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Comparative studies, synthesis, spectroscopic and characterization of N-methylisatin-3-Girard’s T and P hydrazone complexes
Accepted Manuscript Comparative studies, synthesis, sprctroscopic and characterization of N-methylisatin-3-Girard’s T and P hydrazone complexes Shaker J. Azhari, Sabah Salah, Rabei S. Farag, Mohsen M. Mostafa PII: DOI: Reference:
S1386-1425(14)01603-5 http://dx.doi.org/10.1016/j.saa.2014.10.106 SAA 12921
To appear in:
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy
Received Date: Revised Date: Accepted Date:
16 July 2014 13 October 2014 23 October 2014
Please cite this article as: S.J. Azhari, S. Salah, R.S. Farag, M.M. Mostafa, Comparative studies, synthesis, sprctroscopic and characterization of N-methylisatin-3-Girard’s T and P hydrazone complexes, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy (2014), doi: http://dx.doi.org/10.1016/j.saa.2014.10.106
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Comparative studies, synthesis, sprctroscopic and characterization of Nmethylisatin-3-Girard’s T and P hydrazone complexes
Shaker J. Azhari1, Sabah Salah2, Rabei S. Farag2, Mohsen M. Mostafa3* 1 2
Chemistry Department, Faculty of Applied Sciences, Umm Al-Qura University, Saudi Arabia
ChemistryDepartment, Faculty of Science, Al-Azhar University, Egypt
3
Chemistry Department, Faculty of Science, Mansoura University, Egypt
_________________________________________________________________________________
ABSTRACT __________________________________________________________________________
Different types of complexes derived from the reactions of N-methylisatin Girard’s T hydrazone, N,N,N-trimethyl-2-[(2z)-2-(1-methyl-2-oxo-1,2-dihydro-3H-indole3-ylidene)
hydrazino]-2-oxo-ethan
ammonium
chloride
(MIGT)
and
N-
methylisatin Girard’s P hydrazone, 1-{2-(2z)-2-[(1-methyl-2-oxo-1,2-dihyrdo-3Hindole-3-ylidene) hydrazino]-2-oxoethyl}pyridinium chloride (MIGP) with Fe3+, Al3+, Sb3+ and Sn2+ salts were synthesized. The isolated complexes were characterized by elemental analyses, molar conductivities, spectral (IR, UV-Vis., 1
H-NMR, mass), magnetic moments and thermal measurements.
The values of
conductance suggest that the complexes are conducting in polar solvents (EtOH, H2O and DMF). The IR spectra suggest that the ligands coordinate in a bidentate and/or tridentate manner via the carbonyl groups of both N-methylisatin and 1
Girards’T and/or P and the (C=N) group. The solvents inside and outside the coordination sphere were determined by weight loss and TGA methods. The octahedral geometry of the complexes is confirmed using spectral, magnetic and DFT method from DMOL3 calculations. The ligands and their metal complexes were tested against different strains of bacteria and fungi. Keywords: Methylisatain complexes, Spectroscopic studies and DFT calculations, Girard’s T and P hydrazone complexes; Biological activity. _______________________________________________________________ *
Corresponding author. Tel.: 00-202-01067446662; Fax: 00-2050-2246781; email: [email protected]
Introduction Girard’s T and P reagents and their derivatives form water-soluble hydrazones, enabling the separation of carbonyl organic substances [1]. These compounds and their derivatives are used in pharmacology [2]. Also, the reagents and their Schiffbases represent an interesting research subject [3].
