Novel structures of Zn(II) biometal cation with the biologically active substituted acetic acid and nitrogen donor ligands: Synthesis, spectral, phosphate diester catalytic hydrolysis and anti-microbial studies

Article abstract of DOI:10.1002/aoc.3829

The complexes [Zn(methoxyacetate)₂1,10-phenanthroline] 1 and [Zn₂(phenylacetate)₄(quinoline)₂] 2, were prepared and characterized by IR-spectroscopy, UV–Visible spectroscopy, ¹H and ¹³C NMR

Full text of DOI:10.1002/aoc.3829

Received: 23 December 2016
DOI: 10.1002/aoc.3829
Revised: 5 March 2017
Accepted: 5 March 2017
F U L L PA P E R
Novel structures of Zn(II) biometal cation with the biologically
active substituted acetic acid and nitrogen donor ligands:
Synthesis, spectral, phosphate diester catalytic hydrolysis and anti‐
microbial studies
†
†
Hijazi Abu Ali
| Shayma Kamel | Amani Abu Shamma
Department of Chemistry, Birzeit University,
West Bank, Palestine
The complexes [Zn(methoxyacetate) 1,10‐phenanthroline] 1 and [Zn (phenylacetate)
2
2
4
(
quinoline) ] 2, were prepared and characterized by IR‐spectroscopy, UV–Visible
2
Correspondence
1
13
spectroscopy, H and C NMR spectroscopy, single crystal X‐ray diffraction.
BNPP hydrolysis of the complexes and their parent nitrogen ligands were
Hijazi Abu Ali, Department of Chemistry,
Birzeit University, P.O. Box 14, West Bank,
Palestine.
Email: habuali@birzeit.edu;
habuali1@yahoo.com
4
scanned, the results indicated that the hydrolysis rates of BNPP were 4.5 × 10
5
and 6.2 × 10 for (1) and (2), respectively. In addition, anti‐bacterial activities
were scanned to investigate the effect of complexation on their activity against
Gram‐positive (S. epidermidis, S. aureus, E. faecalis, M. luteus and B. Subtilis)
and Gram‐negative (K. pneumonia, E. coli, P. Mirabilis and P. Aeruginosa)
bacteria using agar well‐diffusion method. Complex 1 showed high activity
−
+
against G and G bacteria except against E. faecalis and P. Aeruginosa. Complex
−
+
2
did not show any activity against G or G bacteria.
KEYWORDS
anti‐bacterial activity, hydrolysis, methoxyacetate, nitrogen donor ligands, phenylacetate, zinc(II) complexes
1
| INTRODUCTION
dosage, improved anti‐ulcerous, anti‐tumor and anti‐bacterial
activity, and biodistribution of medicine while monitoring its
As natural constituents or substances introduced into the
human body, biometal cations interact easily with molecules
of water and various parts of different organic and inorganic
biomolecules in biological systems forming various
complexes., The complexes which associate via O‐, N‐ and
S‐ donor atoms, have important roles in biological processes.
The products of interaction between M(II) metals and
medicine are fundamentally important for the theory of
coordination chemistry and significant in the development
of new methods for determining micro‐amounts of active
pharmacokinetics, excretion; the reduction in the unwanted
responses, improving anti‐microbial activities and synergistic
[
1,5–12]
effects of the metals and medicine, and
.
Biometals from the series of d‐metals with characteristic
M(II) ions can be found in the human body in small amounts,
and are mainly the active centers of enzymes of various
[
1,13]
functions.
Metals such as iron (Fe), zinc (Zn), and copper (Cu) all
[
14]
play important roles in many of the enzymatic reactions.
Zinc is a biometal necessary for the growth and develop-
ment of mammals, and in the human body, approximately 2
to 3 g of this metal can be found in the structure of more than
twenty metalloenzymes (carbohydrase, alcohol dehydroge-
nase, Cu‐Zn superoxide dismutase, etc). Zinc ion along with
the Cu(II) and Co(II) ions improves the immune system of
[
1–4]
components.
The study of the interaction between M(II)
biometal–O‐donor ligands is interesting for a variety of
aspects including achievement of better balanced medicine
†Author contributions: These authors have contributed equally to this work
Appl Organometal Chem. 2017;e3829.
wileyonlinelibrary.com/journal/aoc
Copyright © 2017 John Wiley & Sons, Ltd.
1 of 13
https://doi.org/10.1002/aoc.3829

