In situ room temperature synthesis and characterization of salicylaldehyde phenylhydrazone metal complexes, their cytotoxic activity on MCF-7 cell line, and their investigation as antibacterial and antifungal agents

Article abstract of DOI:10.1080/15533174.2013.841209

In situ synthesis is usually used in industrial plants. As an approach new series of metal complexes of the salicylaldehyde phenylhydrazone, H₂L, have been synthesized and characterized by elemental analysis, IR, UV, ¹H-NMR, ^13<

Full text of DOI:10.1080/15533174.2013.841209

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In Situ Room Temperature Synthesis and
Characterization of Salicylaldehyde Phenylhydrazone
Metal Complexes, Their Cytotoxic Activity on MCF-7
Cell Line, and Their Investigation as Antibacterial and
Antifungal Agents
Ahmed M. A. El-Seidyab
a Inorganic Chemistry Department, National Research Centre, Dokki, Giza, Egypt
b Chemistry Department, Faculty of Science, Al Imam Mohammad Ibn Saud Islamic University
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(IMSIU), Riyadh, Saudi Arabia
Accepted author version posted online: 15 Sep 2014.Published online: 15 Oct 2014.
To cite this article: Ahmed M. A. El-Seidy (2015) In Situ Room Temperature Synthesis and Characterization of Salicylaldehyde
Phenylhydrazone Metal Complexes, Their Cytotoxic Activity on MCF-7 Cell Line, and Their Investigation as Antibacterial
and Antifungal Agents, Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 45:3, 437-446, DOI:
10.1080/15533174.2013.841209
To link to this article: http://dx.doi.org/10.1080/15533174.2013.841209
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Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry (2015) 45, 437–446
Copyright © Taylor & Francis Group, LLC
ISSN: 1553-3174 print / 1553-3182 online
DOI: 10.1080/15533174.2013.841209
In Situ Room Temperature Synthesis and Characterization
of Salicylaldehyde Phenylhydrazone Metal Complexes,
Their Cytotoxic Activity on MCF-7 Cell Line, and Their
Investigation as Antibacterial and Antifungal Agents
AHMED M. A. EL-SEIDY1,2
1Inorganic Chemistry Department, National Research Centre, Dokki, Giza, Egypt
2Chemistry Department, Faculty of Science, Al Imam Mohammad Ibn Saud Islamic University (IMSIU), Riyadh, Saudi Arabia
Received 8 June 2013; accepted 1 September 2013
In situ synthesis is usually used in industrial plants. As an approach new series of metal complexes of the salicylaldehyde
1
phenylhydrazone, H2L, have been synthesized and characterized by elemental analysis, IR, UV, H-NMR, 13C-NMR and ESR
spectra, magnetic susceptibility, and molar conductivity measurements. The spectral data and magnetic measurements of the
complexes indicated that the geometries are either square planar or octahedral. All complexes showed low to moderate cytotoxic
activity. The antibacterial and antifungal activities of the compounds showed that, all complexes showed higher antifungal activities
than antibacterial activities. Nickel and copper complexes showed higher activity than the standard drug.
Keywords: in situ synthesis, room temperature synthesis, metal complexes, Schiff base, thermal analysis, biological study, cytotoxic
activity
Introduction
activities.[8] In view of the versatile importance of Schiff bases
and their transition metal complexes, I report in this article
2-Hydroxy Schiff base ligands and their complexes derived the in situ synthesis and characterization of the Fe(III), Co
from the reaction of derivatives of salicylaldehyde with (II), Cu(II), Zn(II), Mn(II), and Ni(II) metal complexes of
amines have been extensively studied in great details for their salicylaldehyde phenylhydrazone ((E)-2-((2-phenylhydra-
various crystallographic, structural and magnetic features.[1,2] zono)methyl)phenol). The coordination behavior of the
Numerous biological experiments have demonstrated that Schiff base ligand toward metal ions was investigated via IR,
DNA is the primary intracellular target of anticancer drugs UV, and ESR as well as conductivity and magnetic moment
due to the interaction between small molecules and DNA, measurements. All complexes showed low to moderate cyto-
which cause DNA damage in cancer cells, blocking the divi- toxic activity. The antibacterial and antifungal activities of
sion of cancer cells and resulting in cell death.[3] Of these stud- the compounds showed that, some of the metal complexes
ies, the interaction of transition metal complexes containing exhibited a greater inhibitory effect than standard drug.
multidentate aromatic ligands with DNA has gained much
attention. This is due to their possible application as new
therapeutic agents and their photochemical properties which
Experimental
make them potential probes of DNA structure and confor-
mation.[4,5] Polydentate Schiff bases with various donor
Materials
atoms are well known to coordinate with various metal
ions.[6,7] These types of ligands are able to form varieties of
All the reagents employed for the preparation of the ligand
and its complexes were of the best grade available and used
complexes with different stoichiometry, structure, and mag-
without further purification.
netic and spectral properties. These complexes attracted the
attention of many authors due to their dioxygen uptake, oxi-
dative catalysis, magnetic behavior, and biological
Methods
The ligand and its metal complexes were analyzed for C, H,
N, Cl, S, and metal contents at the Microanalytical Labora-
tory, Faculty of Science, Cairo University, Egypt. Analytical
and physical data of the ligand and its metal complexes are
Address correspondence to Ahmed M. A. El-Seidy, Inorganic
Chemistry Department, National Research Centre, P.O. 12622
Dokki, Giza, Egypt. E-mail: ahmedmaee2@gmail.com.