The biological activity of
complexes is often enhanced; Schiff-bases have also been studied as ligands in coordination chemistry [4-7]. Isatin and its analogs are versatile substrates, which can be used for the synthesis of numerous heterocyclic compounds. Schiff-bases, derived from various heterocycles were reported to possess cytotoxic [8], anticonvulsant [9], antiproliferative [10] activities. A number of Schiff-bases [1114] have been tested for antibacterial [15-18] antifungal [17-19] anticancer [20,21] 2
and herbicidal [22] activities. In continuation of our earlier work, [23] we extend this work to include the hydrazones (MIGT and MIGP) derived from Girard’s T and P reagents with N-methylisatin and their Fe3+, Al3+, Sb3+ and Sn2+ complexes. Also, one of our goals is to make a comparative study with our earlier work [23] and try to know the difference between the hydrazones derived from isatin and methylisatin in the mode of chelation and their effects of biological activity. Experimental Materials and methods All the chemicals, apparatus, methods and procedures used in this investigation are similar to those reported in our previous papers [23]. Synthesis of ligands and metal complexes The ligands were prepared similar to those reported earlier [23] but using methylisatin and Girard’s P and T. All complexes were prepared by refluxing the ligands (1.0 mmol) and anhydrous metal salts FeCl3, AlCl3 and SbCl3 and the hydrated SnCl2.2H2O salt (1.0 mmol) dissolved in EtOH (30 mL) for 2-3 h, except in the Al3+ complexes in which the reflux process continued for 48 h.
The
resulting solid complexes were filtered off hot, washed with cold EtOH followed by diethyl ether and finally dried in vacuum over P4O10. Biological activity
3
Antibacterial and antifungal activity of the ligands and their complexes were tested using the same procedure described in our previous paper [23]. Molecular modeling We performed cluster calculations using DMOL3 program in Materials Studio package as discussed earlier in our previous paper [23]. Results and discussion The analytical data of the ligands and their complexes are listed in table1. All the compounds are stable in air and light. The isolated compounds are soluble in water, ethanol, DMF and DMSO and insoluble in most organic solvents.
The
molar conductivities of the isolated compounds were carried out in water, DMF and EtOH at 18 ºC. The values reported in table 2 suggest that all the compounds are electrolytic in nature [24] due to the existence of at least one ionizable chloride outside the coordination sphere.
Also, the molecular weight determinations
confirm the proposed formulae of the ligands and complexes (Table 1). Table 1 Analytical data and some physical properties for hydrazone ligands and their metal complexes. Compound No. Empirical formula
L1; MIGT C14H19ClN4O2 (310.82) [Fe(L1)(EtOH)3]Cl4 (611.26)
Color
M.p.
Yield
(OC)
%
Pale yellow
287
75
Golden brown
228
65
4
Analytical data (%)a
C
H
N
Cl
54.0
6.3
18.1
11.5
(54.1)
(6.2)
(18.0)
(11.4)
39.3
6.0
(39.3)
(6.1)
--
M --
22.8
9.5
(23.2)
(9.1)
[Al(L1)Cl2(EtOH)2]Cl2.1.5H2O (563.34)
>300
50
215
67
Pale yellow
273
75
Yellow
285
80
[Fe(L2)Cl(EtOH)2]Cl3 (585.16)
Brownish yellow
220
65
[Al(L2)Cl2(H2O)2]Cl.2H2O (536.21)
Pale yellow
[Sb(L2)(EtOH)3(H2O)]Cl4 (715.16)
Pale yellow
250
67
Yellow
269
75
[Sb(L1)Cl2(H2O)]Cl2.2H2O (592.98)
Deep yellow Pale yellow
[Sn(L1)(EtOH)2(H2O)2]Cl3 (628.61)
L2; MIGP C16H15ClN4O2 (330.80)
[Sn(L2)Cl(H2O)3]Cl2 (574.45)
>30 0
50
Carbide
28.3
9.9
25.1
4.9
(10.0)
(25.2)
(4.8)
4.3
--
24.0
28.3
(23.9)
(28.4)
16.9
33.6
(16.9)
(33.5)
(28.4)
(4.3)
33.6
4.1
(33.5)
(3.7)
58.1
4.6
16.4
10.5
(58.1)
(4.6)
(16.9)
(10.7)
41.1
4.7
(41.1)
(4.7)
Carbide
37.1
6.0
(37.0)
(5.0)
33.6
4.1
(33.5)
(3.7)
--
--
10.6 (10.5) ---
--
24.5
9.3
(24.2)
(9.5)
26.7
5.1
(26.4)
(5.0)
20.0
17.1
(19.8)
(17.0)
18.6
20.5
(18.5)
(20.7)
Table 2 Magnetic moments, electronic spectral bands and molar conductance of the ligands and their metal complexes.
Molar conductance Absorption bands (nm) Compound No.