2
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ABU ALI ET AL.
[
15]
humans.
Many biological processes require transition
metals such as cell division which requires (Fe, Co), respira-
tion requires (Fe, Cu), nitrogen fixation which requires (Fe,
[
16]
Mo, V), and photosynthesis which requires (Mn, Fe).
In this work, phenylacetic acid and methoxyacetic acid,
Figure 1, were selected to synthesize the complexes which
were characterized using different technique. Phenylacetic
acid belongs to an important class of compounds that is used
in several industrial applications, such as flavors and
fragrances in cosmetics or food. It also plays an important
role in pharmaceutical industry as precursors or drugs. For
example, phenylacetic acid can act as a precursor for
analgesics like diclofenac. Moreover, penicillin‐based
9 2 8
FIGURE 2 BNPP (C12H N O P)
2
2
| EXPERIMENTAL
.1 | Chemicals, materials and biological
species
All reagents, chemicals and solvents used in the present work
were purchased from Sigma‐Aldrich with high purity and
were used without further purification.
[
17]
antibiotics can be synthesized from phenylacetic acid.
The second carboxylic acid is methoxyacetic acid, a
primary metabolite of phthalates ester that is used in many
manufacturing products. It was also reported that
methoxyacetic acid has anti‐cancer activities, especially
prostate cancer. Researchers have found that methoxyacetic
acid can induce apoptosis and inhibits the growth of prostate
2
.2 | Physical measurements
Solid samples with anhydrous potassium bromide (KBr)
were ground and compressed into a disc to use them for IR
spectral measurements which were recorded in the 200–
000 cm− region using TENSOR II FT‐IR Spectrometer
1
[
18,19]
4
cancer cells.
(BRUKER). UV–Vis spectra were recorded using an Agilent
Metals can have many catalytic activity applications such
as the hydrolysis of phosphate esters, and also in the
detoxification of man‐made phosphorous(V) toxin of some
chemical weapons and pesticides. Actually the hydrolysis of
these phosphate esters is very important in chemistry,
biochemistry, and the mechanism of phosphodiester bond
hydrolysis, both non‐enzymatic and enzymatic, have been
8
453 photodiode array (PDA) spectrophotometer in the 200–
6
00 nm region using CH OH as a solvent. NMR spectra were
3
recorded using a Varian Unity Spectrometer operating at
1
13
3
00 MHz for H and C nucleus. Melting points were deter-
mined using capillary tubes with Electrothermal apparatus,
and X‐ray analyses were performed using SMART APEX
CCD X‐ray diffractometer (Bruker).
[20]
highly important for physical organic chemists.
Different studies showed that the spontaneous reaction
for the hydrolysis of a phosphodiesters bond under physio-
logical conditions is first order with rate constant (k) which
2
.3 | Synthesis and characterization of zinc(II)
compounds
has been approximated to be 1*10−11
s
−1
and 1*10
−10 −1
s
[
21]
for double strand and single strand DNA, respectively.
All zinc(II) compounds were prepared at room temperature.
These rates can be improved by changing the pH, the
concentration of metal ions and controlling the tempera-
ture at 37°C on a physiologically relevant time scale.
2
.3.1 | Zinc methoxyacetate1,10‐
phenanthroline [Zn(methoxy) 1,10‐phen] (1)
2
‘
bis(p‐nitrophenyl)phosphate’ (BNPP) shown in Figure 2
[22]
is a distinctive example of phosphate esters,
rapid
In (1:1) ratio sodium hydroxide (4.9 mmol, 0.20 g), and
methoxyacetic acid (0.32 g) in 50 ml of MeOH were mixed
and dissolved. Then (3.5 mmol, 0.48 g) ZnCl in minimum
amount of MeOH was added and the reaction mixture was
stirred for an additional 12 h. The solid product was filtered
and washed with cold water and air dried to give 1 g of solid
product. The prepared Zn‐methoxy (2.6 mmol, 0.41 g) was
dissolved in 50 ml MeOH and 1,10‐phenanthroline
hydrolysis of the high stable phosphate diester bond in
bis‐(p‐nitrophenyl) phosphate (BNPP) by enzymes or
catalysts containing metal ion complexes have recently
2
[
23,24]
been achieved.
(2.6 mmol, 0.41 g) dissolved in a minimum amount of MeOH
was added to the stirred Zn‐methoxy solution. Immediately a
white precipitate was formed and the reaction mixture was
stirred for an additional 24 h. The solution was filtered, the
filtrate was then allowed to evaporate slowly and solid crys-
tals were obtained. Recrystallization from MeOH gave single
crystals suitable for X‐ray analysis.
FIGURE 1 Carboxylic acids used in the present work:
A) Phenylacetic acid, B) Methoxyacetic acid

ABU ALI ET AL.
3 of 13
[
9
Zn(methoxy) 1,10‐phen] (1)
0% yield; m.p. 190–196°C; H NMR (CDCl ): δ (ppm) 3.50
2
2.4 | X‐ray crystallography
1
3
Single crystal X‐ray analysis of complexes 1 and 2 were car-
ried out by attaching single crystal to a glass fiber with epoxy
glue, and then it was transferred to X‐ray diffractometer sys-
tem (Bruker SMART APEX CCD) which was controlled by a
Pentium‐based PC equipped with SMART software pack-
(
2
s, 3H, CH ), 4.03 (s, 2H, CH ),7.83 (m, 2H, CH), 7.94 (s,
3
2
3
H, CH), 8.46 (d, 2H, CH, J
= 7.8 Hz), 9.18 (dd, 2H,
H‐H
3
13
1
CH, JH‐H = 6.3 Hz); C{ H}‐NMR (CDCl ): δ (ppm)
3
5
1
1
1
9.01 (CH ), 71.21 (CH ), 124.25 (CH), 124.29 (CH),
3 2
26.79 (CH), 128.80 (CH), 149.97 (CH), 150.01(CH)
[
25]
−
1
age.
tion λ = 0.71073 Å) was detected on a phosphor screen at ‐
4°C and it was held at 6.0 cm from the crystal. A detector
array of 512 X 512 pixels (a pixel size ≈120 μm) was used
The diffracted graphite‐monochromated (Kα radia-
73.84 (C = O); IR (cm , KBr): 3046, 2995, 1597.1,
514.22, 1425.9, 1342, 1101, 849.01, 726.37; UV–Vis
MeOH, λ (nm)): 271, 292.
4
(
[
26]
to collect the data.
Results of X‐ray crystallography and
structure refinements are shown in Table 1.
2
.3.2 | Zinc phenylacetate complex
Sodium hydroxide (1.0 mmol, 1.5 g), and phenylacetic acid
1.0 mmol, 5.0 g) were mixed in 100 ml of MeOH and
stirred for 3 h. Then the solvent was evaporated to give a
2
.5 | Kinetic measurements of BNPP
(
hydrolysis
Optimal concentrations and conditions for the BNPP hydro-
lysis were chosen by running different UV–visible kinetic
experiments and the best absorbance versus time plots were
used to determine the optimal conditions.
The following conditions were used for all hydrolysis
reactions:
HEPES'4‐(2‐hydroxyethyl)‐1‐piperazineethanesulfonic
acid') buffer at concentration of 50 μM was prepared by dis-
solving the appropriate amount of HEPES in minimum
amount of deionized water, then adjusting the pH to 7.91
using HCl or NaOH and the final volume was completed to
needle solid which was re‐dissolved in MeOH, and ZnCl2
(1.0 mmol, 5.0 g) dissolved in 15 ml of MeOH was added
with stirring. The reaction mixture was stirred for addi-
tional 12 h; the white precipitate of Zinc phenylacetate
was then filtered, washed with cold water and air dried to
give 4.4 g of solid product. Percentage yield was 89%;
1
m.p. > 200°C; H NMR (CDCl ): δ (ppm) 3.39 (s, 2H,
3
1
3
1
CH ), 7.21 (s, 5H, CH); C{ H}‐NMR (CDCl ): δ (ppm)
2
3
4
1
1
2
3.11 (CH ), 126.21 (CH), 128.31 (CH), 129.69 (CH),
2
−
1
37.91 (C), 176.98 (C = O); IR(cm , KBr): 3444, 2350,
531, 1439, 1391, 723; UV–Vis (MeOH, λ (nm)): 214,
59, 265.
1
00 ml. (0.036 g) of BNPP was dissolved in the prepared
−
3
buffer to obtain a certain concentration of 1.0x10 M. The
desired complex concentration was prepared in methanol,
the two solutions were kept in a water bath at 25°C for
2
.3.3 | Zinc phenylacetatequinolinecomplex
1
0 minutes, then (1.5 ml) of the two solutions were mixed
[
Zn (phenyl) (quin) ] (2)
2
4
2
in a quartz cell at 25°C, the rate of release of p‐nitrophenol
was directly measured using UV–Vis spectrophotometer at
λ = 400 nm and an extinction coefficient of 13400 Lmol
Zn‐phenyl (2.0 mmol, 0.40 g) was dissolved in 50 ml
MeOH (insoluble) and quinoline (4.0 mmol, 0.52 g) dis-
solved in minimum amount of MeOH was added to the
Zn‐phenyl solution with stirring. The reaction mixture was
stirred for 12 h. Dichloromethane was then added until
the solution became clear, and the solution was allowed to
evaporate slowly to give solid crystals suitable for X‐ray
analysis.
−1
−1
cm . The effect of BNPP concentration on the hydrolysis
process was studied by measuring the rate of hydrolysis at 10
−4
−5
[27]
and 10 M.
3
3
| RESULTS AND DISCUSSION
.1 | Synthesis of Zn(II) complexes
[
Zn (phenyl) (quin) ] (2)
2 4 2
1
Percentage yield was 87%; m.p. = 144°C; H NMR (DMSO):
One equivalent of ZnCl was reacted with 1 equivalent of
2
δ (ppm) 3.39 (s, 2H, CH ), 7.22 (bs, 5H, CH), 7.56 (m, 2H,
sodium methoxyacetate and sodium phenylacetate in metha-
nol to give [Zn(methoxy) (H O) ] and [Zn(phen) (H O) ],
respectively, as shown in Scheme 1. (Table 2)
2
CH), 7.75 (m, 1H, CH), 7.98 (m, 2H, CH), 8.35 (d, 1H,
2
2
2
2
2
2
3
13
1
CH, J
= 8.1 Hz), 8.88 (bs, 1H, CH); C{ H}‐NMR
H‐H
(
1
CDCl ): δ (ppm) 43.99 (CH ), 122.68 (CH), 126.97 (CH),
27.81 (CH), 129.10 (C), 129.32 (C), 129.99 (CH), 130.48
Different nitrogen donor ligands were mixed with the
synthesized zinc methoxy and zinc phenyl acetate and their
structures are shown in Schemes 2 and 3 respectively. The
proposed structures are also supported by their single crustal
X‐ray structure analysis.
3
2
(CH), 130.80 (CH), 137.47 (C), 138.74 (CH), 151.82 (CH),
−1
1
1
77.64 (C = O); IR (cm , KBr): 3027, 2362, 1946, 1588,
403, 1316, 809; UV–Vis (MeOH, λ (nm)): 276, 287.

