Study molecular modeling and the effect of some biological metals on the efficiency of norfloxacin in presence of 3-(bromoacetyl)coumarin

Article abstract of DOI:10.1002/aoc.6448

A series of new mixed ligand metal complexes of Mn(II), Fe(II), Co(II), Ni(II), Cu(II), and Zn(II) have been synthesized by the reaction of norfloxacin (NOR) with 3-(bromoacetyl)coumarin (BAC) in 1:1:1 (Mⁿ⁺:NOR:BAC) molar ratio, which characterized by elemental analysis, spectroscopic measurements (FT-IR, UV–Vis) molar conductance, effective magnetic moments, and thermogravimetric analysis (TG) and (DTG). All the complexes soluble in DMSO and the conductivity measurement indicate that the complexes are electrolyte with ratio 1:1 for Mn(II), Fe(II), and Zn(II) and 1:2 for Co(II), Ni(II), and Cu(II). Electronic and magnetic data elucidated the octahedral structure for all complexes. Assorted thermodynamic factors are calculated, and the results are explicated. Molecular modeling calculations (bond angles, dihedral angles, total energy, heat of formation, and dipole moment) confirm the structural geometry of the complexes and indicate the very good agreement between the computed and experimental geometrical parameters. The calculated data for the hardness (η) and absolute softness (σ) showed that all complexes are soft with respect to ligands. The two ligands and their metal complexes have also been screened for their antibacterial and antifungal activity against some selected species; the data showed that the complexes have remarkable potency as compared with the parent ligands.

Full text of DOI:10.1002/aoc.6448

Received: 24 July 2021
DOI: 10.1002/aoc.6448
Revised: 31 August 2021
Accepted: 31 August 2021
F U L L P A P E R
Study molecular modeling and the effect of some biological
metals on the efficiency of norfloxacin in presence of
3-(bromoacetyl)coumarin
Walaa H. El-Shwiniy1,2
Wael A. Zordok1
| Manar A. Gamil1
| Sadeek A. Sadeek1
|
1Department of Chemistry, Faculty of
Science, Zagazig University, Zagazig,
Egypt
2Department of Chemistry, College of
Science, University of Bisha, Bisha,
Saudi Arabia
Abstract
A series of new mixed ligand metal complexes of Mn(II), Fe(II), Co(II), Ni(II),
Cu(II), and Zn(II) have been synthesized by the reaction of norfloxacin (NOR)
with 3-(bromoacetyl)coumarin (BAC) in 1:1:1 (Mn+:NOR:BAC) molar ratio,
which characterized by elemental analysis, spectroscopic measurements
(FT-IR, UV–Vis) molar conductance, effective magnetic moments, and
thermogravimetric analysis (TG) and (DTG). All the complexes soluble in
DMSO and the conductivity measurement indicate that the complexes are
electrolyte with ratio 1:1 for Mn(II), Fe(II), and Zn(II) and 1:2 for Co(II),
Ni(II), and Cu(II). Electronic and magnetic data elucidated the octahedral
structure for all complexes. Assorted thermodynamic factors are calculated,
and the results are explicated. Molecular modeling calculations (bond angles,
dihedral angles, total energy, heat of formation, and dipole moment) confirm
the structural geometry of the complexes and indicate the very good agreement
between the computed and experimental geometrical parameters. The
calculated data for the hardness (η) and absolute softness (σ) showed that all
complexes are soft with respect to ligands. The two ligands and their metal
complexes have also been screened for their antibacterial and antifungal
activity against some selected species; the data showed that the complexes
have remarkable potency as compared with the parent ligands.
Correspondence
S. A. Sadeek, Department of Chemistry,
Faculty of Science, Zagazig University,
Zagazig, Egypt.
Email: s_sadeek@zu.edu.eg
K E Y W O R D S
3-(bromoacetyl)coumarin DFT, antimicrobial activity, mixed ligand complexes,
norfloxacin
1 | INTRODUCTION
betalactamase producing organisms,[1–4] consequently,
much research concerning the complexation of fluoro-
Fluoroquinolone is an important antibiotic family; they
are particularly interesting for application due to their
ability to chelate with metal ions. In general, it is active
against a wide variety of aerobic gram-negative and
gram-positive bacteria specifically and active against
aminoglycoside-resistant, Pseudomonas aeruginosa and
quinolone with different metal ions has been discussed in
the literature.[5–8] The crystal structures of several free
fluoroquinolone molecules indicate that in some cases,
the carboxylic group is protonated and the molecule thus
exists in a zwitterionic form with protonated terminal
nitrogen of the piperazine ring, or in other cases, the
Appl Organomet Chem. 2021;e6448.
wileyonlinelibrary.com/journal/aoc
© 2021 John Wiley & Sons, Ltd.
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https://doi.org/10.1002/aoc.6448

