses,
Fourier transform infrared spectra (FTIR), X-ray powder diffraction (XRD), and thermogravimetry and differential
scanning calorimetry (TG–DSC). The crystal structure of the complexes belongs to monoclinic system with the lattice
parameters: a = 0.6807 nm, b = 1.3818 nm, c = 1.2011 nm, β = 95.80° for [Zn(C10H9O4N)(H2O)3], and a = 0.7457 nm,
b = 1.3331 nm, c = 1.2560 nm, β = 91.89° for [Ni(C10H9O4N)(H2O)3]·1.5H2O. The experimental results indicate that
the zinc and nickel ions are all six-coordinated by imino nitrogen, carboxylic oxygen, and phenolic oxygen from the
Schiff base ligand, and oxygen from three coordinated water molecules, respectively. The possible pyrolysis reactions
in the thermal decomposition processes of the complexes and the experimental and calculated percentage mass loss
are also given. The two complexes have the most intense antibacterial activities against Escherichia coli.
Keywords: room temperature solid–solid reaction; complex of vanillin Schiff base; crystal structure; thermal
decomposition; antibacterial activity

1. Introduction This method had the disadvantages of long response

Schiff bases are a series of organic compounds which time, the use of a large amount of solvents, environ-
mental pollution, and low yield. Solid–solid chemical
contain the azomethine group (–C=N–). These com-
reaction at room temperature is the method used in a
pounds are easily synthesized by the reaction of a
wide range of methods for the preparation of some
primary amine and an active carbonyl compound
compounds, and the method has a high yield rate and
(aldehyde or ketone). Because of some special func-
selectivity (33–35).
tions and a wide range of biological activities and
Amino acids constitute the building blocks of
industrial application, Schiff bases continue to occupy
proteins and are chemical species indispensable for
an important position as ligands in metal coordination
performing a huge number of biological functions. The
chemistry (1–10). Schiff bases and their complexes
complexes of the amino acid Schiff base synthesized by
have been found to possess the pharmacological
the one-step solid–solid reaction at room temperature
activities, such as antibacterial (11–14), antifungal
have not been previously reported in literatures. Based
(14, 15), antitumor (16, 17), antimalarial (18), anticon-
on the concept of green chemistry, in this work we have
vulsant (19), and antiviral agents (20). Amino acid is
synthesized the zinc(II) and nickel(II) complexes of the
not only a kind of aminocarboxylic acids but also a
glycine–vanillin Schiff base ligand, and studied their
kind of important biological compounds for the body.
crystal structure, infrared spectra, thermal decomposi-
Studying Schiff bases of amino acids and their com-
tion process, and antibacterial activity.
plexes has important significance to bioinorganic
chemistry and medicine field. The use of Schiff bases
as ligands in the formation of transition-metal com-
2. Results and discussion
plexes had been extensively studied, but the Schiff base
ligands and its complexes were previously synthesized 2.1. The composition and properties of the complexes
in some solvent, and most synthetic methods were The results of elemental analyses and the melting point
performed in ethanol or methanol solution (21–32). of the ligand and the complexes are listed in Table 1.

*Corresponding author. Email: zgq316@163.com

© 2014 The Author(s). Published by Taylor & Francis.

This is an Open Access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits
unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. The moral rights of the named author(s) have been
asserted.
 Green Chemistry Letters and Reviews 237

Table 1. Elemental analyses results and the melting point of the ligand and the complexes.

m.p.
Schiff base and complex Formula (°C) w(M) (%) w(C) (%) w(H) (%) w(N) (%) w(O) (%)

K(gly-van) KC10H10O4N 81–82 – 48.69 (48.57) 4.23 (4.08) 5.76 (5.67) 25.69 (25.88)
[Zn(gly-van)(H2O)3] ZnC10H15O7N – 19.89 (20.02) 36.67 (36.77) 4.47 (4.63) 4.15 (4.29) 34.82 (34.29)
[Ni(gly-van) NiC10H18O8.5N – 17.25 (16.92) 35.26 (34.62) 5.38 (5.23) 3.85 (4.04) 38.26 (39.20)
(H2O)3]·1.5H2O
Note: Calculated values are in brackets.