µeff (BM)
L1; MIGT
--
State
π -π*
5.75
DMF
288, 354
Nujol
265, 328
[Al(L1)Cl2(EtOH)2]Cl2.1.5H2O
Diam.
DMF
270, 324, 353
[Sb(L1)Cl2(H2O)]Cl2.2H2O
Diam.
DMF
310
[Sn(L1)(EtOH)2(H2O)2]Cl3
Diam.
DMF
258,322
--
DMF
304
L2; MIGP
d-d
H2O
DMF
EtOH
92.4
56.5
37.9
441.3
197.7
175.8
256.8
95.8
88.2
--
279.2
106.9
76.4
--
369.1
127.5
97.8
--
127.0
67.9
42.8
transitions
DMF [Fe(L1)(EtOH)3]Cl4
n- π*
(Ω-1 cm2 mol-1)
5
432, 458, 498 424. 460 386, 438 412, 452, 494 360, 400, 470 427, 453, 500 340, 410,
-538 522 --
[Fe(L2)Cl(EtOH)2]Cl3
5.71
DMF
--
[Al(L2)Cl2(H2O)2]Cl2.2H2O
Diam.
Nujol
288
[Sb(L2)(EtOH)3(H2O)]Cl4
Diam.
DMF
268
[Sn(L2)Cl(H2O)3]Cl2
Diam.
Nujol
288
450, 570 434, 464 348, 398, 445 349, 429, 473 350, 388, 438
592
329.1
132.3
143.5
--
145.9
55.8
47.9
--
394.8
134.2
137.3
--
235.6
96.4
151.7
Molecular modeling Molecular modeling of ligand MIGT and its metal complexes The molecular structures along with atom numbering of MIGT are shown in Figure 1. The molecular structures of the metal complexes are shown in Figure S 1. Analysis of the data (S 2-4) including comparison between the bond lengths and bond angles and some energetic data of the ligand and its metal complexes; one can conclude the following remarks: • The intra-molecular hydrogen bond length is 1.825 Å where the bond angle is 139.866o. • The C(8)-O(10), C(9)-N(11) and C(13)-O(14) bond lengths of the ligand become slightly longer or smaller in complexes as the coordination takes place via these groups. • In the case of Al3+ and Sn2+ the stretching of the bonds (C=O)GT and (C=O)mi is attributed to the formation of hydrogen bonds with the coordinated groups (EtOH or water), respectively. 6
• The bond angles of the hydrazone moiety of MIGT are altered somewhat upon coordination; the largest change affects N(7)-C(8)-O(10), C(9)-C(8)O(10), C(9)-N(11)-N(12), N(12)-C(13)-O(14) and O(14)-C(13)-C(15) in complexes structures. • The previous angles are reduced or increased on complex formation due to participating in the coordination sphere.
(a)
(b)
(c)
(d)
7
(ei) (eii) Fig. 1. Molecular structures of (a) MIGT (b) electron density (c) HOMO (d) LUMO (e) the
intra-molecular hydrogen bond (i) length and (ii) angle. Molecular modeling of MIGP and its metal complexes The molecular structures along with atom numbering of the ligand (Fig. 2) while its metal complexes are shown in S 5. Analysis of the data (S 6-8) includes comparison between the bond lengths and bond angles and some energetic data of the ligand and its metal complexes, one can conclude the following remarks: • There is an intra-molecular hydrogen bond (H- O16). The bond length of the hydrogen bond is 1.918 Å where 134.560o is the bond angle. • The C(8)-O(16), C(9)-N(10) , N(10)-N(11) and C(8)-O(15) bond lengths of the ligand were changed in numbering to C(8)-O(11), C(9)-N(10), N(10)N(12) and C(13)-O(14) for Sb3+, and C(8)-O(15), C(9)-N(26), N(26)-N(10) and C(11)-O(12) for the Sn2+ complexes. • These bond lengths of the ligand become slightly longer in complexes as the coordination takes place via these groups. 8
• The C(8)-O(16) bond distance in all complexes becomes longer due to the formation of the M-O bond which makes the C-O bond weaker. • The bond angles of the hydrazone moiety of MIGP are altered somewhat upon coordination; the largest change affects N(7)-C(8)-O(16), C(9)-C(8)O(16), C(9)-N(10)-N(11), N(11)-C(12)-O(13) and O(13)-C(12)-C(14) in complexes structures as these sites participate in the coordination sphere. • The lower HOMO energy values show that molecules donating electron ability is the weaker. On the contrary, the higher HOMO energy implies that the molecule is a good electron donor. LUMO energy presents the ability of a molecule-receiving electron [25].