4
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ABU ALI ET AL.
TABLE 1 Structure refinement and results of X‐ray crystallography of compounds (1) and (2)
Complex (1)
Complex (2)
Zn
2
Empirical formula
Formula weight
Temperature
C
18
H
22
N
2
O
8
Zn
C
50
H
42
N
2
O
8
459.75
295(2) K
929.60
296(1) K
Wavelength
0.71073 Å
Monoclinic
C2/c
0.71073 Å
Triclinic
P‐1
Crystal system
Space group
Unit cell dimensions
a = 14.287(2) Å α = 90°.
b = 10.137(1) Å β = 104.011(2)°.
c = 28.861(4) Å γ = 90°.
a = 8.464(2) Å α = 95.179(3)°.
b = 11.165(2) Å β = 108.293(3).
c = 12.160(3) Å γ = 93.175(3)°.
3
3
Volume
4055.2(9) Å
1082.4(4) Å
Z
8
1
3
3
Density (calculated)
Absorption coefficient
F(000)
1.506 Mg/m
1.259 mm−
1.426 Mg/m
1
1.166 mm−1
1904
480
3
3
Crystal size
0.40 x 0.29 x 0.14 mm
0.52 x 0.51 x 0.40 mm
Theta range for data collection
Index ranges
2.49 to 28.03°.
2.41 to 26.00°.
−18 < =h < =18,‐13 < =k < =13,
−10 < =h < =10,‐13 < =k < =13,
−14 < =l < =14
−
38 < =l < =37
Reflections collected
22840
10335
4095 [R(int) = 0.0323]
96.1%
Independent reflections
Completeness to theta =28.03°
Absorption correction
4880 [R(int) = 0.0268]
98.9%
Semi‐empirical from equivalents
0.8435 and 0.6329
4880 / 0 / 264
Semi‐empirical from equivalents
0.6527 and 0.5823
4095 / 0 / 280
Max. and min. transmission
Data / restraints / parameters
2
Goodness‐of‐fit on F
1.199
1.140
Final R indices [I > 2sigma(I)]
R indices (all data)
R1 = 0.0508, wR2 = 0.116
R1 = 0.0562, wR2 = 0.1191
0.478 and −0.400 e.Å−
R1 = 0.0546, wR2 = 0.1662
R1 = 0.0583, wR2 = 0.1675
1.274 and −0.362 e.Å−3
3
Largest diff. peak and hole
a R1 = ∑|| Fo| –| Fc|| / ∑| Fo and wR2 = ∑[w(F02 – Fc2)2]/ ∑[w(Fo2)2] 1/2
TABLE 2 Physical properties and yield of zinc(II) complexes
Complex
%Yield
m.p (°C)
Solubility
1
2
90
87
190–196
Hot CH
3
OH, DMSO
144
2 2
DMSO,CH Cl
SCHEME 1 Synthesis and proposed structure of zinc(II) complexes
SCHEME 2 Synthesis and proposed structure of zinc(II) complex 1