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EL-SHWINIY ET AL.
carboxylic group is deprotonated, and the hydrogen atom
of this group is hydrogen bonded to an adjacent 4-oxo
atom in a solid state.[9] Fluoroquinolones behaved as
bidentate ligands through one oxygen of carboxylic
group and oxygen of pyridon group.[10] In the literature
survey, fluoroquinolones may be coordinated with metal
ions as monodentate through only one nitrogen of
piperazine ring or as a bridging ligand between two metal
ions.[9,11–14] NOR (Scheme 1A) is a one of second genera-
tion synthetic fluoroquinolone with a broad-spectrum
antibacterial agent for oral administration. The coordina-
tion chemistry of NOR with metal ions of biological and
pharmaceutical importance is considerable interest.[15,16]
The NOR interacted with metal particles for formaliza-
tion complexes interact accordingly a bidentate through
the oxygen atoms of carboxylic and pyridon groups.[17–19]
Coumarin is the parent component of a family of
numerous compounds found in a wide range of natural
products. It is thought that coumarin's antibacterial
action comes from either killing or inhibiting the
microbe's active site.[20] Coumarin compounds have been
shown to produce a wide range of metal chelates with
various chelated modes, spectroscopic characteristics, and
possible uses. The complexation of coumarin-derived
ligands with different transition metals, in particular, has
been identified as a viable path to the creation of novel
medicinal medicines. A number of coumarin derivatives
and transition complexes were previously produced. The
coordination capabilities and complexation behaviors of
liable ligands need to be investigated more. Coumarin
exists in a number of forms due to the numerous substitu-
tions that may be made to their basic framework, which
influence their bioactivity.[21–23] 3-(Bromoacetyl)couma-
rin (BAC) (Scheme 1B) is a coumarin counterpart with
the substitute bromoacetyl in position 3. It is well known
that the existence of a metal ion bonded to biologically
active materials may enhance their activity by changing
electronic and geometrical structure. The goal of this
research is to synthesize and investigate the influence of
Mn(II), Fe(II), Co(II), Ni(II), Cu(II), and Zn(II) ions on
the antibacterial efficiency of NOR in the presence of
BAC. In order to evaluate the binding of the new mixed
ligand complexes, the magnetic, spectral, and thermal
methods were used. Density functional theory (DFT) was
used to quantify the cation type impact on conceptual of
the chelates and predict their minimized architecture, as
well as the total energy, heat of formation, and total
dipole moment. Indeed, the antimicrobial activity of
ligands and their metal complexes were screened against
selected kind of pathogenic bacteria and fungi.
2 | EXPERIMENTAL
2.1 | Materials and instruments
Whole chemicals utilized were of analytical reagent grade
and applied with no additional purifying. ZnSO4
SCHEME 1 (A) 1-Ethyl-
6-fluoro-4-oxo-7-(piperazin-1-yl)-
1,4-dihydroquinoline-
3-carboxylic acid and its
zwitterion and (B) 2-bromo-
1-(2-methylene-2H-chromen-
3-yl)ethanone

EL-SHWINIY ET AL.
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(99.90%), CuCl2.2H2O (99.90%), NiCl2.6H2O (99.90%),
CoCl2.6 H2O (99.90%), FeSO4 (99.90%), and MnSO4.6H2O
(99.90%) were obtained from Aldrich Chemical Co. While
NOR was obtained from Merck Chemical Co. BAC, ace-
tone, DMSO, AgNO3, BaCl2, K2CrO4, and NaOH were
purchased from Fluka Chemical Co. Table S1 lists all of
the instruments that were utilized.
fungi. After autoclaved, it cooled to 47ꢀC and then seeded
with tested microorganisms. After solidification prepare
disks were used approximately 6 mm in diameter and
placed in a petri dish, and 5-mm diameter holes were
punched by borer sterile cork-borer. The investigated
compounds were dissolved in DMSO (1 ꢁ 10ꢂ3 M). Cip-
rofloxacin and moxifloxacin were utilized as standard
material. The antimicrobial effect was determined after
24 h at 37ꢀC for bacteria and 7 days at 30ꢀC for fungi, by
measuring the diameter of inhibition zones (mm). The
experiment was carried out in triplicate with SDs.
2.2 | Synthesis of mixed ligand
complexes
The buff [Mn (NOR)(BAC)(H2O)2]SO4.2H2O complex,
(1), was prepared by blending 1 mmol (0.26 g) of
MnSO4.6H2O with 20-ml acetone drop by drop into an
agitated suspending mixture 1 mmol (0.27 g) of BAC in
1-mmol (0.32 g) NOR with 50-ml acetone. The mixture
was refluxed for 6 h before being drained and dried in
vacuo. The brown, light brown, faint green, light green,
and pale brown solid complexes [Fe (NOR)(BAC)(H2O)2]
SO4.2H2O (2), [Co (NOR)(BAC)(H2O)2]Cl2.2H2O (3),
[Ni (NOR)(BAC)(H2O)2]Cl2.2H2O (4), [Cu (NOR)(BAC)
(H2O)2]Cl2 (5), and [Zn (NOR)(BAC)(H2O)2]SO4.2H2O
(6) were set in identical technique qualified above by uti-
lizing FeSO4, CoCl2.6H2O, NiCl2.6H2O, CuCl2.2H2O, and
ZnSO4, respectively.
3 | RESULTS AND DISCUSSION
NOR interacts with manganese (II), iron (II), cobalt (II),
nickel (II), copper (II), and zinc (II) ions, respectively, in
the existence of BAC to form a variety of complexes (1),
(2), (3), (4), (5), and (6). On the premise of its elemental
analysis, the complexes' stoichiometry was determined
(Table 1). The complexes' formulae and architecture were
determined using physical and chemical characteristics
such as magnetic properties, melting points, molar con-
ductance, and spectral measurement. The results of ana-
lytical data indicate that all the complexes contain water
molecules and the number of bound water molecules in
these complexes being different. The molar conductivity
for freshly prepared DMF solutions (1 ꢁ 10ꢂ3 M) of the
complexes was measured at room temperature. The data
show the molar conductance value of the complexes (1),
(2), and (6) with sulphate as counter ions found around
142.00 S cm2 molꢂ1 indicating these complexes as 1:1
electrolytes, while the complexes (3), (4), and (5) with
Clꢂ counter ions with molar conductance value nearly
around 122.00 S cm2 molꢂ1 are 1:2 electrolytes.[25] The
results are consistent with qualitative studies that indi-
cated the existence of chloride and sulphate anions as
counter ions.[26] At ambient temperature, the magnetic
properties (as B.M) were recorded, revealing that all of
chelates are paramagnetic, with the exception of complex
(6), which has diamagnetic properties, and that all of
them had octahedral.[27,28]
2.3 | Antimicrobial investigation
2.3.1 | Tested bacteria and fungi
The tested bacterial strains were Staphylococcus aureus
(S. aureus), Listeria monocytogens (L. monocytogens),
Bacillus cereus (B. cereus), and Acnietobacter baumanii
(A. bauamanii). The tested phytopathogenic fungi were
Aspergillums niger (A. niger), Aspergillums terreus
(A. terreus), Candida albicans (C. albicans), and Fusarium
oxysporium (F. oxysporium). All tested strains have been
conserved as pure cultures in the collection of the micro-
biological laboratory, at Faculty of Science, Zagazig
University, Egypt.
2.3.2 | Bactericidal and fungicidal evaluation
3.1 | FT-IR data and bonding
The disc diffusion technique has been used.[24] Each iso-
late was suspended in sterilized Millipore water, after
that put into Müller-Hinton agar medium (MHA)
(0.2 g/L beef extract, 17.5 g/L acid hydro lysate of casein,
1.5 g/L starch and 17 g/L agar) (0.7%) for bacteria and
Czapex-Dox agar medium (30 g/L sucrose, 3 g/L NaNo3,
1 g/L K2HPO4, 0.5 KCL, 0.01 FeSO4, and 20 g/L agar) for
The significant IR spectral data of NOR, BAC, and their
metal complexes were listed in Table 2 lists and showed
in Figure S1. The main bands were discussed in order to
determine the site and kind of coordination that may be
involved in chelation from ligands to metal ions. The
NOR spectrum has two peaks at 1736 and 1619 cmꢂ1 that
are attributed to ν(C=O)COOH and ν(C=O)pyr
,