438
El-Seidy
reported. IR spectra of the ligand and its metal complexes Metal Complexes
were measured using KBr discs with a Jasco FT/IR 300E
[H2LFeCl3(H2O)].3H2O, complex 2
Fourier transform infrared spectrophotometer covering the
range 400–4000 cm¡1 and in the 500–100 cm¡1 region using
polyethylene-sandwiched Nujol mulls on a Perkin Elmer FT-
IR 1650 spectrophotometer. Electronic spectra of the ligand
and its complexes were obtained in Nujol mulls using a Shi-
madzu UV–240 UV–Vis recording spectrophotometer. Mag-
netic susceptibilities were measured at 25ꢀC by the Gouy
method using mercuric tetrathiocyanatocobaltate(II) as the
magnetic susceptibility standard. Diamagnetic corrections
were estimated from Pascal’s constant.[9] The magnetic
Ethanol solution (10 mL) of 2-hydroxybenzaldehyde (0.25 g,
2.05 mmol) was added dropwise to ethanol solution (10 mL)
of phenylhydrazine (0. 22 g, 2.05 mmol). After 5 min a meth-
anol solution (20 mL) of FeCl3.6H2O (0.55 g, 2.05 mmol)
was added dropwise with stirring. A few drops of trimethyl
amine were added to allow precipitation. The precipitate was
then filtered off, washed with methanol, and dried in a vac-
uum desiccator over P4O10 (0.68 g, 74% yield). Conductance
Lm: 16 V¡1cm2mol¡1 UV (Nujol mul (nm)): λ D 540, 660
and 854 nm. Magnetic moment: 5.87 B. M. IR (KBr):
n(H2O) 3455(br), n(OH) 3285 (sh), n(NH) 3280(s), n(CHN)
1614(m), n(C-O) 1255 (m), n(M-N) 435, n(M-O) 560, n(M-
Cl) 341, n(M-Cl) 365. TGA (Found (calcd., temp.): 3 H2O
13.06 (13.18, 75ꢀC), 1 H2O 4.46 (4.39, 128ꢀC), 3 Cl atoms
25.81 (25.94, 210ꢀC), 1/2 Fe2O3 19.25 (19.47, 595ꢀC). Elemen-
tal analysis for C26H22CuN4O7 (410.05): Anal. Calcd. C
38.08, H 4.67, N 6.83, Fe 13.62; Found C 37.88, H 4.85, N
6.92, Fe 13.47.
moments
were
calculated
from
the
equation:
pffiffiffiffiffiffiffiffiffiffiffiffiffi
meff: D 2:84 xcMorr:T. Thermal analyses were carried out in air
using a Shimadzu DT-30 thermal analyzer. 1H and 13C
NMR spectra were obtained on Bruker Avance 300-DRX or
Avance 400-DRX spectrometers. Chemical shifts (ppm) are
reported relative to TMS. Molar conductances were mea-
sured on a Tacussel type CD6NG conductivity bridge using
10¡3M DMF solutions. ESR measurements of solid com-
plexes at room temperature were made using a Varian E-109
spectrophotometer, with DPPH as a standard material.
[HLFeSO4(H2O)2].4H2O, complex 3
Ethanol solution (9 mL) of 2-hydroxybenzaldehyde (0.20 g,
1.64 mmol) was added dropwise to ethanol solution (9 mL)
of phenylhydrazine (0. 18 g, 1.64 mmol). After 5 min a meth-
anol solution (20 mL) of FeSO4¢7H2O (0.46 g, 1.64 mmol)
was added dropwise with stirring. A few drops of trimethyl
amine were added to allow precipitation. The precipitate was
then filtered off, washed with methanol, and dried in a vac-
uum desiccator over P4O10 (0.66 g, 85% yield). Conductance
Lm: 10 V¡1cm2mol¡1 UV (Nujol mul (nm)): λ D 543, 650
and 834 nm Magnetic moment: 5.94 B. M. IR (KBr): n(H2O)
3435(br), n(NH) 3279(s), n(CHN) 1611(m), n(CꢁꢁO) 1260
(m), n(SO4) 1224, 1156, 1068, 965, n(M-N) 430, n(MꢁꢁO)
565. TGA (Found (calcd., temp.): 4 H2O 15.45 (15.30, 70ꢀC),
The Ligand, H2L1
Ethanol solution (10 mL) of 2-hydroxybenzaldehyde (1.00 g,
8.19 mmol) was added dropwise to ethanol solution (10 mL)
of phenylhydrazine (0.89 g, 8.19 mmol) over 15 min with stir-
ring and continue stirring for 0.5 h. The yellow precipitate
(see Figure 1) was then filtered off, washed with methanol,
and dried in a vacuum desiccator over P4O10 (1.23 g, 71%
yield). 1H NMR (400 MHz, DMSO): d D 10.61 ppm [s, 1H,
H(8)], 10.40 ppm [s, 1H, H(10)], 820 ppm [s, 1H, H(7)],
7.55 ppm [d, 1H, H(6)], 7.28 ppm [pst, 1H, H(2)], 720 ppm
[t, 2H, J D 7.6, H(12) and H(16)], 7.01 ppm [t, 2H, J D 7.6, H
(13) and H(15)], 690 ppm [m, 2H, H(1) and H(3)], 6.80 [t,
1H, J D 7.6, H(14)]. 13C NMR (300 MHz, DMSO, 300 K):
155.67 C(8), 144.70 C(7) and C(11), 137.36 C(2) and C(5),
129.35 C(6), 129.26 C(15) and C(13), 120.41 C(14), 119.35 C
(1), 115.98 C(3), 111.70 C(12) and C(16). IR (KBr): n(OH)
3291 (br), n(NH) 3281(Sh), n(CHN) 1622(s), n(C-O) 1250
(m). Elemental analysis for C13H12N2O (212.25): Anal.