ABU ALI ET AL.
5 of 13
[
31,32]
nitrogen base ligands.
N‐Zn bond distances (2.128(2)
Å and 2.115(2) Å) are also similar to previously reported
[
31,32]
values i.e. (2.097 Å).
(Table 3)
Complex 1 adapted slightly distorted octahedral geome-
try around the central Zn(II) cation due to unsymmetrical
bond angles. O(4)‐Zn(1)‐O(6) = 76.00(8)°, O(2)‐Zn(1)‐O
(6) = 94.62(10)°, O(2)‐Zn(1)‐O(1) = 76.93(8)°, O(1)‐Zn
(1)‐N(1) = 101.79(8)° and O(4)‐Zn(1)‐N(2) = 99.33(8)°, N
(1)‐Zn(1)‐N(2) = 79.11(9)°.
Table 2.7 shows the H‐bond distances in (Å), these bonds
are between O(3), O(4) and O(5) of the methoxyacetate and
H of water molecules.(Table 4)
SCHEME 3 Synthesis and proposed structure of zinc(II) complex 2
Moreover, in the crystals of complex 1 a π‐π interaction
with 3.473 Å between the 1,10‐phenanthroline ligands are
found as shown in Figure 4 which further stabilizes the
structure.
3
.2 | Crystallographic study
3
.2.1 | X‐ray crystal structure of [Zn(methoxy)
1
2
,10‐phen] (1)
3
.2.2 | X‐ray crystal structure of Zn (phenyl)
2
4
Figure 3 shows the crystal structure of complex 1 with two
bidentate methoxyacetate groups and one bidentate 1,10‐
phenligand, both ligands formed stable five member ring
with Zn as the metal center.
Further stability of the crystal lattice was achieved by the
intramolecular hydrogen bonding between the two water
molecules and the carbonyl oxygen atom of one
methoxyacetate groups as illustrated by the dashed lines
(
quin) ] (2)
2
The dinuclear with a paddlewheel structure of complex 2 is
shown in Figure 5. Two Zn(II) cations are bonded to four
bidentate phenylacetate groups in (syn‐syn) bridging coordi-
nation mode and two monodentate quin groups.
The bond distances of O(1)‐Zn(1) 2.060(4) Å, O(2)‐Zn
(1)#1 2.039(4)Å, O(3)‐Zn(1)2.057(4)Å, O(4)‐Zn(1)#12.026
(4)Å. The coordination distances of N(1)‐Zn(1) 2.064(4) Å.
Selected bond distances and bond angles are listed in
Table 5.
Complex 2 adapted slightly distorted square based pyra-
midal geometry around the central Zn(II) centers with O(1)‐
Zn(1)‐O(3) = 85.7(2)°, O(1)‐Zn(1)‐N(1) = 96.35(17)°, N
(1)‐Zn(1)‐O(3) = 97.07(16)°, O(4)#1‐Zn(1)‐N(1) = 104.37
(17)°, O(2)#1‐Zn(1)‐N(1) = 104.97 (17)°, O(2)#1‐Zn(1)‐Zn
(1)#1 = 80.64(12)° and O(4)#1‐Zn(1)‐Zn(1)#1 = 80.18(12)°.
[
28]
which occur within one single molecule.
In addition, both
intramolecular and intermolecular hydrogen bonding play a
crucial role in the enhancement of complex stability, for
example, H‐bonds give conformational stability of protein
and other complex structures such as
tances of O‐Zn (2.0269(19) Å, 2.155(2) Å, 2.0253(19) Å
[
29,30]
. The bond dis-
and 2.201(2) Å) are similar to previously reported values
(1.84–2.33 Å) in Zn(II) diclofenac, valproate, indomethacine,
ibuprofen, naproxen and sulindac complexes with various
3.3 | IR spectroscopy
IR spectroscopy is a functional group technique which plays
an important role in structure elucidation. Infrared spectral
data of sodium methoxyacetate, complex 1, sodium
−
1
phenylacetate, and complex 2 in the 400–4000 cm range
as KBr pellet are summarized in Tables 6 and 7, respectively.
In metal carboxylate complexes, the major characteristic
of the IR spectra is the frequency of the υ asymmetric (υ )
as
−
and υ symmetric (υ ) of carbonyl (COO ) stretching vibra-
tions and the difference between them Δυ(COO ). The fre-
s
−
quency of these bands depends upon the coordination mode
of the carboxylate ligand. Monodentate complexes exhibit
−
Δυ(COO ) values that are much greater than those of the
ionic carboxylates. Chelating (bidentate) complexes exhibit
−
FIGURE 3 Molecular structure of complex 1 showing the labeling
atom scheme
Δυ(COO ) values that are significantly less than those of
−
the ionic values. Δυ(COO ) values for bridging complexes