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EL-SHWINIY ET AL.

EL-SHWINIY ET AL.
5 of 15
TABLE 2 Selected infrared absorption frequencies (cmꢂ1) of NOR, BAC, and their metal complexes
ν(O–H);
ν(C=O)α,β
unsaturated
νas
νs
Compounds H2O; COOH ν(C=O)lactone
ν(C=O)COOH (COOꢂ) ν(C=O)pyr (COOꢂ) ν(M–O)
Nor
BAC
(1)
3425w
-
-
-
1736vs
-
1619vs
-
-
-
-
1729vs
1736s
1674s
1605 m
-
-
-
-
3372mbr
1678 m
1547s
1419 m
605 m, 555 m,
513w, 463w
(2)
(3)
(4)
(5)
(6)
3417mbr
3426sbr
1736s
1736s
1736s
1736s
1734 ms
1632s
-
-
-
-
-
1674 m
1674s
1551 m
1551 m
1547w
1581 m
1550w
1408 m
1404 m
1408 m
1408 m
1410w
670 m, 617w,
513 m
1624s
664w, 629w,
513w
3410mbr
3441mbr
3422mbr
1612 m
1631s
1674 m
1674s
633vw, 555 m,
509w
629w, 601w,
517 m
1624 m
1670w
621 m, 555vw,
505vw
Abbreviations: s, strong; w, weak; m, medium; br, broad; ν, stretching; v, very.
respectively.[16–18] The ν(C=O)COOH peak at 1736 cmꢂ1
disappeared in the spectra of the complexes. Two very
strong bands are present around 1674 cmꢂ1 and
1415 cmꢂ1 assigned to (COO-) asymmetric and symmetric
stretches, respectively, with an average Δν around
259 cmꢂ1, indicating a monodentate coordination of car-
boxylate group.[29,30] The shift of the peak assigned to
pyridone group (1619 cmꢂ1) to lower value around
1555 cmꢂ1 indicates that the oxygen of pyridone group is
coordinated to the metal ions.[31] The BAC spectrum has
two distinct peaks that have been ascribed to ν(C=O)α,
3.2 | Electronic spectra and magnetic
moments
The assignments of the spotted electronic absorption
bands of the NOR, BAC, and their metal complexes were
listed in Table 3. In fact, the electronic spectrum of NOR
exhibit various peaks at 305 and 340, 370 nm, and BAC
exhibits peaks at 305 and 335, 370 nm (Figure S2) that
may be referred to π–π* and n–π* transitions, respec-
tively.[32,35] The shift of the absorption bands to higher
values (bathochromic shift) and to lower values (hyp-
sochromic shift) and presence of new bands in the spec-
tra of complexes indicate that the formation of their
metal complexes. In addition, the existence of new peaks
in the range 505–515 nm that can be ascribed to ligand–
metal charge transfer[36–38] and the development of new
bands in the range 610–645 nm in all complexes except
complex (6) can be ascribed to d-d transition.[39–42] The
absorbance spectrum of complex (1) (with magnetic 5.36
B.M.) showed two identified bands at 610 and 645 nm,
and ν(C=O)lactone at 1674 and 1729 cmꢂ1
,
β-unsaturated
respectively.[32] In the IR spectra of the complexes, the
band corresponding to the ν(C=O)α, β-unsaturated shifted to
lower frequency, which indicate the participation of the
oxygen moiety's of α, β-unsaturated ketone with the metal
ions. Also, the band of ν(C=O)lactone is shifted to higher
values in all complexes (Table 2), which is a good
indication that the inclusion of lactone carbonyl oxygen
atom of coumarin in chelation with metal ions.[32,33] The
broad band at 3420 cmꢂ1 showed the vibrational mode
of ν(O–H), due to the presence of lattice water. The
appearance of bands around 3350, 840, and 600 cmꢂ1 in
the spectra of all complexes were attributed to ν(O–H),
rocking and wagging vibration of the coordinated
water.[34] The presence of new peaks with different inten-
sities which characteristics for ν(M–O) were observed at
605, 555, 513, and 463 cmꢂ1 for Mn(II), 670, 617, and
513 cmꢂ1 for Fe(II), 664, 629, and 513 cmꢂ1 for Co(II),
633, 555, and 509 cmꢂ1 for Ni(II), 629, 601, and 517 cmꢂ1
for Cu(II), and 621, 555, and 505 cmꢂ1 for Zn(II). The pro-
posed structures for complexes are shown in Figure 1.
4
4
which may be assigned to 6A1 ! T2 (G) and 6A1g ! T2g
(4G) transition, respectively.[43] The absorption peak at
625 nm in complex (2) spectrum with the magnetic
5
moment (4.90 B.M.) can be attributed to T2g (D)–5Eg
transition.[28,44] Complex (3) absorption spectrum
4
exhibited peak at 620 nm which may be ascribed to T1g
4
(F) ! T1g (P) transition in support of octahedral shape
with magnetic moment (3.89 B.M.).[45] The complex
(4) showed absorption peak at 615 nm, which may be
3
assigned to 3A2g ! T1g (P) transition and supporting dis-
torted octahedral geometry.[28] The peak observed at
2
2
630 nm for complex (5) may be assigned to B1g ! E1g