Calcd. C 73.56, H 5.70, N 13.20; Found C 73.61, H 5.92, N
13.09.
1
2 H2O 7.49 (7.65, 127ꢀC), 1 H2SO4 20.60 (20.81, 310ꢀC), /2
Fe2O3 16.64 (16.94, 590ꢀC). Elemental analysis for
C13H23FeN2O11S (471.24): Anal. Calcd. C 33.13, H 4.92, N
5.94, Fe 11.85, S, 6.80; Found C 32.97, H 5.02, N 6.03, Fe
11.79, S, 6.78
[H2LNiCl2(H2O)2].H2O, complex 4
Ethanol solution (12 mL) of 2-hydroxybenzaldehyde (0.27 g,
2.29 mmol) was added dropwise to ethanol solution (12 mL)
of phenylhydrazine (0.25 g, 2.29 mmol). After 5 min a metha-
nol solution (20 mL) of NiCl2.6H2O (0.55 g, 2.29 mmol) was
added dropwise with stirring. A few drops of trimethyl amine
were added to allow precipitation. The precipitate was then fil-
tered off, washed with methanol, and dried in a vacuum desic-
cator over P4O10 (0.72 g, 73% yield). Conductance Lm: 13
V
¡1cm2mol¡1 UV (Nujol mul (nm)): λ D 530 and 1150 nm.
Magnetic moment: 4.78 B. M. IR (KBr): n(H2O) 3458(br),
n(OH) 3286 (m), n(NH) 3279(s), n(CHN) 1609(m), n(CꢁꢁO)
1254 (m), n(MꢁꢁN) 440, n(MꢁꢁO) 562, n(MꢁꢁCl) 356. TGA
(Found (calcd., temp.): H2O 4.44 (4.55, 68ꢀC), 2 H2O 9.23
(9.10, 129ꢀC), 2 Cl atoms 17.78 (17.91, 220ꢀC), NiO 18.64
(18.87, 515ꢀC). Elemental analysis for C13H18Cl2N2NiO4
(395.89): Anal. Calcd. C, 39.44; H, 4.58; Cl, 17.91; N, 7.08;
Fig. 1. Preparation of the ligand H2L.

Salicylaldehyde Phenylhydrazone Metal Complexes
439
Ni, 14.83; Found C, 39.25; H, 4.71; Cl, 18.07; N, 7.18; Ni, (y2) 1043 cm¡1; (y4) 1372 cm¡1 and (y5) 715 cm¡1, n
14.62
(MꢁꢁN) 455, n(MꢁꢁO) 571. TGA (Found (calcd., temp.): 4
H2O 13.13 (13.25, 65ꢀC), 1 H2O 3.33 (3.31, 124ꢀC), 3 HNO3
34.57 (34.74, 350ꢀC), 1/2 Fe2O3 14.77 (14.67, 589ꢀC). Elemen-
tal analysis for C13H22FeN5O15 (544.18): Anal. Calcd. C,
28.69; H, 4.07; Fe, 10.26; N, 12.87; Found C, 28.57; H, 4.23;
Fe, 10.41; N, 12.64
[H2LCoCl2(H2O)2].3H2O, complex 5
Ethanol solution (13 mL) of 2-hydroxybenzaldehyde (0.28 g,
2.29 mmol) was added dropwise to ethanol solution (13 mL)
of phenylhydrazine (0.25 g, 2.29 mmol). After 5 min a meth-
anol solution (22 mL) of CoCl2.6H2O (0.55 g, 2.29 mmol)
was added dropwise with stirring. A few drops of trimethyl
[H2LMnSO4(H2O)2].3H2O, complex 8
amine were added to allow precipitation. The precipitate was Ethanol solution (9 mL) of 2-hydroxybenzaldehyde (0.24 g,
then filtered off, washed with methanol, and dried in a vac- 1.97 mmol) was added dropwise to ethanol solution (9 mL)
uum desiccator over P4O10 (0.72 g, 73% yield). Conductance of phenylhydrazine (0.21 g, 1.97 mmol) . After 5 min a meth-
Lm: 18 V¡1cm2mol¡1 UV (Nujol mul (nm)): λ D 530 and anol solution (18 mL) of MnSO4.H2O (0.33 g, 1.97 mmol)
1150 nm. Magnetic moment: 4.78 B. M. IR (KBr): n(H2O) was added dropwise with stirring. A few drops of trimethyl
3465(br), n(OH) 3282 (sh), n(NH) 3278(s), n(CHN) 1615(m), amine were added to allow precipitation. The precipitate was