6
of 13
ABU ALI ET AL.
TABLE 3 Selected bond angles (°) and bond distances (Å) of 1
Bond distance (Å)
Bond angle (Å)
N(1)‐Zn(1)
N(2)‐Zn(1)
O(1)‐Zn(1)
O(2)‐Zn(1)
O(4)‐Zn(1)
O(6) ‐Zn(1)
C(1)‐N(1)
2.128(2)
2.115(2)
2.0269(19)
2.155(2)
2.0253(19)
2.201(2)
1.328(4)
1.355(3)
1.347(4)
1.334(4)
1.269(4)
1.416(4)
1.422(4)
1.265(4)
1.418(4)
1.403(4)
N(1)‐Zn(1)‐N(2)
O(4)‐Zn(1)‐N(2)
N(1)‐Zn(1)‐O(1)
O(2)‐Zn(1)‐O(1)
O(2)‐Zn(1)‐O(6)
O(4)‐Zn(1)‐O(6)
C(1)‐N(1)‐C(5)
79.11(9)
99.33(8)
101.79(8)
76.93(8)
94.62(10)
76.00(8)
118.5(2)
C(5)‐N(1)
C(1)‐N(1)‐Zn(1)
C(5)‐N(1)‐Zn(1)
C(6)‐N(2)‐C(10)
C(10)‐N(2)‐Zn(1)
C(6)‐N(1)‐Zn(1)
Zn(1)‐O(1)‐C(13)
C(14)‐O(2)‐Zn(1)
C(15)‐O(2)‐Zn(1)
C(14)‐O(2)‐C(15)
Zn(1)‐O(4)‐C(16)
Zn(1)‐O(6)‐C(17)
Zn(1)‐O(6)‐C(18)
C(17)‐O(6)‐C(18)
129.1(2)
C(6)‐N(2)
112.34(17)
118.4(2)
C(10)‐N(2)
C(13)‐O(1)
C(14)‐O(2)
C(15)‐O(2)
C(16)‐O(4)
C(17)‐O(6)
C(18)‐O(6)
128.7(2)
112.89(18)
120.22(19)
114.54(17)
130.0(2)
113.8(3)
121.84(19)
113.77(18)
130.8(2)
114.3(3)
are greater than those of chelating complexes, and close to
TABLE 4 Hydrogen bonds in complex 1 [Å and °]
[
33]
the values of the ionic carboxylates.
The stretching vibrations for sodium phenylacetate υ
D‐H...A
d(D‐H) d(H...A) d(D...A) <(DHA)
as
−1
−
−
(
COO ) and υ (COO ) have been observed at 1562.2 cm
O(2 W)‐H(2 W2)...O(5)#1
O(1 W)‐H(2 W1)...O(4)#1
O(1 W)‐H(1 W1)...O(3)
0.87
0.93
0.90
2.62
2.02
2.00
3.035(6)
2.914(4)
2.900(5)
110.8
161.2
173.1
s
−
1
−
and 1387.1 cm , respectively, and (ΔυCOO ) is 175.1 cm
−
1
−
−
.
For sodium methoxyacetate υ (COO ) and υ (COO )
as s
−1
−1
are observed at 1610.9 cm and 1427.4 cm , respectively
−
−1
Symmetry transformations used to generate equivalent atoms: #1 x, y + 1, z
and (ΔυCOO ) is 183.5 cm .
FIGURE 4 π‐π interaction between the 1,10‐phenanthroline ligands in complex 1

ABU ALI ET AL.
7 of 13
1
13
3
.4 | H and C nuclear magnetic resonance
1
13
The H and C NMR spectral data of complex 1, Zn‐
[
35]
methoxyacetate and methoxyacetic acid
are shown in
1
Table 8. The relative intensities of H NMR signals are in
agreement with the proposed structure. Due to complex
formation, change in the resonance chemical shift takes
1
place, where comparison of the H NMR spectra of 1 and
Zn‐methoxy showed a downfield shift in complex 1, this
deshielding effect is caused by the donation of electrons from
the carboxylate group to the zinc ion through σ bond. In addi-
tion, the O‐H resonance in the spectra of complex 1 was
absent confirming the coordination with the metal center as
shown in Figure 3.
As shown in Tables 8–10 and 11 slight upfield and down-
field shifts in methoxyacetic acid and phenylacetic acid were
observed due to complexation with Zn metal or/and nitrogen
donor ligands.(Figure 6)
FIGURE 5 Molecular structure of complex 2 showing the labeling
atom scheme
−
−
In complex 1; υ (COO ) and υ (COO ) are observed at
as
s
1
−1
−
1
597.1 cm− and 1425.9 cm , respectively, with ΔυCOO
at 171.2 cm , which is less than that of sodium
methoxyacetate, this is supporting a bidentate (chelating)
−
1
3.5 | Electronic absorption spectroscopy
1
0
coordination mode. The O‐H vibration frequency at
3
Zn(II) complexes with a spatial configuration of d and
completely filled d orbital's have no d‐d electronic transi-
tion bands. From the results shown in Tables 12 and 13,
no ligand to metal charge transfer “LMCT” can be
observed due to filled d orbitals. The bands are assigned
to MLCT charge transfer and intra ligand transition e.g.
440 cm− indicates the presence of water molecules in the
1
crystal structure. Generally, the ν(M‐O) and ν(M‐N) for metal
complexes appear as weak bands in the ranges between 430–
1
−1 [34]
4
74 cm− and 524–576 cm .
These bands for complexes
1
and 2 are shown in Tables 6 and 7 respectively.
−
−1
*
In complex 2; ΔυCOO is 132.3 cm , which is less than
that of sodium phenylacetate, this is supporting a bidentate
syn‐syn bridging) coordination mode.
π‐π transition, the spectra of the complexes are similar to
those of nitrogen parent ligands with very small blue or
red shifts caused by zinc coordination. MLCT bands are
(
TABLE 5 Selected bond distances (Å) and bond angles (°) of 2
Bond distance (Å)
Bond angle (°)
N(1)‐Zn(1)
Zn(1)‐Zn(1)#1
O(1)‐Zn(1)
O(2)‐Zn(1)#1
O(3)‐Zn(1)
O(4)‐Zn(1)#1
C(1)‐N(1)
2.064(4)
2.9773(12)
2.060(4)
2.039(4)
2.057(4)
2.026(4)
1.368(6)
1.308(7)
1.246(6)
1.236(6)
O(1)‐Zn(1)‐O(3)
85.7(2)
96.35(17)
97.07(16)
104.37(17)
104.97(17)
80.64(12)
77.81(12)
78.25(11)
80.18(12)
115.5(4)
126.2(4)
118.2(5)
129.0(4)
126.3(4)
128.7(4)
O(1)‐Zn(1)‐N(1)
N(1)‐Zn(1)‐O(3)
O(4)#1‐Zn(1)‐N(1)
O(2)#1‐Zn(1)‐N(1)
O(2)#1‐Zn(1)‐Zn(1)#1
O(1)‐Zn(1)‐Zn(1)#1
O(3)‐Zn(1)‐Zn(1)#1
O(4)#1‐Zn(1)‐Zn(1)#1
C(9)‐N(1)‐Zn(1)
C(9)‐N(1)
C(10)‐O(1)
C(18)‐O(3)
C(1)‐N(1)‐Zn(1)
C(9)‐N(1)‐C(1)
C(10)‐O(1)‐Zn(1)
C(10)‐O(2)‐Zn(1)#1
C(18)‐O(3)‐Zn(1)