The composition formulae of the zinc(II) and nickel(II)
complexes are ZnC10H15O7N and NiC10H18O8.5N,
respectively. The calculated results of mass fraction of
each element in the complexes are very close to the
measured ones. Therefore, combined with the results of
the infrared spectra and the thermal analysis, the
possible molecular formulae of the complexes are [Zn
(C10H9O4N)(H2O)3] and [Ni(C10H9O4N)(H2O)3]·1.
5H2O, or [Zn(gly-van)(H2O)3] and [Ni(gly-van)
(H2O)3]·1.5H2O. The molar ratio of the Schiff base
ligand and metal ions of the complexes is 1:1. The
decomposition of the complexes occurs near the melt-
ing point. The complexes are all stable at room
temperature, non-hygroscopic, and partially soluble
in water and ethanol.
2.2. Analysis of X-ray powder diffraction
The X-ray powder diffraction (XRD) patterns of the
complexes are shown in Figure 1. Compared with the
raw material, the strong peak locations of the resul-
tants are changed obviously. The main strong peaks,
which come from the reactants glycine, vanillin, and
zinc acetate or nickel acetate, are disappeared in X-ray
powder diffraction patterns of the complexes. At
the same time, the new strong peaks show the new
compounds formation rather than the mixture of the
reactants. There is the small background, and the high
and intense of diffraction peaks in the XRD patterns of
the complexes, which indicate that the complexes have
a fine crystalline state. All the diffraction data can be
very well indexed by a set of cell parameters according
to monoclinic system, and the index results of the
powder X-ray diffraction patterns are shown in Tables
2 and 3, respectively. As Tables 2 and 3 show, the
calculated spacing dcal are consistent with the experi-
mental spacing dexp, and the largest relative deviation is
less than 0.5%. The results indicate that the complexes
are all single phase, and the crystal structures of the
complexes belong to monoclinic system. The lattice
parameters of the glycine–vanillin Schiff base com-
plexes are: a = 0.6807 nm, b = 1.3818 nm, c = 1.2011
nm, and β = 95.80° for [Zn(C10H9O4N)(H2O)3], and
a = 0.7457 nm, b = 1.3331 nm, c = 1.2560 nm, and
β = 91.89° for [Ni(C10H9O4N)(H2O)3]·1.5H2O.
2.3. FTIR spectra
The infrared spectra of the complexes are shown in
Figure 2. The absorption peaks from the stretching
vibration of the bonds in the water molecule are in the
range of 3550–3200 cm−1(36). As Figure 2 shows, there

(a) 15000 (b) 17500

12500 15000

12500
10000
Intensity (a.u.)

Intensity/a.u.

10000
7500
7500
5000
5000

2500
2500

0 0
10 20 30 40 50 60 70 10 20 30 40 50 60 70
2q (°) 2q (°)

Figure 1. X-ray powder diffraction patterns of the complexes [Zn(C10H9O4N)(H2O)3] (a) and [Ni(C10H9O4N)
(H2O)3]·1.5H2O (b).
238 G.-Q. Zhong and Q. Zhong

Table 2. Experimental data and calculated results for powder X-ray diffraction pattern of the complex [Zn(gly-van)(H2O)3]
(monoclinic system: a = 0.6807 nm, b = 1.3818 nm, c = 1.2011 nm, and β = 95.80°).