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EL-SHWINIY ET AL.
FIGURE 1 The
coordination mode of Mn(II),
Fe(II), Co(II), Ni(II), Cu(II), and
Zn(II) with NOR and BAC
TABLE 3 UV–Vis spectra of NOR, BAC, and their metal complexes
Mixed ligand complex with
Assignments (nm)
π–π* transitions
NOR
BAC
Mn(II)
300
Fe(II)
295
Co(II)
295
Ni(II)
300
Cu(II)
295
Zn(II)
295
305
305
n–π* transitions
340, 370
335, 370
325, 370
515
335, 410
515
330, 370
505
325, 370
515
335, 385
515
335, 370
510
Ligand–metal charge transfer
d–d transition
-
-
-
-
610, 645
625
620
615
630
-
transition with the magnetic moment (1.74 B.M.) is very
close to spin value (1.73 B.M.) expected for an octahedral
geometry.[33,46]
decomposition stage for all complexes involving the loss
of BAC moiety, two coordinated water and lost species
3C2H2 + 5CO + 2H2 + HBr (Table 4). The third step
indicated by DTG within the temperature range 464–
647ꢀC of all complexes, resulting from the decomposition
of NOR, a stable metal oxide are formed in case of com-
plexes (2), (3), (4), and (6), MnSO4 for complex (1) and
Cu metal for complex (5) as a final residue. Kinetic and
thermodynamic variables such as E*, H*, S*, and G* of
the thermal process were computed using coats-Red-
fern[47] and Horowitz-Metzger[48] equations, as shown in
Table 5. The E* values were found to be in the range
8.295–3.11 ꢁ 105 KJ molꢂ1; the high values reflect the
thermal stability of the complexes (Figure S3). The fact
that the final residue free energy was larger than that of
the starting compounds, suggesting that all breakdown
processes were non-spontaneous, was proven by the posi-
tive sign of G* for complexes. The activation, G*, values
3.3 | Thermogravimetric analyses
Thermal studies were used to investigate the chemical
composition of the resulting volatile decomposing con-
stituents and the characteristics of the complexes. The
majority of compounds including organic metal com-
plexes suffer physical and chemical changes when sub-
jected to heat under defined experimental conditions.
These changes are characteristic of substances and can be
used for qualitative and quantitative analysis. The elimi-
nation of hydrated water molecules of the present mixed
ligands metal complexes recorded on heating up to ꢃ
150 OC in the TG thermograms (Figure 2) the second

EL-SHWINIY ET AL.
7 of 15
FIGURE 2 TGA and DTG
diagram for NOR, BAC, and
their metal complexes
for successive breakdown steps of a particular compound
rose considerably. This seems to be attributable to the
fact that significantly increasing S* quantities from one
phase to the next exceeds the amounts of H*. On the
other hand, the negative S* readings, indicated that
the activated compound was better organized than the
reactants or that the reaction was delayed.[49–51]
(2) followed by (4), (5) and then (1), (3) compared with
NOR and BAC. In respect to L. monocytogens, the com-
plexes (1), (3) gave the highly significant followed by
complex (6) with no significant variations for complexes
(2), (5) in contrast to the NOR and BAC. In the case of
B. cereus, the newly synthesized complexes (1), (3), (5),
and (6) possess highly biological activity followed by
complexes (2) and (4). In terms of A. baumanii shows no
significant variations for complexes (1), (2), (4), and (5),
and the complex (6) shows significant activity compared
with NOR and BAC. The high sensitivity of the
complexes have been attributed to hyper-conjugation of
the coordinated aromatic Lewis bases, which increases
the net electron density on the coordinated metal ion
and consequently higher antimicrobial activity. In gen-
eral, metal complexes are more active than the ligand
because metal complexes may serve as a vehicle for
3.4 | Antimicrobial efficiency
The data depicted in Figure 3 revealed that remarkable
antimicrobial activities when all tested therapies shown
antibacterial activity against all tested bacteria, particu-
larly at higher tested doses and no antifungal observed
(Table S2). The best bactericidal activity was observed in
terms of S. aureus with the newly synthesized complex