8
of 13
ABU ALI ET AL.
1
TABLE 6 Summary of principle peaks in the IR spectra of sodium
TABLE 8 H–NMR spectral data of complex 1, Zn‐methoxyacetate
−1
methoxyacetate and complex 1 in (cm
)
and methoxyacetic acid
Assignments
Na (methoxy)
Complex 1
Complex 1
Zn‐methoxy
H methoxy
11.00 (OH)
ν(O‐H)
‐
3440
‐
‐
‐
ν(C‐H)aliph
ν(C‐H)ar
ν(C‐O)
2940, 2829
3.50, (s, 3H, CH
3
)
)
3.90 (s, 2H, CH
3.25 (s, 3H, CH
2
)
)
4.12 (s, 2H, CH
3.48 (s, 3H, CH
2
)
)
‐
3046, 2995
1101
4.03, (s, 2H, CH
2
3
3
1208, 1110
7.83, (m, 2H, CH)
γ(C‐H)
932
1333
1610.9
1427.4
183.5
‐
849.01
1514.22
1597.1
1425.9
171.2
7.94, (s, 2H, CH)
3
δ(C‐H)
8.46, (d, 2H, CH, JH‐
H
= 7.8 Hz)
.18, (dd, 2H, CH, JH‐
= 6.3 Hz)
νas(COO‐)
3
9
νs(COO‐)
Δν(COO‐)
ν(ring)
H
726.37
1342
trend and rates in the BNPP hydrolysis process by complexes
and 2.
The results revealed that the rate of BNPP hydrolysis was
better in complex 2 compared to those in complex 1.
ν(ring) + δ(C‐H)
ν(Zn‐O)
‐
1
‐
430
TABLE 7 Summary of principle peaks in the IR spectra of sodium
1
3
phenylacetate and complex 2 in (cm−1
TABLE 9
C NMR spectral data of complex 1, Zn‐methoxyacetate
)
and methoxyacetic acid
Assignments
Na‐phenyl
Complex 2
1
3
C NMR
ν(C‐H)ar
γ(C‐H)
3025
3027
Complex 1
Zn‐methoxy
Hmethoxy
933,710
809
1
7
5
1
1
1
1
1
1
73.84 (C = O)
174.02 (C = O)
174.83 (C = O)
ν(C‐H)alph
2000
2362,1946
1.21 CH
9.01 CH
2
3
71.44 CH
58.25 CH
2
3
69.33 CH
2
3
ν
as(N‐H)
(N‐H)
‐
‐
‐
59.35 CH
ν
s
‐
26.79 CH
24.29 CH
24.25 CH
50.01 CH
49.97 CH
28.80 CH
δ(NH
N‐H) wagging
ν(C‐NH
2
)
‐
‐
(
‐
‐
2
)
‐
‐
ν(C‐C)ring
ν(C‐C)ring + δ(CH)
ν(C‐N)
1496
1588
1316
1403
483
561
1281,1186
‐
‐
‐
ν(Zn‐O)
1
ν(Zn‐N)
TABLE 10 H–NMR spectral data of complex 2, Zn‐phenylacetate
and phenylacetic acid
1
H NMR
observed around (201–296 nm) with є values around 3000
Lmol cm .
−
1
−1 [36,37]
Complex 2
Zn‐phenyl
Hphenyl
‐
‐
11.00 (OH)
3
.39 (s, 2H, CH
2
)
3.39 (s, 2H, CH
2
)
2
3.49 (s, 2H, CH )
3
.6 | BNPP hydrolysis
7
.22 (bs, 5H, CH)
7.21 (s, 5H, CH) 7.32 to 7.25 (s, 5H, CH)
The ability of metal complexes for phosphate diester hydroly-
sis is studied in the present work. The initial rate of the
hydrolysis is determined by measuring the absorption of p‐
nitrophenolate ion at 400 nm and various plots of absorbance
versus time were obtained. One of these is shown in Figure 7.
The prepared complexes were used as catalysts for the
phosphate diester group hydrolysis. The results showed good
7.56 (m, 2H, CH)
7
7
8
.75 (m, 1H, CH)
.98 (m, 2H, CH)
3
.35 (d, 1H, CH, JH‐
= 8.1 Hz)
H
8
.88 (bs, 1H, CH)

ABU ALI ET AL.
9 of 13
1
3
TABLE 11
C NMR spectral data of complex 2, Zn‐phenylacetate
TABLE 12 UV–visible spectral data for the prepared complexes
and phenylacetic acid
Є(Lmol− cm−1
1
)
Compounds
λmax (nm)
Complex 2
Zn‐phenyl
Hphenyl
Zn‐phenyl
214
259
2280.3
202.9
203.68
1
4
1
1
1
1
1
1
1
1
1
1
77.64 C = O
176.98 C = O
178.00 C = O
2
65
271
92
271
92
3.99 CH
2
43.11CH
2
41.30 CH
137.35 CH
139.09 CH
128.90 CH
127.30 CH
2
Zn‐methoxy
1454.2
565.02
51.82 CH
38.74 CH
37.47 CH
30.80 CH
29.99 CH
29.32 CH
29.10 (CH)
27.81 (CH)
26.97 (CH)
22.68 (CH)
137.91 CH
129.69 CH
128.31 CH
126.21 CH
2
1
2
49119
14563
2
276
287
5606.4
5359.8
TABLE 13 UV–visible spectral data for pure N‐ligands
є(Lmol− cm−1
)
1
Ligands
,10‐phen (1*10− M)
λmax (nm)
5
1
266.0
45919
45488
2
25.0
quin (1*10− M)
5
204.0
44107
41442
3605.9
Moreover, Michaelis–Menten equation was used for calculat-
ing the initial rate at different concentrations of BNPP, the
results are summarized in Table 14.
2
2
25.0
76.0
One of the suggested mechanisms is shown in Scheme 4:
nitrophenol and phosphoric acid, where H O is bonded again
2
(
1) H O molecule coordinate with metal complex to produce
2
to the metal(II) ion rapidly, and thus completes the catalytic
complex A, (2) the oxygen atom on the P = O of the substrate
BNPP) is coordinated to the complex metal ion, forming the
[
27,38,39]
cycle.
(
intermediate B, (3) intramolecular metal hydroxide attacks
the positive P atom of BNPP molecule to enhance the release
of the p‐nitrophenol with first order‐rate constant (k). This
step is considered to be the key step for the hydrolysis, (4)
3
.7 | Anti‐bacterial activity
Before measurement of their biological activity, the solution
stability of the complexes was tested and checked periodi-
cally by H and C NMR in chloroform and DMSO solvents
after that H O coordinates again with the metal ion quickly,
2
1
13
D is formed, (5) the intermediate D quickly loses p‐
1
FIGURE 6 H–NMR spectra of complex 2