(a)
(b)
9
(c)
(d)
(ei)
(eii)
Fig. 2. Molecular structures of (a) MIGP (b) electron density (c) HOMO (d) LUMO (e) the intra-molecular hydrogen bond (i) length and (ii) angle. IR and 1H-NMR spectra of ligands and their metal complexes The IR spectrum of MIGT (Fig. 3) shows a band at 3016 cm-1 assigned to υ(NH)GT vibration [26]. The bands observed at 1708, 1674, 1525 and 993 cm-1 are attributed to υ(C=O)mi, υ(C=O)GT [27], υ(C=N)hy and the hydrazinic υ(N-N) [28] vibrations, respectively.
The bands in the 3492-3323 cm–1 region support the
existence of intra-molecular hydrogen bond. All the band assignments are recorded in table 3.
10
Fig. 3. IR spectrum of MIGT. Table 3 Significant IR spectral bands (cm-1) of the ligands and their metal complexes. Compound No.
υ(NH)hy
υ(C=O)mi
υ(C=O)hy
υ(C=N)
υ(M-N)
υ(M-O)
L1; MIGT
3224
1708
1689
1525
--
--
[Fe(L1)(EtOH)3]Cl4
3207
1722
1683
1533
403
523
[Al(L )Cl2(EtOH)2]Cl2.1.5H2O
3210
1719
1684
1560
398
525
[Sb(L1)Cl2(H2O)]Cl2.2H2O
3201
1714
1686
1518
398
515
[Sn(L1)(EtOH)2(H2O)2]Cl3
3232
1708
1679
1545
448
538
L2; MIGP
3226
1724
1688
1578
--
--
[Fe(L2)Cl(EtOH)2]Cl3
3215
1719
1677
1587
426
539
[Al(L2)Cl2(H2O)2]Cl2.2H2O
3146
1727
1681
1524
398
532
[Sb(L )(EtOH)3(H2O)]Cl4
3218
1709
1689
1542
401
505
[Sn(L2)Cl(H2O)3]Cl2
3183
1701
1691
1527
491
628
1
2
11
The 1H-NMR spectrum of MIGT (Fig. 4) shows a weak singlet signal at δ 12.68 ppm downfield of TMS. This signal is assigned to (NH)GT proton. The multiple signals at δ 7.20–7.64 ppm are attributed to the aromatic C-H of the bisubstituted ring [29]. The signal of the methylene group (CH2) appears at δ 4.99 ppm. The signal at δ 3.38 ppm corresponds to the protons of the aliphatic (CH3)3 [26] where the methyl group of the methylisatin ring is observed at δ 2.51 ppm.
Fig. 4. 1H-NMR spectrum of MIGT. The IR spectrum of MIGP (Fig. 5) shows a medium broad band at 3226 cm-1. This band is due to ν(NH)GP vibration. The strong band and its shoulder at 1688 and 1724 cm-1 are attributed to ν(C=O)GP and ν(C=O)mi vibrations, respectively. The 12
shoulder band at 1578 cm-1 is assigned to ν(C=N)imine vibration. The bands at 680 and 416 cm-1 are attributed to the pyridine ring in plane and out of plane deformation . The weak band at 972 cm-1 is attributed to ν(N-N) vibration. The broad band in the 3461–3405 cm-1 regions is taken as an evidence for the involvement of the NH proton in the formation of intra-molecular hydrogen bonding [30].
Fig. 5. IR spectrum of MIGP. The 1H-NMR spectrum of the ligand (MIGP; Fig. 6) shows a signal at δ 12.8 ppm, downfield relative to TMS, which disappears upon deuteration. This signal is
13
assigned to the (NH)GP proton . The multiple signals at δ 7.21-7.63 ppm are attributed to the aromatic protons. The pyridine protons are represented by the multiple signals at δ8.2-9.1 ppm. The signal due to CH2 protons appears at 6.2 ppm . The methyl protons of the methylisatin ring appear as a singlet signal at δ3.4 ppm.