Number 2θ (°) h k l dexp (nm) dcal (nm) I/I0 Number 2θ (°) h k l dexp (nm) dcal (nm) I/I0

1 13.061 1 0 0 0.6773 0.6772 100 22 42.417 2 5 −1 0.2129 0.2131 4.0

2 16.922 1 1 1 0.5235 0.5231 30.9 23 44.109 2 0 −5 0.2051 0.2053 1.5
3 18.382 1 2 0 0.4823 0.4836 5.1 24 45.284 2 4 3 0.2001 0.2004 1.7
4 18.799 1 0 −2 0.4716 0.4723 45.4 25 45.931 0 7 0 0.1974 0.1974 2.8
5 20.579 0 3 1 0.4312 0.4298 6.2 26 47.879 2 6 −1 0.1898 0.1897 4.8
6 23.197 0 1 3 0.3831 0.3827 4.7 27 48.763 2 0 5 0.1866 0.1866 2.1
7 24.080 1 3 −1 0.3693 0.3690 20.8 28 49.225 2 1 5 0.1850 0.1849 3.7
8 24.640 1 0 −3 0.3610 0.3596 8.0 29 50.437 0 5 −5 0.1808 0.1808 8.5
9 25.025 1 3 1 0.3555 0.3570 9.7 30 51.502 0 7 3 0.1773 0.1769 1.7
10 27.080 2 1 0 0.3290 0.3289 19.7 31 51.839 3 4 2 0.1762 0.1759 1.7
11 29.058 1 4 0 0.3070 0.3077 7.9 32 52.204 3 5 −1 0.1751 0.1750 2.2
12 30.863 2 2 1 0.2895 0.2885 2.7 33 53.283 3 1 −5 0.1718 0.1717 1.4
13 32.101 1 4 −2 0.2786 0.2788 7.5 34 54.938 3 2 4 0.1670 0.1668 1.3
14 33.157 0 5 1 0.2700 0.2693 5.8 35 55.754 0 7 −4 0.1647 0.1647 2.1
15 33.998 1 0 4 0.2635 0.2637 12.9 36 57.352 1 1 7 0.1605 0.1606 2.6
16 35.461 2 2 −3 0.2529 0.2530 7.4 37 59.732 2 5 5 0.1547 0.1546 1.2
17 38.737 1 5 2 0.2323 0.2320 9.0 38 61.282 2 7 −4 0.1511 0.1515 2.1
18 39.683 0 5 3 0.2269 0.2271 5.4 39 61.779 4 3 2 0.1500 0.1501 2.1
19 40.041 3 0 0 0.2250 0.2257 6.6 40 64.200 2 6 5 0.1450 0.1450 2.0
20 40.474 3 1 0 0.2227 0.2228 3.9 41 66.372 4 4 −4 0.1407 0.1408 1.0
21 41.856 1 6 −1 0.2157 0.2157 1.2 42 67.993 3 6 4 0.1378 0.1378 0.8

are some strong peaks in the range of 3550–3200 cm−1 the existence of the coordinated water or lattice water
in the infrared spectra of the complexes. This indicates molecules in the complexes and support the molecular
that there are water molecules in the crystals of the formulae of the complexes. As Figure 2(a) shows, the
complexes. Therefore, the infrared spectra demonstrate infrared spectrum of [Zn(C10H9O4N)(H2O)3] makes

Table 3. Experimental data and calculated results for powder X-ray diffraction pattern of the complex [Ni(gly-van)
(H2O)3]·1.5H2O (monoclinic system: a = 0.7457 nm, b = 1.3331 nm, c = 1.2560 nm, and β = 91.89°).

Number 2θ (°) h k l dexp (nm) dcal (nm) I/I0 Number 2θ (°) h k l dexp (nm) dcal (nm) I/I0