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EL-SHWINIY ET AL.
TABLE 4 The maximum temperature Tmax (οC) and weight loss values of the decomposition stages for NOR, BAC, and their metal
complexes
Weight loss (%)
Compounds
Decomposition
Tmax (οC)
Calc.
Found
Lost species
NOR
First step
Second step
Total loss
Residue
116
330, 423, 654
8.77
83.69
92.46
7.54
8.75
83.73
92.48
7.52
C2H4
6C2H2 + 3NO + HF + 0.5H2
BAC
(1)
First step
Total loss
Residue
268
91.01
91.01
8.99
91.03
91.03
8.97
3C2H2 + 3CO + HBr
2C
First step
Second step
Third step
Total loss
Residue
94
189, 440
641
4.45
37.46
29.05
70.96
28.93
4.34
37.22
29.10
70.66
29.32
2H2O
3C2H2 + 5CO + 2H2 + HBr
3C2H2 + 3CO + 3NH3 + HF + H2
MnSO4 + 7C
(2)
(3)
First step
Second step
Total loss
Residue
213
464
39.15
45.35
84.5
39.11
45.37
84.48
15.49
3C2H2 + 5CO + 2H2 + HBr
6C2H2 + 2NO2 + NH3 + HF + SO2 + H2
FeO + 4C
15.5
First step
Second step
Third step
Total loss
Residue
77
230, 403
560
6.7
6.68
37.61
31.48
75.77
24.21
3H2O
37.59
31.51
75.8
3C2H2 + 5CO + 2H2 + HBr
2C2H4 + 2CO + 3NH3 + HF + Cl2
CoO + 10C
24.2
(4)
(5)
(6)
First step
Second step
Third step
Total loss
Residue
94
241, 382
603
6.7
37.6
40.46
84.76
15.24
6.67
37.56
40.44
84.67
15.29
3H2O
3C2H2 + 5CO + 2H2 + HBr
5C2H2 + HF + NH3 + 2HCl + 2CO + H2 + N2
NiO + 4C
First step
Second step
Third step
Total loss
Residue
83
234, 378
647
4.54
38.22
49.2
91.96
8.04
4.52
38.19
49.29
92.01
7.96
2H2O
3C2H2 + 5CO + 2H2 + HBr
7C2H2 + HF + NH3 + Cl2 + 2CO + N2O
Cu
First step
Second step
Third step
Total loss
Residue
79.62
228, 342
557
4.39
36.97
41.37
82.73
17.27
4.36
36.98
41.35
82.69
17.28
2H2O
3C2H2 + 5CO + 2H2 + HBr
4C2H2 + 3CO + SO2 + HF + 2NH3 + NO+0.5H2
ZnO + 5C
activation of ligands as the principle cytotoxic spe-
cies.[52–55] Ciprofloxacin and moxifloxacin were utilized
as standard material. The order of efficiency of the drug
NOR and BAC mixed ligand metal complexes found as
the following, in case of S. aureus decrease in order:
complex (2) > complexes (4) and (5) > complexes
(1) and (3) > ciprofloxacin standard > moxifloxacin
standard > Nor > complex (6) > BAC, L. monocytogens
decrease in order: complexes (1) and (3) > complex (6)
> NOR > ciprofloxacin standard > BAC > moxifloxacin
standard > complexes (2) and (5) > complex (4),
B. cereus decrease in order: complex (5) > complex (1)
> complex
(6) > complex
(2) > complex
(4)
>
> ciprofloxacin standard > moxifloxacin standard
BAC > NOR, A. baumanii decrease in order: complex
(6) > BAC > NOR > moxifloxacin standard > ciprofloxa-
cin standard > complex (4) > complex (2) > complexes
(1) and (5) > complex (3).
3.5 | Theoretical calculations
The optimized structures of the NOR, BAC, (1), (2),
(3), (4), (5), and (6) compounds and related energies