Fig. 6. 1H-NMR spectrum of MIGP.
14
A careful comparison of the IR spectra of the free ligands and their metal complexes reveals that the ligands coordinate to the metal ions without deprotonation.
Also, they coordinate to the metal ions in a bidentate and/or
tridentate manners through the carbonyl and the azomethine groups. The bands in the 382–492 and 503–526 cm-1 regions are assigned to ν(M–N) [31-33] and ν(M– O) [34-36] vibrations, respectively, which are absent in the free ligand. Mass Spectra The mass spectrum of MIGT (Fig. 7) shows the molecular ion peak at m/z = 311.05 which agree with the molecular formula C14H19ClN4O2; 310.82. Also, the spectrum shows numerous peaks corresponding to the various fragments and their intensity gives an idea on the stability of the fragments. The decomposition steps for the ligand are shown in S 9.
15
Fig. 7. Mass spectrum of MIGT. The mass spectrum of the Sn2+ complex derived from MIGT (Fig. 8) shows the molecular ion peak at m/z = 628.65 (Calcd.: 628.61) which agree with the molecular formulae C18H35Cl3N4O6Sn Scheme (S 10) shows the proposed fragmentation route of the complex.
16
Fig. 8. Mass spectrum of [Sn(L1)(EtOH)2(H2O)2]Cl3. The mass spectrum of MIGP (Fig. 9) shows the molecular ion peak at m/z = 331.4 which agree with the molecular formula, C16H17ClN4O2; 330.80. Also, the mass spectrum shows numerous peaks corresponding to various fragments and their intensity gives an idea on the stability of the fragments. Scheme (S 11) shows the proposed path of the decomposition steps for the ligand (L2; MIGP).
17
Fig. 9. Mass spectrum of MIGP.
The mass spectrum of Sb3+ complex (Fig. 10) shows the molecular ion peak at m/z=715.05, which agree with the molecular formulae C22H35Cl4N4O6Sb; 715.16. Scheme (S 12) shows the proposed fragmentation pattern of the complex.
18
Fig. 10. Mass spectrum of [Sb(L2)(EtOH)3(H2O)]Cl4.
Magnetic moments and electronic spectra of the ligands and their metal complexes The electronic spectra of the ligands show absorption bands at 354 and 340 nm (Table 2). These bands correspond to the transition from the azomethine groups in ligands of the type MIGT and MIGP, respectively. The presence of this band confirms the existence of the ligand in the hydrazo form [37]. The value of magnetic moments for the Fe3+ complexes are µ eff = 5.75 and 5.71 BM indicating a high-spin configuration where the unpaired spin complex has more stable arrangement than the low-spin [38,39]. The electronic spectra of the other complexes show bands due to π→π* and n→π* transitions which are shifted to lower or to higher wavenumber due to the 19
coordination of the ligand to the metal ions through these groups. The complexes are diamagnetic in nature in accordance with the d0 or d10 configuration. Thermogravimetric analysis TGA data of the metal complexes was used as a probe to proof the amounts of solvents (H2O or EtOH) in the coordination sphere or in the crystalline form. The TGA thermogram of the Fe3+ [Fe(L1)(EtOH)3]Cl4 complex, shows three stages of decomposition (S 13). The first step lies in the 206-383 ºC range and represents the