1 11.881 1 0 0 0.7443 0.7453 100 21 40.198 0 5 3 0.2242 0.2249 1.2

2 18.118 1 0 −2 0.4892 0.4881 6.3 22 40.816 3 2 −2 0.2209 0.2205 3.0
3 19.338 1 2 1 0.4586 0.4585 30.7 23 41.414 0 3 5 0.2178 0.2186 9.4
4 21.259 0 0 3 0.4176 0.4184 6.5 24 42.178 3 1 −3 0.2141 0.2140 3.3
5 22.499 1 2 −2 0.3948 0.3938 48.5 25 43.753 0 1 −6 0.2067 0.2067 1.0
6 22.958 1 2 2 0.3871 0.3855 15.8 26 44.092 2 0 5 0.2052 0.2051 1.3
7 24.682 2 0 −1 0.3604 0.3605 3.9 27 45.177 0 4 −5 0.2005 0.2005 2.1
8 25.554 2 1 −1 0.3483 0.3480 2.1 38 46.777 2 5 −3 0.1940 0.1940 5.1
9 25.990 2 1 1 0.3426 0.3422 5.1 29 50.029 0 7 −2 0.1822 0.1822 1.8
10 29.357 1 4 0 0.3040 0.3042 15.7 30 51.223 2 1 6 0.1782 0.1783 1.8
11 30.299 1 4 1 0.2947 0.2948 16.1 31 53.185 3 1 5 0.1721 0.1723 2.9
12 30.761 2 2 −2 0.2904 0.2922 7.0 32 53.679 2 3 −6 0.1706 0.1708 1.8
13 31.193 1 1 −4 0.2865 0.2859 2.4 33 54.398 2 7 −1 0.1685 0.1684 1.4
14 34.176 2 3 −2 0.2621 0.2624 4.2 34 54.882 4 3 −2 0.1672 0.1670 2.9
15 35.101 0 3 4 0.2554 0.2563 13.3 35 55.837 0 5 −6 0.1645 0.1646 1.3
16 36.175 2 4 0 0.2481 0.2484 1.8 36 56.352 1 6 −5 0.1631 0.1631 1.8
17 37.609 2 3 −3 0.2390 0.2387 1.4 37 58.114 4 4 −2 0.1586 0.1585 1.4
18 38.457 1 5 −2 0.2339 0.2340 2.6 38 63.049 2 8 2 0.1473 0.1474 0.9
19 39.154 3 1 −2 0.2299 0.2301 5.9 39 63.960 5 2 0 0.1454 0.1455 1.2
20 39.923 3 1 2 0.2256 0.2252 2.4 40 64.345 4 5 −3 0.1447 0.1447 2.1
 Green Chemistry Letters and Reviews 239

(a)
Transmittance (%) (b)

Transmittance (%)
478
913

596 547
718
660
1305

940
3460

1060

592 519
3268

1394

775
1351

731
1608

1628
1421

1086
3313

627
4000 3500 3000 2500 2000 1500 1000 500 4000 3500 3000 2500 2000 1500 1000 500
Wavenumbers (cm )
–1 Wavenumbers (cm–1)

Figure 2. Infrared spectra of the complexes [Zn(C10H9O4N)(H2O)3] (a) and [Ni(C10H9O4N)(H2O)3]·1.5H2O (b).