EL-SHWINIY ET AL.
9 of 15
TABLE 5 Thermal behavior and Kinetic parameters determined using Coats–Redfern (CR) and Horowitz–Metzger (HM) operated for
NOR, BAC, and their metal complexes
Parameter
Decomposition Ts
Compounds range (K) (K) Method (KJ/mol)
E*
S*
H*
G*
A (sꢂ1
)
(KJ/mol. K) (KJ/mol) (KJ/mol) Ra
SDb
NOR
537–734
844–996
453–582
763–992
322–557
750–933
563–743
430–537
537–738
696 CR
HM
8.295
11.585
13.183
14.512
127.59
351.82
5.944 ꢁ 102 ꢂ1.958
6.838 ꢁ 104 ꢂ1.020
7.716
11.006
12.412
13.742
ꢂ4.370
ꢂ4.146
268.355
306.045
59.828
24.106
267.614
231.563
167.106
88.609
91.978
48.526
159.102
67.343
2.135
1.810
0.921 0.310
0.866 0.200
0.934 0.190
0.929 0.090
0.995 0.097
0.998 0.061
0.965 0.222
0.963 0.225
0.996 0.079
0.992 0.117
0.960 0.250
0.955 0.265
0.962 0.259
0.954 0.283
0.998 0.088
0.998 0.097
0.955 0.280
0.947 0.302
927 CR
HM
15.73 ꢁ 102
14.68 ꢁ 103
ꢂ1.357
ꢂ1.176
2.499
2.465
BAC
(1)
541 CR
HM
2.59 ꢁ 10ꢂ6 ꢂ0.357
188.665
59.515
232.410
133.344
89.145
52.003
253.430
139.224
188.575
94.057
108.725
56.085
181.445
84.270
8.04 ꢁ 106
3.25 ꢁ 1016
4.65 ꢁ 1029
3.11 ꢁ 105
6.91 ꢁ 105
2.45 ꢁ 1014
4.79 ꢁ 1021
9.04 ꢁ 109
ꢂ0.118
0.066
816 CR
HM
2.73 ꢁ 105
3.11 ꢁ 105
6.16 ꢁ 104
2.59 ꢁ 104
2.72 ꢁ 105
2.36 ꢁ 105
1.70 ꢁ 105
9.18 ꢁ 104
9.39 ꢁ 104
5.05 ꢁ 104
1.62 ꢁ 105
7.02 ꢁ 104
0.318
(2)
487 CR
HM
ꢂ0.137
ꢂ0.130
0.025
(3)
833 CR
HM
0.164
(4)
654 CR
HM
ꢂ0.056
1.42 ꢁ 1012 ꢂ0.014
(5)
507 CR
HM
8.90 ꢁ 108
ꢂ0.072
1.00 ꢁ 1011 ꢂ0.032
(6)
615 CR
HM
2.75 ꢁ 109
ꢂ0.065
1.85 ꢁ 1010 ꢂ0.049
aCorrelation coefficients of the Arrhenius plots.
bStandard deviation.
were calculated utilizing DFT[56] in addition to the
B3LYP functional[57,58] and Lee, Yang, Parr,[59] as well
as the Hartree-Fock local exchange function.[60]
3.5.2 | Structural parameters and models
of BAC
The calculated dihedral angle for the optimized
geometrical of BAC (Table S4) confirms that the cou-
marin and carbonyl units are nearly planar. The end
C1 = O6 and C4 = O10 of coumarin moiety bonds do
not assume different orientations as predicted for
binding of BAC as a bidentate ligand via the two car-
bonyl groups oxygen (O6 and O10), which lie in the
same trend as the cis conformer (Figure 4). The aver-
age difference between B3LYP/CEP-31G and practical
bond lengths and bond angles is 0.04 Å and 0.5ꢀ,
respectively; these data are drawing to give the opti-
mized geometry of molecule. The bond lengths and
bond angles reflect that the type of hybridization sp2 is
common on all central atoms. The values of bond
lengths, bond angles, and dihedral angles are com-
pared nicely with that obtained from the experimental
data.[60–63] Because of the significant buildup of charge
density on the donating oxygen atoms, the BAC com-
pound reacts as a bi-dentate ligand (O6 and O10) with
a highly dipole = 12.17D, which is credited to the
3.5.1 | Structural parameters and models
of NOR
According to the calculated dihedral angles (Table S3),
the NOR molecule is highly sterically hindered, and the
piperazine group found out of the plane of molecule
where the values are not zero or 180ꢀ and O5 found in cis
configuration with O1 while O22 and O5 are in trans con-
figuration and C21-O5 not in the same plane of C2-O22
(Figure 4). The value of bond angle reflects on sp2 hybrid-
ization of C3; the same result is obtained with C2 and C4.
The values of bond lengths are compared nicely with that
obtained from X-ray data.[61] The data of charge distribu-
tion on the optimized geometry of NOR (Table 6) indicate
that a significant built up of charge density on the oxygen
atoms which distributed over all molecule so NOR mole-
cule behaves as bi-dentate ligand (Opyr and OCOOH), and
the molecule is a highly dipole μ = 42.86D.

10 of 15
EL-SHWINIY ET AL.
FIGURE 3 Statistical representation for biological activity of NOR, BAC, and their metal complexes
FIGURE 4 DFT-optimized geometry of NOR and BAC
molecule's planarity excluding the Br atom, which lies
outside the plane dominated with all atoms of the
molecule.
complexes. Table S5 summarizes the bond lengths, bond
angles, total energy, heat of formation, and dipole
moment of each complexes. In all complexes metal ion is
coordinated with six oxygen atoms (O1 and O5) of NOR,
(O6 and O10) of BAC, and (O11 and O12) form water to
complete the regular octahedral structure as shown in
Figures S4–S9. The computational data (bond lengths
and bond angles) show that the equatorial plane is domi-
nated by four donors oxygen atoms, two from NOR
3.5.3 | Geometrical structure of complexes
The main objective of this study is to determine the opti-
mized structure of NOR, BAC, as well as their metal