loss of the coordinated EtOH molecules and the chloride ions (Found: 44.49 %; Calcd.: 45.81 %). The second step is found in the 384-545 ºC range due to the loss of five CH3 groups, CO2 and N2 with experimental mass loss 24.83 % which is close to the theoretical value 24.08 %). The third stage lies in the 546-756 ºC range is attributed to the loss of C7H4N (Found: 16.66 %; Calcd.: 16.71 %). The residual part of the complex was found to be FeN and one carbon atom with a mass of 14.0 % where the calculated value is 13.39 %. The TGA curve of the Al3+ complex, [Al(L2)Cl2(H2O)2]Cl2.2H2O, shows four stages of decomposition as shown in S 14. The first step lies in the 38-191ºC range corresponds to the loss of two molecules of water of hydration, two molecules of water (coordinated) and the CH3 group (Found: 17.27 %; Calcd.: 16.25 %). The second step is found in the 191-296 ºC range attributes to the loss of 2Cl2 + O2 (observed mass loss 32.03 %; theoretical value 21.41 %). The third 20
step corresponds to the loss of one chloride atom and C5H5 is observed in the 296452 ºC range (Found: 12.87 % ; Calcd.:12.14 % ). The fourth step is found in the 452-642 ºC range attributes to the loss of one chloride atom and C2H3N2. The observed mass loss of this step is 10.48 % (Calcd.: 10.27 %). Finally, the observed residue corresponds the loss of C8H4N and AlN (Found: 27.35 %; Calcd.: 28.93%). Antibacterial and antifungal activity The ligand MIGT reveals a moderate inhibition activity against Salmonella typhimurium on increasing concentration; where MIGP shows no inhibition activity towards any of the used strains of bacteria and fungi (Table 4). The Fe3+ complexes, [Fe(L1)(EtOH)3]Cl4 and
[Fe(L2)Cl(EtOH)2]Cl3, reveal a moderate
inhibition activity towards the Gram (-ve) bacteria Salmonella typhimurium. The Sb3+ complex, [Sb(L2)(EtOH)3(H2O)]Cl4 possess a moderate activity against the Gram (+ve) bacteria; Bacillus subtilis. The other complexes reveal a low and/or no activity towards the entire tested microorganism. The results are shown in table 4.
Table 4 Antibacterial and antifungal activity of the ligands and their metal complexes.
Sample
Conc.
Zone diameter (mm)
21
mg/ml Gram (+ve) bacteria
Gram (-ve) bacteria
Staphylococcus Bacillus
L1; MIGT
0.5
[Fe(L1)(EtOH)3]Cl4
0.5
[Al(L1)Cl2(EtOH)2]Cl2.1.5H2O
0.5
[Sb(L1)Cl2(H2O)]Cl2.2H2O
0.5
[Sn(L1)(EtOH)2(H2O)2]Cl3
0.5
L2; MIGP
0.5
[Fe(L2)Cl(EtOH)2]Cl3
0.5
[Al(L2)Cl2(H2O)2]Cl2.2H2O
0.5
[Sb(L2)(EtOH)3(H2O)]Cl4
0.5
[Sn(L2)Cl(H2O)3]Cl2
0.5
Control
1 1 1 1 1 1 1 1 1 1 0.5 1
Yeast and fungi
Salmonella Escherichia Candida
Aspergillus
aureus
subtilis
typhimurium
coli
albicans
fumigatus
2L 4L
2L
8L 13 I
-
2L
-
2L
-
8L 14 I
2L 4L
-
-
2L
2L 4L
7L 10 L
-
-
3L 5L
4L 6L
-
5L 8L
-
2L
-
3L 5L
3L
4L 7L
3L
-
2L 4L
-
2L
2L
2L
4L 6L
-
-
2L
10 I 18 I
2L 5L
4L 8L
2L
2L
2L 4L
7L 10 L
-
-
3L 5L
4L 6L
14 I 18 I
5L 8L
-
4L 9L
-
3L 5L
3L
4L 7L
3L
-
2L 4L
26 35
25 35
28 36
27 38
28 35
26 37
CONCLUSION
Acknowledgment The authors are thankful to Dr. Z.D. Al-Shafey, Chemistry Department, Faculty of Science, Al-Azhar University, Egypt for supporting during the progress of this work.