n(C-O) 1261 (m), n(M-N) 443, n(M-O) 556, n(M-Cl) 368. then filtered off, washed with methanol, and dried in a vac-
TGA (Found (calcd., temp.): 3 H2O 12.39 (12.51, 74ꢀC), 2 uum desiccator over P4O10 (0.72 g, 84% yield). Conductance
1
H2O 8.46 (8.34, 135ꢀC), 2 Cl atoms 16.48 (16.40, 210ꢀC), /2 Lm: 15 V¡1cm2mol¡1 UV (Nujol mul (nm)): λ D 554 nm
Co2O3 19.06 (19.19, 584ꢀC). Elemental analysis for Magnetic moment: 5.14 B. M. IR (KBr): n(H2O) 3429(br),
C13H22Cl2CoN2O6 (432.16): Anal. Calcd. C, 36.13; H, 5.13; n(OH) 3286 (m), n(NH) 3281(s), n(CHN) 1613(w), n(CꢁꢁO)
Cl, 16.41; Co, 13.64; N, 6.48; Found C, 35.99; H, 5.24; Cl, 1259 (m), n(SO4) 1208, 1154, 1072, 972, n(M-N) 440, n
16.55; Co, 13.50; N, 6.61
(MꢁꢁO) 568. TGA (Found (calcd., temp.): 3 H2O 12.11
(11.93, 72ꢀC), 2 H2O 7.78 (7.95, 131ꢀC), 1 H2SO4 21.52
1
(21.64, 315ꢀC), /2 Mn2O3 17.53 (17.41, 590ꢀC). Elemental
[HLCu(NO3)(H2O)].2H2O, complex 6
analysis for C13H22MnN2O10S (453.32): Anal. Calcd. C,
34.44; H, 4.89; Mn, 12.12; N, 6.18; S, 7.07; Found C, 34.28;
H, 5.03; Mn, 12.18; N, 6.31; S, 6.93.
Ethanol solution (14 mL) of 2-hydroxybenzaldehyde (0.30 g,
2.46 mmol) was added dropwise to ethanol solution (14 mL)
of phenylhydrazine (0.27 g, 2.46 mmol). After 5 min a meth-
anol solution (20 mL) of Cu(NO3)2.3H2O (0.59 g,
2.46 mmol) was added dropwise with stirring. A few drops of
[H2LZnSO4].5H2O, complex 9
trimethyl amine were added to allow precipitation. The pre- Ethanol solution (14 mL) of 2-hydroxybenzaldehyde (0.32 g,
cipitate was then filtered off, washed with methanol, and 2.62 mmol) was added dropwise to ethanol solution (14 mL)
dried in a vacuum desiccator over P4O10 (0.73 g, 84% yield). of phenylhydrazine (0.28 g, 2.62 mmol). After 5 min a meth-
Conductance Lm: 9 V¡1cm2mol¡1. UV (Nujol mul (nm)): λ anol solution (24 mL) of ZnSO4.7H2O (0.75 g, 2.62 mmol)
D 550 nm. Magnetic moment: 1.87 B. M. ESR: g 2.31, g
was added dropwise with stirring. A few drops of trimethyl
jj
?
2.06, g///A// 125, G 5.33, giso 2.14. IR (KBr): n(H2O) 3430 amine were added to allow precipitation. The precipitate was
(br), n(NH) 3282(s), n(CHN) 1612(m), n(CꢁꢁO) 1257 (m), then filtered off, washed with methanol, and dried in a vac-
NO3: (y1) 1465 cm¡1; (y2) 1055 cm¡1; (y4) 1377 cm¡1 and uum desiccator over P4O10 (0.85 g, 70% yield). Conductance
(y5) 705 cm¡1, n(MꢁꢁN) 438, n(MꢁꢁO) 573. TGA (Found Lm: 17 V¡1cm2mol¡1 IR (KBr): n(H2O) 3437(br), n(OH)
(calcd., temp.): 2 H2O 10.09 (10.16, 77ꢀC), 1 H2O 5.19 3284 (sh), n(NH) 3280(s), n(CHN) 1616(w), n(CꢁꢁO) 1263
(5.08, 133ꢀC), 1 HNO3 17.59 (17.76, 295ꢀC), CuO 22.29 (m), n(SO4) 1204, 1168, 1054, 984, n(M-N) 457, n(MꢁꢁO)
(22.42, 530ꢀC). Elemental analysis for C13H22Cl2CoN2O6 569. TGA (Found (calcd., temp.): 5 H2O 19.49 (19.43, 71ꢀC),
(432.16): Anal. Calcd. C, 36.13; H, 5.13; Cl, 16.41; Co, 1 H2SO4 21.27 (21.15, 323ꢀC), ZnO 17.42 (17.55, 590ꢀC).
13.64; N, 6.48; Found C, 35.99; H, 5.24; Cl, 16.55; Co, Elemental analysis for C13H22N2O10SZn (463.77): Anal.