EL-SHWINIY ET AL.
11 of 15
TABLE 6 Calculated charges on donating sites and energy values (HOMO, LUMO), energy gap ΔE/eV, hardness (η), global softness (S),
electro negativity (χ), absolute softness (σ), chemical potential (Pi), global electrophilicity (ω), and additional electronic charge (ΔNmax) of
NOR, BAC, and studied complexes by using DFT calculations
Parameters
M
NOR
-
BAC
-
Mn(II)
0.587
Fe(III)
0.163
Co(II)
0.302
Ni(II)
0.140
Cu(II)
0.075
Zn(II)
0.226
O1
ꢂ0.250
ꢂ0.340
-
ꢂ0.283
ꢂ0.380
-
ꢂ0.387
ꢂ0.447
ꢂ0.354
ꢂ0.326
ꢂ0.379
ꢂ0.231
0.379
ꢂ0.366
ꢂ0.447
ꢂ0.297
ꢂ0.253
ꢂ0.341
ꢂ0.235
0.341
ꢂ0.347
ꢂ0.372
ꢂ0.321
ꢂ0.296
ꢂ0.352
ꢂ0.216
0.352
ꢂ0.363
ꢂ0.423
ꢂ0.257
ꢂ0.284
ꢂ0.367
ꢂ0.219
0.367
ꢂ0.350
ꢂ0.365
ꢂ0.256
ꢂ0.286
ꢂ0.359
ꢂ0.187
0.359
ꢂ0.366
ꢂ0.397
ꢂ0.356
ꢂ0.362
ꢂ0.388
ꢂ0.185
0.388
O5
O6
O10
-
-
HOMO, H
LUMO, L
I = ꢂH
A = ꢂL
ΔE = L – H
η = (I – A)/2
χ = ꢂ(H – L/2)
σ = 1/η
ꢂ0.376
ꢂ0.129
0.376
0.129
0.247
0.124
0.253
8.065
4.032
ꢂ0.253
0.258
2.041
ꢂ0.383
ꢂ0.161
0.383
0.161
0.222
0.111
0.272
9.009
4.505
ꢂ0.272
0.333
2.450
0.231
0.235
0.216
0.219
0.187
0.185
0.148
0.106
0.136
0.148
0.172
0.203
0.074
0.053
0.068
0.074
0.086
0.102
0.305
0.288
0.284
0.293
0.273
0.287
13.514
6.757
18.868
9.434
14.706
7.353
13.514
6.757
11.628
5.814
9.804
S = 1/2 η
Pi = ꢂχ
ω = (Pi)2/2 η
ΔNmax = χ/η
4.902
ꢂ0.305
0.629
ꢂ0.288
0.782
ꢂ0.284
0.593
ꢂ0.293
0.580
ꢂ0.273
0.433
ꢂ0.287
0.404
4.122
5.434
4.176
3.959
3.174
2.814
Note: (I) is ionization energy and (A) is an electron affinity.
(O1 and O5), one of BAC (O6), and the latest from water
molecule (O11), whereas the axial plane is inhabited by
BAC and the second water molecule oxygen atoms (O10
and O12). The bond angle O11MO12 is in range (89.79ꢀ–
90.05ꢀ), and this value refers to the two water molecules
are lying in cis-form and then they are perpendicular to
each other. Also, the angles around M(II) with surround-
ing oxygen atoms varied from 86.02ꢀ to 179.77ꢀ; these
values not deviated from a regular octahedron. The bond
lengths between metal ion and bonded oxygen atoms of
NOR (O1 and O5) in all metal complexes varied from
(1.925–2.086 Å) and (1.916–2.074 Å), respectively,[64–68]
also, the bond lengths between central metal ion and oxy-
gen atoms of BAC (O6 and O10) are (1.922–2.079 Å) and
(1.925–2.075 Å), respectively.[69–76]
the Co(II) ion, while in case of other complexes, the
metal ion carry lower charge density and the smallest
charge is located on metal ion of complex (5). The nega-
tive charge was dispersed on the two ligands oxygen
atoms, while all complexes hydrogen atoms afford posi-
tive sign. The NOR oxygen atoms (O1 and O5) have a
higher negative charge than that of BAC in chelates. The
charge density in studied complexes varies from 0.075 on
the Cu-ion to 0.587 on Mn-ion (Table 6). These results
mean that there is an electron back-donation from the
metal sites in a MLCT mode to the π* orbitals of the NOR
in some of these complexes. This conclusion is further
confirmed by comparing the values of the calculated
charge density on the donating atoms, oxygen atom of
NOR, BAC, and in complexes. The distribution of atomic
charges is also important in the determination of the
direction of the dipole moment vector in the complexes
which depends on the centers of negative and positive
charges.
3.5.4 | Charge distribution analysis
The charge distribution of NOR indicates the presence of
a greater net negative and positive pole on the molecule,
as a result the molecule is a strong dipole, μ = 42.86D.
The charge density for NOR, BAC, and their complexes
given in Table 6 show a relatively high charge density on
the metal ion in the complexes (1) and (3) only; the
charge accumulated on Mn(II) ion is 0.587 and 0.302 on
3.5.5 | Molecular orbitals and frontier
Molecular orbitals play an important role in the electric
properties.[77] A system with a lower energy gap ΔE (the
difference between HOMO and LUMO) was more

12 of 15
EL-SHWINIY ET AL.
reactive than one with a larger ΔE.[78] All studied com-
plexes have lower ΔE than free ligands, so these com-
plexes are more reactive; the values of ΔE (Table 6)
varied from 0.106 eV for complex (2) (more reactive) and
0.203 eV for complex (6) (less reactive). The electron
movement between orbitals easily occurs so we observe a
peak around 250 nm in the UV–Vis spectra for all studied
complexes, while the ΔE of the NOR and BAC is
0.247 eV and 0.222 eV, respectively. The ΔE is closely
associated with the reactivity and stability of the executed
molecule, and shows the nature of the molecule with low
kinetic stability and slightly high chemical reactivity. On
the other hand, the adjacent orbitals are often closely
spaced on the frontier region. The nodal properties of
molecular orbitals of studied complexes (Figure 5) are
illustrative and suggest orbital delocalization, strong
orbital overlap, and low number of nodal planes. These
features lead to UV–Vis spectrum characterized by low
energy and high intensity bands presence of charge trans-
fer transitions. The different MOs show a different extent
of localization on the different fragments of the com-
plexes, and the above rationalization is valid for MO
analysis of all the studied complexes. The ΔE for the all
studied complexes varied according to the type of metal
ion as shown in Table 6 and shows the isodensity surface
plots of HOMO and LUMO for free ligands and their
complexes. For NOR, the electron density of HOMO is
delocalized and spreading over the all fragments of NOR
ligand except terminal part of quinoline ring and termi-
nal acetyl group, while the electron density of LUMO is
delocalized and spread over all atoms in NOR molecule
except piperazine ring only as shown in Table 6. The
hardness (η) is defined as (η = (I ꢂ A)/2) where I is
the ionization energy and A is the electron affinity. On
the other hand, the (I ꢂ A) equals the gap between
the HOMO and LUMO. As a result, the hardness of the
compounds was determined by E, which may be com-
puted as η = ΔE/2. The results demonstrate that the all
chelates were softer with η ranging from 0.053 to 0.102
but for NOR and BAC 0.124, 0.111, respectively.[79,80]
FIGURE 5 Molecular orbital surfaces and energy levels of NOR, BAC and their metal complexes using DFT calculations