1
0 of 13
ABU ALI ET AL.
FIGURE 7 BNPP hydrolysis by complex 2 at pH = 7.91, 25°C and [complex] = 1 × 10−4
M
TABLE 14 Kinetic parameters of the BNPP hydrolysis by complexes 1 and 2 at different [BNPP]
b
Concentration
M)
Initial rate,
Max. Rate,
Michaelis constant,
Catalytic rate
constant, Kcat s
2‐order rate constant ,
(
V
0
mol L− s−1
1
V
max mol L s−1
−1
Km mol L
−1
a
−1
K[BNPP] L\mol
−1 −1
s
Complex 1(1 × 10−3 M)
× 10−
× 10−
× 10−
3
3.1 × 10−4
3 × 10−4
1.8 × 10−4
3.16 × 10−4
6.9 × 10−6
0.316
9.487
4.5 × 10
4
1
1
1
4
5
Complex 2 (1 × 10−4 M)
× 10−
× 10−
× 10−
3
9.4 × 10−4
8.1 × 10−4
3.6 × 10−4
9.5 × 10−4
1.5 × 10−5
6.2 × 10
5
1
1
1
4
5
a
:
K
cat = Vmax/[complex],
BNPP = Kcat/K
b
:
K
m
.
and always gave the same data. In addition, the complexes
were crystallized by slow solvent evaporation at room
temperature that took several days and gave the same physi-
cal properties of the compounds. The anti‐bacterial activities
of the synthesized zinc complexes were studied using differ-
ent types of gram‐negative bacteria (K. pneumonia, E. coli, P.
Mirabilis and P. Aeruginosa) and gram‐positive bacteria (S.
epidermidis, S. aureus, E. ferabis, M. luteus and B. Subtilis)
to monitor the effect of complexation on anti‐bacteria activ-
ity. The average (n = 3) IZD inhibition zone diameters with
its associated standard error is summarized in Table 15.
In general, the activity was dependent on the concentra-
tion of the complex; this was obvious by the direct proportion
found between the concentration and the IZD value.
Compounds are considered significantly active when IZD is
larger than 15 mm, moderately active when IZD is between
[
40]
7 and 14 mm and weakly active for IZD less than 7 mm.
Although it is not clear why some compounds exhibit dif-
ferent bacterial activity with Gram‐positive and Gram‐nega-
tive bacteria, it may be ascribed to the difference in the
[
41]
overall structure of their cell walls.
Metal ions are essential for the survival of microbes in the
environment or the host. Therefore, the microbes should
ensure uptake of metal ions according to their physiological
needs as the imbalance in metals homeostasis could be
deleterious to the microbe. Host defense against bacterial
infection consists of either sequestering ions resulting in
bacterial starvation, or increased release of these metals,
which results in toxicity. Zinc is required for optimal bacterial
ZnCl , Zn‐phenyl and Zn‐methoxyacetate did not show
2
any anti‐bacterial activity against all tested micro‐organisms.
DMSO was used as negative control to resist any tested
microorganisms, whereas gentamicin (G) and Erythromycin
(E) were used as positive control for both G‐ and G+ bacte-
ria. Complex 2 showed no activity against all tested bacterial
species. Complex 1 showed high activity against G‐ or G+
bacteria except, against E. ferabis and P. Aeruginosa.
growth at a concentration of 10− to 10 M,
5
−7
[42]
however

ABU ALI ET AL.
11 of 13
[
45]
death.
Intriguingly, the zinc oxide (ZnO) nanoparticles
have a broad spectrum antibacterial activity against both
Gram‐negative and Gram‐positive bacteria including major
foodborne pathogens like Escherichia coli O157:H7,
Salmonella, Listeria monocytogenes, Staphylococcus aureus,
[
46,47]
and Campylobacter jejuni.
The antibacterial activity of
ZnO has been attributed to the disruption of the cell
membrane and the increase in the expression of oxidative
stress response genes such as katA and ahpC) and a general
[
47]
stress response gene (dnaK).
Gram‐positive bacteria has a plasma membrane and a
thick cell wall while the Gram‐negative bacteria has plasma
membrane, cell wall and an outer membrane which adds
another layer of complexity in terms of interaction and pene-
tration of these complexes into the bacteria.
It is not known why complex 2 did not show antibacterial
activity against the tested Gram‐negative and Gram‐positive
bacteria. These complexes harbor the zinc ion, the carboxyl-
ate group and the nitrogen base. It is plausible that the
structural differences in the nitrogen bases of these
complexes hindered their binding to the membrane or DNA
of the tested bacteria.
SCHEME 4 The proposed mechanism of the hydrolysis of BNPP
high concentration of zinc ions exhibit antibacterial proper-
[43]
ties.
The toxicity of high concentration of Zn has been
shown with infections associated with Streptococcus pneu-
[
44]
monia,
where excess zinc competes with manganese
resulting in manganese starvation, and initiation of the
oxidative stress in the bacteria, which ultimately leads to
The site of action of the non‐steroidal anti‐inflammatory
drugs (NASADs) in human body is determined by inhibiting
the synthesis of prostaglandin through effect on cyclooxygen-
[
44]
bacterial death.
It was suggested that zinc exhibit the
[
48]
antibacterial effect by binding to the bacterial membrane,
thus increasing the lag phase and the generation time of the
organism, which prolongs cell division resulting in cell
ase enzyme.
This mechanism is not available in microor-
ganisms due to lack of the presence of cyclooxygenase.
Otherwise, killing activity of ibuprofen in Candida cells
TABLE 15 Anti‐bacterial activity data of complexes 1 and 2
Compounds
B. Subtilis G+
S. epidermidis G+
S. aureus G+
E. faecalis G+
M. luteus G+
Zn‐phenyl
‐
‐
‐
‐
‐
Zn‐methoxy
‐
‐
‐
‐
‐
ZnCl
2
‐
‐
‐
‐
‐
‐
‐
DMSO
‐
‐
‐
G
29.3 Æ 4.4
36.0 Æ 2.1
20.6 Æ 1.1
‐
34.7 Æ 1.4
45.0 Æ 0.7
28.7 Æ 1.1
‐
29.3 Æ 3.2
41.3 Æ 1.4
27.0 Æ 0.8
‐
16.3 Æ 0.9
34.7 Æ 3.4
40.0 Æ 0.1
27.6 Æ 1.1
‐
E
‐
1
‐
2
‐
Compounds
K. pneumonia G‐
P. Mirabilis G‐
E. coli G‐
P. Aeruginosa G‐
Zn‐phenyl
‐
‐
‐
‐
Zn‐methoxy
‐
‐
‐
‐
ZnCl
2
‐
‐
‐
‐
DMSO
‐
‐
‐
‐
G
E
1
34.7 Æ 3.4
21.5 Æ 0.5
24.3 Æ 0.6
‐
27.0 Æ 1.0
17.3 Æ 0.9
25.6 Æ 1.4
‐
25.3 Æ 0.9
24.0 Æ 1.6
22.3 Æ 1.5
‐
20.0 Æ 1.8
21.7 Æ 3.3
‐
2
‐