13.50; N, 6.61
Calcd. C, 33.67; H, 4.78; N, 6.04; S, 6.91; Zn, 14.10; Found
C, 33.54; H, 4.92; N, 6.14; S, 7.02; Zn, 14.00.
[H2LFe(NO3)3(H2O)].4H2O, complex 7
[H2LZn(NO3)2].3H2O, complex 10
Ethanol solution (13 mL) of 2-hydroxybenzaldehyde (0.29 g,
2.37 mmol) was added dropwise to ethanol solution (13 mL) Ethanol solution (12 mL) of 2-hydroxybenzaldehyde (0.26 g,
of phenylhydrazine (0.26 g, 2.37 mmol). After 5 min a meth- 2.13 mmol) was added dropwise to ethanol solution (12 mL)
anol solution (22 mL) of Fe(NO3)3.9H2O (0.96 g, of phenylhydrazine (0.23 g, 2.13 mmol). After 5 min a metha-
2.37 mmol) was added dropwise with stirring. A few drops of nol solution (22 mL) of Zn((NO3)2.6H2O (0.63 g, 2.13 mmol)
trimethyl amine were added to allow precipitation. The pre- was added dropwise with stirring. A few drops of trimethyl
cipitate was then filtered off, washed with methanol, and amine were added to allow precipitation. The precipitate was
dried in a vacuum desiccator over P4O10 (0.93 g, 72% yield). then filtered off, washed with methanol, and dried in a vacuum
Conductance Lm: 25 V¡1cm2mol¡1 UV (Nujol mul (nm)): λ desiccator over P4O10 (0.65 g, 67% yield). Conductance Lm:
D 556, 672 and 860 nm Magnetic moment: 5.90 B. M. IR 19 V¡1cm2mol¡1 IR (KBr): n(H2O) 3444(br), n(OH) 3287 (w),
(KBr): n(H2O) 3440(br), n(OH) 3285 (w), n(NH) 3280(s), n(NH) 3281(s), n(CHN) 1613(m), n(CꢁꢁO) 1259 (m), NO3:
n(CHN) 1610(m), n(CꢁꢁO) 1258 (m), NO3: (y1) 1460 cm¡1
;
(y1) 1470 cm¡1; (y2) 1037 cm¡1; (y4) 1382 cm¡1 and (y5)

440
El-Seidy
720 cm¡1, n(M-N) 438, n(M-O) 539. TGA (Found (calcd., n(CꢁꢁO) 1256 (m), n(M-N) 436, 447, n(MꢁꢁO) 549, 553.
temp.): 3 H2O 12.11 (11.86, 68ꢀC), 1 HNO3 13.97 (13.83, TGA (Found (calcd., temp.): 2 H2O 5.52 (5.61, 79ꢀC), 2
330ꢀC), ZnO 17.83 (17.86, 510ꢀC). Elemental analysis for CH3COOH 18.54 (18.70, 305ꢀC), CuO 12.44 (12.39, 530ꢀC).
C13H18N4O10Zn (455.68): Anal. Calcd. C, 34.26; H, 3.98; Elemental analysis for C30H34CuN4O8 (642.16): Anal. Calcd.
N, 12.30; Zn, 14.35; Found C, 34.22; H, 4.09; N, 12.42; C, 56.11; H, 5.34; Cu, 9.90; N, 8.72; Found C, 55.99; H, 5.43;
Zn, 14.26.
Cu, 9.77; N, 8.79
[(HL)2Co(H2O)2].2H2O, complex 11
In Vitro Antibacterial and Antifungal Activities
Ethanol solution (16 mL) of 2-hydroxybenzaldehyde (0.39 g,
3.19 mmol) was added dropwise to ethanol solution (16 mL)
of phenylhydrazine (0.35 g, 3.19 mmol). After 5 min a meth-
anol solution (22 mL) of CoCl2.6H2O (0.38 g, 1.60 mmol)
was added dropwise with stirring. A two drops of trimethyl
amine were added to increase precipitation. The precipitate
was then filtered off, washed with methanol, and dried in a
vacuum desiccator over P4O10 (0.70 g, 79% yield). Conduc-
tance Lm: 11 V¡1cm2mol¡1 UV (Nujol mul (nm)): λ D 562
and 1110 nm Magnetic moment: 4.65 B. M. IR (KBr):
n(H2O) 3467(br), n(NH) 3282(s), n(CHN) 1609(m), n(C-O)
1257 (m), n(M-N) 453, n(M-O) 559. TGA (Found (calcd.,
The investigation of the biological activities of the newly
synthesized Schiff base ligand, its metal complexes, and
their corresponding metal salts were carried out in the
Botany Department, Laboratory of Microbiology, Fac-
ulty of Science, El-Menoufia University. The antibacterial
and antifungal activities were investigated by disc diffu-
sion method.[10,11] The antibacterial activities were done
using Escherichia coli and Aspergillus niger at 2000 ppm
concentrations in DMSO. DMSO poured disc was used
as negative control. The bacteria was subcultured in
nutrient agar medium which was prepared using (g.L¡1
distilled water) NaCl (5 g), peptone (5 g), beef extract
(3 g), and agar (20 g). The fungus was subcultured in
Dox’s medium, which was prepared using (g.L¡1 distilled
water) yeast extract (1 g), sucrose (30 g), NaNO3, agar
(20 g), KCl (0.5 g), KH2PO4 (1 g), MgSO4.7H2O (0.5 g),
and traces of FeCl3 .6H2O. These mediums were then
sterilized by autoclaving at 120ꢀC for 15 min. After cool-
ing to 45ꢀC the medium was poured into 90 mm diameter
Petri dishes and incubated at 37 or 28ꢀC, respectively.