EL-SHWINIY ET AL.
13 of 15
The electronic transition of complexes is easy as indicated
from the ΔE of complexes which are in agreement with
the values for stable transition metal complexes. For
NOR, BAC, and their complexes, quantum chemical fac-
tors such as global softness (S), electro negativity (χ),
absolute softness (σ), chemical potential (Pi), global elec-
trophilicity (ω), and extra electronic charge (ΔNmax) were
computed based on the energy values of HOMO and
LUMO. According to these estimates, the complex (2) is
ultimate soft (σ = 18.868 eV), whereas the complex (6) is
hard complex (σ = 9.804 eV). NOR and BAC have (σ) of
8.065 eV and 9.009 eV, respectively.
result, the electronic transition might be characterized as
a mixture of n ! π* and π ! π* transitions with a tiny
part on the peprazin ring, allowing for MLCT from metal
ion to either BAC (π*).
4 | CONCLUSION
Reactions of NOR and BAC with Mn(II), Fe(II), Co(II),
Ni(II), Cu(II), and Zn(II) ions yielded new mononuclear
complexes. The metal complexes were characterized and
their structures clarified using various analytical
and spectral techniques. The data showed that NOR and
BAC functioned as bidentate ligands. All complexes have
a coordination number of six. The results of the study
back up the proposed octahedral architecture of metal
complexes and produce a beneficial molecular arrange-
ment. The Coats-Redfern and Horowitz-Metzeger tech-
niques were used to determine kinetic parameters from
the complexes' thermal degradation stages. Density func-
tional theory calculations were carried out to investigate
the optimized structure of the two ligands and their
metal complexes and the obtained result indicate that
there are agreement between the computed and experi-
mental geometrical parameters is very good. The metal
complexes had a stronger bactericidal impact than the
ligands against several bacteria strains, including
S. aureus, L. monocytogens, B. cereus, and A. bauamanii,
but no antifungal action.
3.5.6 | Excited state
The UV–Vis spectra were accurately described using
time-dependent density functional response theory (TD-
DFT) at the B3LYP level using the G03W software.[80,81]
The TD-DFT has subsequently been rewritten to calculate
precise transition energies and oscillation strengths, and
it has been used on a variety of atoms and molecules. In
the
computation
of
the
excitation
energies,
Bauernschmitt and Ahlrichs[82,83] used hybrid func-
tionals. These hybrid techniques are usually a significant
improvement over traditional Hartree-Fock (HF) based
methods. The optimal architecture was determined in
this study and was employed in all ensuing computations;
the wave functions of SCF MOs were studied explicitly.
The computed wave functions of the various MOs depict
and imply the proportion of distinct complex pieces con-
tributing to the overall wave functions of various phases.
The findings show that there is a significant amount of
electron delocalization in the various chemical orbitals.
The electronic transition is a combination of n ! π* and
π ! π* transitions. Table 6 lists the energies of the
HOMO and LUMO states for NOR, BAC, and all investi-
gated chelates. In a reaction profile, the HOMO can serve
as an electron donor and the LUMO as an electron accep-
tor. In the complexes (3), (5), and (6), the electron density
of HOMO is localized mainly on the peprazin ring only of
NOR only, the electron density of HOMO in case of com-
plex (4) localized on BAC and around central metal ion,
while the electron density of HOMO in case of complex
(2) localized mainly on peprazin ring and all donating
oxygen atoms around the central metal ion, but in case of
complex (1) the electron density of HOMO localized on
the quinoline ring and the central metal ion with its sur-
rounding donating oxygen atoms only. The electron den-
sity of LUMO in the complexes localized mainly on BAC
molecules and small portion on central metal ion on the
surrounding oxygen atoms but in case of complex (1) the
electron density localized on peprazin ring only. As a
ACKNOWLEDGMENTS
The authors gratefully acknowledge Zagazig University,
Egypt, and University of Bisha, Saudi Arabia, for the sup-
port of this research work.
AUTHOR CONTRIBUTIONS
Walaa El-Shwiniy: Formal analysis; software; supervi-
sion; validation; visualization; writing-original draft;
writing-review and editing. Manar A. Gamil: Formal
analysis; funding acquisition; investigation; methodology;
project administration. Sadeek Sadeek: Supervision; val-
idation; visualization; writing-review and editing. Wael
A. Zordok: Conceptualization; data curation; software;
validation; visualization.
CONFLICT OF INTEREST
This research holds no conflict of interest and is not
funded through any source.
DATA AVAILABILITY STATEMENT
The data that support the findings of this study are avail-
able from the corresponding author upon reasonable
request.

14 of 15
EL-SHWINIY ET AL.
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Walaa H. El-Shwiniy https://orcid.org/0000-0002-7577-
8090
Manar A. Gamil https://orcid.org/0000-0002-6619-3058
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How to cite this article: W. H. El-Shwiniy, M.
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