out broad peaks at 3460 cm−1 and 3268 cm−1 due to absorption peak at 1351 cm−1 arises from the v(ph–O)
the v(O–H) bond in a water molecule. The absorption stretching vibration. The band at 627 cm−1 is assigned
peaks at 913 cm−1 and 718 cm−1 are assigned to the to the v(Zn N) bond, and the peaks at 592 cm−1 and 519
rocking and wagging vibrations of the hydroxyl, and cm−1 arise from the v(Ni–O) bond (36). From the IR
which indicate that there are the coordinated water results, it may be concluded that the Schiff base ligand
molecules in the complexes (28). This is in accord with is tridentate and coordinates with the metal ion through
the result of thermal analysis. The absorption peak at the azomethine nitrogen, phenolic oxygen, and carb-
the range of 1700–1740 cm−1 of carbonyl in the oxylic oxygen atoms.
glycine–vanillin Schiff base ligand disappears in the
complexes. The broad absorption peaks at 1608 cm−1
and 1394 cm−1 can be assigned to the absorption peak 2.4. Thermal analysis
overlap of the νas(COO) and v(C=N) stretching vibra- Studying the thermal decomposition process of various
tion (13), and the νs(COO) stretching vibration, Schiff base complexes is helpful to the understanding of
respectively. The difference value of 214 cm−1 between the coordination structure of the complexes (37–41).
νas(COO) and νs(COO) is in line with a monodentate The thermogravimetry and differential scanning
type of coordination (23). The absorption peak at 1305 calorimetry (TG–DSC) curves of the complexes from
cm−1 is assigned to the phenolic v(ph–O) stretching room temperature to 650°C are shown in Figure 3.
vibration. Compared with the ligand, the peak in the The possible thermal decomposition processes and the
complex shifts obviously toward higher wavenumber, experimental and calculated results for the thermal
and this indicates that the phenolic oxygen is coordi- analysis of the complexes are summarized in Table 4.
nated with Zn2+ ion. In the low-frequency region, the Figure 3(a) shows that there are one endothermic peak
absorption peak at 596 cm−1 is assigned to the and two exothermic peaks in the DSC curve. First, the
stretching vibration of the Zn−N bond, and the endothermic peak at 148°C accompanies evidently
absorption peaks at 547 cm−1 and 478 cm−1 arise mass loss, and the sample will gradually lose 3H2O
from the stretching vibration of the Zn−O bond (36). molecules. The experimental percentage mass loss
As Figure 2(b) shows, a broad band at 3313 cm−1 (15.72%) closes to the calculated one (16.55%). This is
in the infrared spectrum of [Ni(C10H9O4N) consistent with the results of elemental analyses and
(H2O)3]·1.5H2O is assigned to the v(O–H) in a water infrared spectra of the zinc(II) complex. The coordi-
molecule, and the absorption peaks at 940 cm−1 nated water molecules are eliminated at higher tem-
and 731 cm−1 arise from the rocking and wagging peratures than the water molecules of hydration. The
vibrations of the coordinated water molecules. The water of coordination is usually eliminated in
broad absorption peaks at 1628 cm−1 and 1421 cm−1 the temperature range 100–316°C (42). Because of the
can be assigned to the absorption peak overlap of the high temperature of loss water, the three water
νas(COO) and v(C=N) stretching vibration, and the molecules should be of coordinated water. The organic
νs(COO) stretching vibration, respectively. The differ- part of the complexes may decompose in one or more
ence value of 207 cm−1 between νas(COO) and νs(COO) steps with the possibility of the formation of one or
is in line with a monodentate type of coordination. The two intermediates. These intermediates may finally
240 G.-Q. Zhong and Q. Zhong

(a) 367 °C
10 (b) 20
424 °C
100 100
8 16
TG 15.72% TG 8.31%

6 15.28%
80 12
80

Heat Flow (W/g)

Heat Flow (W/g)

Weight (%)
Weight (%)

4
59.78% 8
60 296 °C
2 60
DSC
DSC 4
0 54.32%
40
40 100 °C 0
–2
148 °C 293 °C
20 -4
–4
20
100 200 300 400 500 100 200 300 400 500 600
Temperature/°C Temperature/°C

Figure 3. TG–DSC curves of the complexes [Zn(C10H9O4N)(H2O)3] (a) and [Ni(C10H9O4N)(H2O)3]·1.5H2O (b).