1
2 of 13
ABU ALI ET AL.
was found through direct damage in their cytoplasmic
[6] A. Andrade, S. F. Namora, R. G. Woisky, G. Wiezel, R. Najjar, A.
[
49]
A. Sertiéj, S. D. de Oliveira, J. Inorg. Biochem. 2000, 81, 23.
membrane.
Intriguingly, it has been shown that Ibuprofen
exhibit antibacterial activity against six periodontal microor-
[7] N. H. Gokhale, S. S. Padhye, S. B. Padhye, C. E. Anson, A. K.
[
50]
Powell, Inorg. Chim. Acta 2001, 319, 90.
ganisms.
The exact mechanism of antibacterial activity
of NASIDs is unclear. However, studies have proposed
[8] Z. Trávníček, M. Maloň, Z. Šindelář, K. Doležal, J. Rolčík, V.
Kryštof, M. Strnad, J. Marek, J. Inorg. Biochem. 2001, 84, 23.
[51]
inhibition of bacterial DNA synthesis
membrane activity.
or impairment of
[
50]
[
9] A. T. H. Chaviara, P. C. Christidis, A. Papageorgiou, E.
Chrysogelou, D. J. Hadjipavlou‐Litina, C. A. Bolos, J. Inorg.
Biochem. 2005, 99, 2102.
4
| CONCLUSION
[
10] N. Jiménez‐Garrido, L. Perelló, R. Ortiz, G. Alzuet, M. González‐
Alvarez, E. Cantón, E. M. Liu‐González, S. García‐Granda, M.
Pérez‐Priede, J. Inorg. Biochem. 2005, 99, 677.
The new Zn(II) complexes with phenylacetic acid and
methoxyacetic acid in the presence of the following nitrogen
donor ligands; 1,10‐phen, quin, were synthesized and charac-
[
[
11] V. Milacic, D. Chen, L. Giovagnini, A. Diez, D. Fregona, Q. P.
Dou, Toxicol Appl Pharm 2008, 231, 24.
1
13
1
terized. IR, UV–Vis, H and C{ H}‐NMR spectroscopic
techniques were used to study and characterize the new com-
plexes. X‐ray single crystal diffraction measurements were
also studied for complexes 1 and 2 as an additional strong
evidence for their structure elucidation. Different metal
geometries and carboxylate coordination modes were
obtained and proved. The structure of complex 1 revealed
slightly distorted octahedral geometry with two bidentate
methoxy ligands and one bidentate 1,10‐phen ligand bonded
to the Zn(II) cations. In complex 2, slightly distorted square‐
based pyramidal geometry of the binuclear Zn units was
obtained with four phenyl bridging bidentate ligands and
two monodentate quin ligands were bonded to the two Zn
12] A. Pérez‐Rebolledo, L. R. Teixeira, A. A. Batista, A. S. Mangrich,
A. G. Aguirre, H. Cerecetto, M. González, P. Hernández, A. M.
Ferreira, N. L. Speziali, Eur. J. Med. Chem. 2008, 43, 939.
[
[
[
13] R. R. Crichton, Biological Inorganic Chemistry An Introduction,
Elsevier B. V. 2008 369.
14] Y. Arafat, S. Ali, S. Shahzadi, M. Shahid, Bioinorg. Chem. Appl.
2
013, 2013.
15] N. Lipscomb, W. N. Strater, Chem. Rev. 1996, 96, 2375.
[16] I. Bertini, H. B. Gray, Bioinorganic Chemistry, University Science
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[17] M. Oelschlägel, S. R. Kaschabek, J. Zimmerling, M. Schlömann,
D. Tischler, Biotechnol. Reports. 2015, 6, 20.
(II) catinos. The results of the kinetic experiments revealed
[18] R. Keshab, Q. Zhang, L. Sen, K. Neil, L. Hua, S. Zeng, W.
that these complexes scan act as potent BNPP hydrolysis,
these activities were decreased in the order: complex 2 > 1.
Complex 1 exhibited high activity against G‐ and G+ bacte-
ria except against E. faecalis and P. Aeruginosa. Complex 2
Guangdi, C. Z. Y. Zhang, Am. J. Clin. Exp. Urol. 2014, 2, 300.
[
19] K. R. Parajuli, Q. Zhang, S. Y. Z. Liu, Int. J. Mol. Sci. 2015, 16,
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20] L. W. Karena, A. M. Rebecca, M. U. Lyann, H. Paul, V.‐P.
Dominik, A. B. S. Sidhu, F. Hisashi, D. R. Paul, A. F. David,
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−
+
did not exhibit any activity against G or G bacteria.
[
[
[
21] K. Dong, M. Xiang‐Guang, J. D. Ying Liu, K. Xing‐Ming, Z. Xian‐
ACKNOWLEDGEMENT
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The authors thank the office of Vice President for Academic
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How to cite this article: Abu Ali H, Kamel S, Abu
Shamma A. Novel structures of Zn(II) biometal cation
with the biologically active substituted acetic acid and
nitrogen donor ligands: Synthesis, spectral, phosphate
diester catalytic hydrolysis and anti‐microbial studies.
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