After few hours, Petri dishes were stored at 4ꢀC. Micro-
organisms were spread over each dish by using sterile
bent Loop rod. The test is carried out by placing filter
paper disks with a known concentration of the com-
pounds on the surface of agar plates inoculated with a
test organism. Standard antibacterial drug (tetracycline),
antifungal drug (Amphotericin B), and solution of metal
salts were also screened under similar conditions for com-
parison. The Petri dishes were incubated for 48 h at 37
or 28ꢀC, respectively. The zone of inhibition was mea-
sured in millimeters carefully. All determinations were
made in duplicated manner for each of the compounds.
An average of the two independent readings for each
compound was record.
temp.): 2 H2O 6.41 (6.51, 68ꢀC), 2 H2O 6.63 (6.51, 128ꢀC),
1
/
Co2O3 15.12 (14.98, 582ꢀC). Elemental analysis for
2
C26H30CoN4O6 (553.47): Anal. Calcd. C, 56.42; H, 5.46; Co,
10.65; N, 10.12; Found C, 56.29; H, 5.55; Co, 10.51; N,
10.23.
[(HL)2FeCl(H2O)].3H2O, complex 12
Ethanol solution (15 mL) of 2-hydroxybenzaldehyde (0.38 g,
3.11 mmol) was added dropwise to ethanol solution (15 mL)
of phenylhydrazine (0.34 g, 3.11 mmol). After 5 min a meth-
anol solution (20 mL) of FeCl3.6H2O (0.42 g, 1.56 mmol)
was added dropwise with stirring. A few drops of trimethyl
amine were added to allow precipitation. The precipitate was
then filtered off, washed with methanol, and dried in a vac-
uum desiccator over P4O10 (0.69 g, 76% yield). Conductance
Lm: 14 V¡1cm2mol¡1 UV (Nujol mul (nm)): λ D 558, 667
and 855 nm. Magnetic moment: 5.98 B. M. IR (KBr):
n(H2O) 3464(br), n(NH) 3281(s), n(CHN) 1615(s), n(CꢁꢁO)
1257 (m), 1261(m), n(MꢁꢁN) 432(m), 437(w), n(M-O) 552
(m), n(MꢁꢁCl) 347(w). TGA (Found (calcd., temp.): 3 H2O
9.41 (9.23, 72ꢀC), 1 H2O 7.91 (3.08, 125ꢀC), 1 Cl atoms 6.12
1
(6.05, 210ꢀC), /2 Fe2O3 13.49 (13.63, 595ꢀC). Elemental
analysis for C26H30ClFeN4O6 (585.84): Anal. Calcd. C,
53.30; H, 5.16; Cl, 6.05; Fe, 9.53; N, 9.56; Found C, 53.19;
H, 5.24; Cl, 6.13; Fe, 9.41; N, 9.64.
Cytotoxicity Assays
The cell culture cytotoxicity assays were carried out as
described previously,[12] at the National Cancer Institute,
Cairo University, Cairo, Egypt.
[(H2L)2Cu(CH3COO)2].2H2O, complex 13
Ethanol solution (18 mL) of 2-hydroxybenzaldehyde (0.45 g,
3.68 mmol) was added dropwise to ethanol solution (16 mL)
of phenylhydrazine (0.4 g, 3.68 mmol). After 5 min a metha-
nol solution (22 mL) of Cu(CH3COO)2.H2O (0.37 g, Results and Discussion
1.84 mmol) was added dropwise with stirring. The precipitate
was then filtered off, washed with methanol, and dried in a The analytical and physical data, spectral data are compati-
vacuum desiccator over P4O10 (1.03 g, 87% yield). Conduc- ble with the suggested structures (Figure 2). The complexes
tance Lm: 11 V¡1cm2mol¡1. UV (Nujol mul (nm)): λ D 540 are colored, stable in air, and insoluble in H2O, ethanol and
and 610 nm. Magnetic moment: 1.95 B. M. ESR: g 2.19, g
nonpolar solvents such as benzene. However, they dissolve in
jj
?
2.04, g///A// 165, G 5.26, giso 2.09. IR (KBr): n(H2O) 3454 polar solvents such as DMF and DMSO. All the complexes
(br), n(OH) 3285 (w), n(NH) 3281(s), n(CHN) 1608(m), are nonelectrolytes.

Salicylaldehyde Phenylhydrazone Metal Complexes
441
Fig. 2. The proposed structures of metal complexes of the ligand H2L.
Infrared Spectra
formation.[13–17] In complexes 3, 6, 11, and 12 the signal due
to hydroxyl group disappeared, indicating the subsequent
deprotonation of the phenolic proton prior to coordination.