decompose to stable metal oxides. Thereafter, sequential molecules. Finally the exothermic peak at 424°C
exothermic peaks at 296°C and 367°C correspond to corresponds to oxidation and decomposition of the
step-by-step oxidation and decomposition of the ligand ligand and loss of CH3CN, CO2, and –CH3OC6H3
and loss of CH3CN, CO2, and –CH3OC6H3 group, the group. The final remnant mass from the TG curve is
mass loss of 59.78% in thermogravimetry (TG) curve is 22.09%, and it is in agreement with the calculated result
in agreement with the calculated result of 58.53%. The (21.53%) of the residue nickel oxide.
complex is decomposed completely at about 450°C. The In summary, the two complexes have similar space
final residue is zinc oxide, and the experimental result structure, and the zinc and nickel ions are coordinated
(24.50%) is in agreement with the calculated result by imino nitrogen, carboxylic oxygen, and phenolic
(24.92%). Figure 3(b) shows that there are two obvious oxygen from the Schiff base ligand, and oxygen from
endothermic peaks and one exothermic peak in the three coordinated water molecules, respectively. Based
on the results gained from elemental analyses, IR, and
DSC curve. First the endothermic peak at 100°C
TG–DSC, the possible structural formula of the
accompanies 8.31% of mass loss from 1.5 water
formed complexes is shown in Scheme 1.
molecules. Because of the low temperature of loss
water, the water molecules should be of crystal water.
Thereafter, the endothermic peak at 293°C accompanies 2.5. Qualitative antimicrobial activity
15.28% of mass loss from three coordinated water Preliminary screening for antimicrobial activities of
Table 4. Thermal decomposition data of the Schiff base the stock solutions of the complexes was performed
complexes. qualitatively using the disk diffusion assay in Table 5.
Moxifloxacin was used as a standard drug. The
Mass loss (%) complexes yielded clear inhibition zones around the
Reaction TDSC (°C) Wexp. Wtheor. disks. Each of the compounds was tested three times
and recorded the average data. The results showed
[Zn(C10H9O4N)(H2O)3] that the complexes had significant antibacterial activ-
↓ −3H2O 148 (endo.) 15.72 16.55 ities against four bacteria; the antibacterial activities
[Zn(C10H9O4N)] of the sequence were Escherichia coli, Bacillus subtilis,
↓ −CH3CN 296 (exo.)
Staphylococcus epidermidis, and Staphylococcus aur-
↓ −CO2, −CH3OC6H3 367 (exo.) 59.78 58.53
eus, respectively. The two complexes had the most
ZnO 24.50a 24.92b
[Ni(C10H9O4N)(H2O)3]·1.5H2O effective antibacterial activity against E. coli, and the
↓ −1.5H2O 100 (endo.) 8.31 7.79 average diameter of inhibition zone of the zinc(II) and
[Ni(C10H9O4N)(H2O)3] nickel(II) complexes was 16.6 mm and 18.7 mm with
↓ −3H2O 293 (endo.) 15.28 15.58 the concentration of 1.0 mg mL−1.
[Ni(C10H9O4N)]
↓−CH3CN, −CO2, 424 (exo.) 54.32 55.10
−CH3OC6H3 3. Conclusion
a b
NiO 22.09 21.53 The nickel(II) and zinc(II) complexes of glycine–vanillin
a
The experimental percentage mass of the residue in the sample. Schiff base had been synthesized by one-step solid–solid
b
The calculated percentage mass of the residue in the sample. reaction at room temperature. The complexes were
 Green Chemistry Letters and Reviews
H 2O H2O H O
H 2O H2O H2O
O CH N M O CH N
H2C O H2C
OCH3 C OCH3 C n
O O
Scheme 1. Molecular structure of the complexes.
characterized by elemental analyses, XRD, FTIR, and
TG–DSC. The results of indexing to data of the XRD
indicate that the complexes belong to monoclinic system
with the lattice parameters: a = 0.6807 nm, b = 1.3818
nm, c = 1.2011 nm, and β = 95.80° for [Zn(C10H9O4N)
(H2O)3], and a = 0.7457 nm, b = 1.3331 nm, c = 1.2560
nm, and β = 91.89° for [Ni(C10H9O4N)(H2O)3]·1.5H2O.
The zinc and nickel ions are all six-coordinated by imino
nitrogen, carboxylic oxygen, and phenolic oxygen from
the Schiff base ligand, and oxygen from the three
coordinated water molecules, respectively. The thermal
decomposition processes of the complexes include
dehydration, and pyrolysis of the ligand, and the final
residue is metallic oxide. The complexes displayed a
strong activity against E. coli. The advantages of the
synthetic method are simple and convenient operation,