In other complexes this signal was shifted to lower wave num-
ber accompanied by a decrease in its intensity indicating it is
coordinated to the central metal.[18] The two new signals in
the 430–457 and 539–573 cm¡1 ranges may be assigned to n
(MꢁꢁN) and n(MꢁꢁO) respectively.[15,19,20] The presence of
water molecules in all complexes was supported by the pres-
ence of bands in the 3467–3429 cm¡1regions.[1,21] The spectra
of the complexes 2, 4, 5, and 12 showed an assignable, weak
intensity n(M-Cl) band in 347–368 cm¡1 range indicating a
IR spectra of the complexes were recorded to confirm their
structures. The assignments of the characteristic vibrational
frequencies of the complexes were made by comparison with
the vibrational frequencies of the free ligand. The ligand
behaved as neutral or monobasic bidentate ligand coordinat-
ing through the imine nitrogen and the phenolic oxygen. In
all complexes the signal of the imine group was shifted to
lower wave number accompanied by a decrease in its inten-
sity while the signal due to phenolic CꢁꢁO was shifted to
higher wave number, indicating they are involved in complex

442
El-Seidy
3
3
terminal chloro ligand.[22,23] Complexes 6, 7, and 10 showed transitions at 960 and 687 nm assigned to A2g(F)! T2g(F)
3
bands in the 1460–1470 cm¡1 (y1), 1037–1055 cm¡1 (y2), (y1) and 3A2g(F) ! T1g(F) (y2) spin allowed electronic tran-
1372–1382 cm¡1 (y4), and 705–720 cm¡1 (y5) ranges with sitions, which are characteristic of Ni2C in an octahedral con-
y—y4 separation of 88 cm¡1, characteristic of monodentate figuration.[33–35] The 10 Dq D 10410 cm¡1 and calculated B
nitrato group.[23,24] The sulfate ion has a regular tetrahedral D 771 cm¡1 are in good agreement with the predicted values
structure belonging to the point group Td.[25] In its ionic state, for octahedral complexes of Ni(II). The calculated value for
3
3
SO4 has nine vibrational degrees of freedom, distributed in the transition A2g(F) ! T1g(P) (y3) was found at 508 nm,
four normal modes of vibration. Out of these, only two are which is masked with the more intense C. T. The effective
infrared active.[25] When SO4 functions as a monodentate magnetic moment value of 3.12 BM of the nickel complex
ligand, the oxygen coordinating to a metal atom is no longer also indicates the octahedral structure of the complex.[33,36]
symmetrically equivalent to the other three oxygen’s and the Complexes 5 and 11 showed signals in 530–562 and 1110–
effective symmetry of SO4 is lowered to C3, C3v.[25] In C3, 1150 nm ranges, which can be assigned to the transitions
4
4
4
C3v, symmetry, six infrared absorption bands are observed. 4T1g(F)! T1g(P) and T1g(F)! T2g(F) in an octahedral
When SO4 functions as a bidentate group, its effective sym- geometry. The magnetic moments were in 465–4.78 B. M.
metry is further lowered to C2v. In C2v symmetry, eight rang, together with the positions of the absorption bands sug-
modes of vibration, out of the total of nine, are infrared gest octahedral geometries around the Co(II) ions.[37–39] The
active.[9] The sulfato complexes 3, 8, and 9 showed bands in UV–Vis absorption spectrum of the complex 6 showed single
the 965–984, 1064–1072, 1154–1168, 1205–1224 cm¡1 d–d transition band at 550 nm as is expected for a square pla-
regions, indicating a bidentate coordinating sulfato group.[26] nar copper(II) Schiff base. The magnetic moment (1.87 BM)
IR spectral studies reported on metal aceto complexes [24] suggests a square-planar geometry.[39–42] The Cu(II) complex
indicated that the acetate ligand may coordinate to a metal 13 showed two bands at 540 nm and 610 nm, which can be
2
2
center in either a monodentate, bidentate, or bridging man- assigned to the 2B1g! B2g and 2B1g! Eg transitions, respec-
ner. The nasym.(CO2) and nsym.(CO2) of the free acetate ions tively indicating that copper(II) have tetragonal distorted
are at 1560 cm¡1 and 1416 cm¡1, respectively. In monoden- octahedral geometry.[43,44] Its magnetic moment was 1.95 B.
tate coordination n(CHO) is found at higher energy than M., which falls within the range normally observed for octa-
nasym.(CO2) and n(CꢁꢁO) is lower than nsym.(CO2). As a hedral copper complexes.[34] The Mn(II) complex 8 showed
result, the separation between the two v(CO) bands is much broad bands near 554 nm, which were attributed to
4
larger in monodentate complexes than the free ion.[17] The 6A1g! T1g(G) transition in octahedral structures.[45,46] The
opposite trend is observed in bidentate aceto coordination; magnetic moment value of 4.14 B.M. indicates a high-spin
the separation between n(CO) is smaller than for the free ion. 3d5 system.[45]
For bridging acetate with both oxygens coordinated as in
copper(II) acetate; however, the two n(CO) bands are close to
the free ion values.[27,28] Complex 13 showed two new bands
ESR
at 1554 cm¡1 and 1344 cm¡1, which may be attributed to
nasym.(COO¡) and nsym.(COO¡), respectively, with D > 210 Further insight about the environment around copper center
indicating monodentate acetates.[27] Further, the complex was provided using X-band ESR spectra of the complexes.
exhibits d(COO) at 750 cm¡1, which is considered diagnostic The ESR spectra of the solid copper(II) complexes 6 and 13
for monodentate acetates.[29]
at room temperature showed the g values: g D 2.19–2.31
k
and g? D 2.04–2.06. These complexes showed an axial shape
2
with g > g , characteristic of complexes with B1(dx2¡y2
)
k
?
Molar Conductivity
ground state. The average g values were calculated accord-
ing to the equation gav D 1/3[g C2g ] (2.09–2.14). Com-
k
?
The molar conductance of the metal complexes is in the 9–25
V¡1 cm2 mol¡1 range, indicating their non-electrolytic
nature.[30]
plex 13 exhibits g < 2.3, suggesting covalent characters of
k
the copper–ligand bonding, while complex 6 exhibits g >
k
2.3 suggesting ionic characters around the copper. The
parameter G D (gk ¡2.0023)/(g? ¡2.0023) shows the possi-
bility of exchange interaction in the Cu(II) complex. The G
values for all complexes (G > 4) indicated that there is no
Electronic Spectra
The magnetic moments of the complexes 2, 3, 7, and 12 are in direct copper–copper interaction in the solid state.[47] The
5.87–598 BM range, which is closer to the spin only value g /A is taken as an indication for the stereochemistry of
k
k
[31]
indicating an octahedral structure for the complexes,
the copper(II) complexes. Addison[48] suggested that this
which was further supported by the appearance of very week ratio may be an empirical indication of the tetrahedral dis-
signals in the 540–556, 650–672, and 834–860 nm ranges tortion of the square planar geometry. The values lower
6
4
which can be assigned to the transitions A1g! A1g(G), than 135 cm are observed for square planar structures and
4
6
4
6A1g! T2g(G), and A1g! T1g(G) in an octahedral geome- those higher than 150 cm¡1 for tetragonal distorted com-
try.[31,32] The magnetic moment of complex 3 was 5.94, indi- plexes. The value of gk/Ak for complexes 13 lies above 150
cating five unpaired electron which support that iron is indicating tetragonal distorted complex. Complex 6 showed
present as Fe(III), this assumption was further supported by gk/Ak below 135 cm, indicating square planar geometry
the d-d transitions pattern. Complex
4 showed d–d around copper in this complex.

Salicylaldehyde Phenylhydrazone Metal Complexes
443
Fig. 3. Antibacterial activity of the ligand and its metal complexes against gram-negative bacterium (E. coli).
Thermal Analysis of Metal Complexes
(210–350ꢀC range) then the organic constituents of the com-
plexes start to decompose, finally leaving the metal oxides
(515–595ꢀC range), while complex 11 showed only three of
these stages eliminating the stag losing the anion from the
previous four. The thermal decomposition of the complexes
9, 10, and 13 take place in three main stages. These stages
lose lattice water (68–79ꢀC range) and the anion (305–
330ꢀC range), then the organic constituents of the com-
plexes start to decompose, finally leaving the metal oxides
(510–590ꢀC).
The results of TGA of complexes were in good agreement
with the proposed structures. The thermo-gravimetric anal-
ysis (TG) was measured in the 20–800ꢀC temperature range
and showed that all complexes are thermally stable up to
50ꢀC, when dehydration begins. The thermal decomposition
of the complexes 2–8 and 12 take place in four main stages.
These stages are losing lattice water (65–77ꢀC range), losing
coordinated water (124–135ꢀC range), losing of the anion
Fig. 4. Antifungal activity of the ligand and its metal complexes against fungus (Aspergillus niger).

444
El-Seidy
Fig. 5. Cytotoxic activities of the ligand and its complexes against human breast cancer cell line (MCF-7).
Antibacterial and Antifungal Screening
class of compounds.[49–51] All compounds under investigation
showed higher antifungal activities than antibacterial activi-
ties. Complexes 4 and 6 (nickel and copper, respectively)
showed higher activity than the standard drug. The overall
results indicated that Ni(II), Cu(II), Zn(II), and Co(II) com-
plexes exhibited the maximum antibacterial and antifungal
activities, while Mn(II) and Fe(III) complexes showed
The results of biological activity tested for the ligand and its
complexes are given in Figures 3 and 4. Diameter of inhibi-
tion zone (mm) including the disc diameter was measured for
each treatment. The results was in agreement with the previ-
ously reported antibacterial and antifungal properties of this
Fig. 6. Ratio of the IC50 of standard drug to that of ligand and its metal complexes against human breast cancer cell line (MCF-7;
reactivity ratio).

Salicylaldehyde Phenylhydrazone Metal Complexes
445
moderate antibacterial and antifungal activities in this study. antibacterial activities. The results indicate that the com-
The results indicate that the complexes showed more activity plexes showed more activity than the ligand.
than the ligand. This would suggest that the chelation could
facilitate the ability of a complex to cross a cell membrane
and can be explained by Tweedy’s chelation theory.[28] Chela- References
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