solvent-free, high yield, energy-saving, and being envir-
onmental friendly, and it is in accordance with the
requirements of green chemistry.
4. Experimental
4.1. Materials and physical measurements
All chemicals used in the experiments were analytical
reagents as received from commercial sources with no
further purification. Vanillin and glycine were pur-
chased from Sinopharm Chemical Reagent Co., Ltd.,
and zinc acetate, nickel acetate, and potassium hydrox-
ide were received from Chengdu Kelong Chemical
Reagent Company. S. aureus, E. coli, B. subtilis, and
S. epidermidis were provided by the 404 hospital of
Sichuan Mianyang.
The content of carbon, hydrogen, nitrogen, and
oxygen in the complexes was obtained by an Elementar
Vario EL CUBE elemental analyzer. Zinc and nickel
Table 5. Antibacterial activity of the Schiff base and the complexes.
Compound Concentration (mg/mL)
Gly-van Schiff base 1.0
[Zn(C10H9O4N)(H2O)3] 1.0
[Ni(C10H9O4N)(H2O)3]·1.5H2O 1.0
Moxifloxacin 1.0
241
were determined by ethylenediaminetetraacetic acid
2
(EDTA) complexometric titration. The X-ray powder
M diffraction patterns of the complexes were recorded by
O a Rigaku D/Max-RB X-ray diffractometer, Cu Kα
radiation at room temperature (λ = 0.154056 nm, step
width: 2θ = 0.2°, scan speed: 8°/min). The infrared
spectra of the complexes were measured by a Nicolet
5700 Fourier Transform Infrared spectrometer using
potassium bromide pellets in the region 400–4000
cm−1. Thermal analyses of the complexes were per-
formed by a TA Q500 thermal analyzer, and the
heating rates were suitably controlled at 10°C min−1
under nitrogen atmosphere, and the weight loss was
measured from ambient temperature up to 650°C.
4.2. Synthesis of the complexes
Glycine (5 mmol) and potassium hydroxide (5 mmol)
were weighed and placed in an agate mortar, and
continually grinded until they became sticky. Then,
vanillin (5 mmol) was added and grinded continuously,
the color of the reactants turned into yellow quickly,
and the loose yellow powder solid was obtained after
about 30 minutes. Afterward zinc acetate or nickel
acetate (5 mmol) was added to the agate mortar and
grinded continuously about 30 minutes. The reaction
was carried out at room temperature. The resultants
were washed repeatedly with distilled water and a little
dehydrated ethanol. Lastly, the resultants were filtered
and dried about 24 h in a vacuum drying oven at 40°C.
The zinc complex of the glycine–vanillin Schiff base
was pale–yellow powder, and the yield was about 82%.
The nickel complex of the glycine–vanillin Schiff base
was pale–blue powder, and the yield was about 86%.
4.3. Qualitative antimicrobial assay
Four pathogenic bacteria were used to test the
biological potential of the zinc(II) and nickel(II)
complexes of glycine–vanillin Schiff base ligand. They
were S. aureus, E. coli, B. subtilis, and S. epidermidis.
The culture maintenance and preparation of inoculum
were referenced by the literature method (43). The
antimicrobial activity of these compounds was
Inhibition zone (mm)
S. aureus E. coli B. subtilis S. epidermidis
12.1 14.9 14.1 12.3
11.4 16.6 14.9 14.2
10.8 18.7 16.3 13.0
21.3 24.8 33.6 30.2
242 G.-Q. Zhong and Q. Zhong
determined qualitatively by Oxford cup diffusion
method (43, 44). A lawn of microorganisms was
prepared by pipetting and evenly spreading inoculums
(106–107 CFU cm−3; CFU = colony forming units)
onto agar set in petri dishes, using nutrient agar for
the bacteria. The Oxford cups were sticked on the
previously inoculated agar surface and injected solu-
tion of the complex (0.15 mL) under sterile condi-
tions. The plates were incubated for 24 h at 37°C. The
antimicrobial activity was indicated by the presence of
clear inhibition zones around the disks.
Acknowledgments
This work was supported by the Scientific Research Funds
of Sichuan Provincial Education Department in China
(10ZA016). The authors are very grateful to State Key
Laboratory Cultivation Base for Nonmetal Composite and
Functional Materials, and Engineering Research Center of
Biomass Materials of Education Ministry for the testing of
elemental analyses, XRD, FTIR, and TG–DSC.
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