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c) Z.H. Chohan, Mahmood-ul-Hassan; K.M. Khan, C.T. Supuran, J. Enzyme Inhib. Med. Chem. 20 (2005) 183. d) Z.H. Chohan, H. Pervez, A. Rauf, K.M. Khan, G.M. Maharvi, C.T. Supuran, J. Enzyme Inhib. Med. Chem. 19 (2004) 51. e) W. Rehman, M.K. Baloch, B. Muhammad, A. Badshah, K.M. Khan, Chin. Sci. Bull. 49 (2004) 119. f) W. Rehman, A. Badshah, M.K. Baloch, S. Ali, G. Hameed, K.M. Khan, J. Chin. Chem. Soc. 2004, 51, 929. [12] A.S. Kabeer, M.A. Baseer, N.A. Mote, Asian. J. Chem. 13 (2001) 496. [13] A.H. El-Masry, H.H. Fahmy, S.H.A. Abdelwahed, Molecules 5 (2000) 1429. [14] P.G. More, R.B. Bhalvankar, S.C. Patter, J. Indian Chem. Soc. 78 (2001) 474. [15] S.N. Pandeya, D. Sriram, G. Nath, E.D. Clereq, II Farmaco 54 (1999) 624. [16] W.M. Singh, B.C. Dash, Pesticides 22 (1988) 33. [17] S. B. Desai, P.B. Desai, K.R. Desai, Heterocycl. Commun. 7 (2001) 83. [18] P. Pathak, V.S. Jolly, K.P. Sharma, Orient J. Chem. 16 (2000) 161. [19] S. Samadhiya, A. Halve, Orient J. Chem. 17 (2001) 119. [20] a) A.I. Vogel; “A Text-book of Practical Organic Chemistry”, 24
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Pelosi, C. Pelizzi, F. Zani; J. Inorg. Biochem. 101 (2007) 138. [28] D.N. Sathyanarayana, D. Nicholls, Spectrochim. Acta. 34 (1978) 263. [29] K.M. Khan, M. Khan, M. Ali, M. Taha, S. Rasheed, S. Perveen, M.I. Choudhary; Bioorg. Med. Chem. 17 (2009) 7795. [30] K. Nakamoto, “Infrared Spectra of Inorganic and Coordination Compounds”, Wiley, New York, (1970). S.M. Al-Ashqar, M.M. Mostafa, Spectrochim. Acta. 71 (2008) 1321. [31] J.R. Ferraro, Low Frequency Vibrations of Inorganic and Coordination Compounds, New York, Plenum Press (1971). [32] K. Mohanan and S.N. Devi; Russ. J. Coord. Chem. 32 (2006) 600. [33] M.A. Affan, Y.Z. Liew, B.A. Fasihuddin, B.S. Mustaffa, M.Y. Bohari; Ind. J. Chem. 46 A (2007) 1063. [34] M. Jain, S. Gaur, S.C. Diwedi, S.C. Joshi, R.V. Sing, A. Bansal; Phosphorus Sulpher Silicon 179 (2004) 1517. [35] Z.Y. Yang, B.D. Wang, Y.H. Li, J. Organomet. Chem. 691 (2006) 4159. [36] A. Szorcsik, L. Nagy, L. Pellerito, T. Yamaguchi, K. Yoshida, J. Radioanal. Nucl. 256 (2003) 3. [37] C.H. Yao; J. Org. Chem. 29 (1964) 2959. [38] P.R. Mandlik and A.S. Aswar; Polish J. Chem. 77 (2003) 129. [39] 26
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27
GRAPHICAL ABSTRACT
Molecular structures of L2
28
HIGH LIGHTS
•Methylisatin Girard’s T and P hydrazones.
• Biological activity of the ligands and complexes. • Fe3+, Al3+, Sb3+ and Sn2+ complexes. • DFT calculations.
29
S1386-1425(14)01603-5 http://dx.doi.org/10.1016/j.saa.2014.10.106 SAA 12921
To appear in:
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy
Received Date: Revised Date: Accepted Date:
16 July 2014 13 October 2014 23 October 2014
Please cite this article as: S.J. Azhari, S. Salah, R.S. Farag, M.M. Mostafa, Comparative studies, synthesis, sprctroscopic and characterization of N-methylisatin-3-Girard’s T and P hydrazone complexes, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy (2014), doi: http://dx.doi.org/10.1016/j.saa.2014.10.106
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Comparative studies, synthesis, sprctroscopic and characterization of Nmethylisatin-3-Girard’s T and P hydrazone complexes
Shaker J. Azhari1, Sabah Salah2, Rabei S. Farag2, Mohsen M. Mostafa3* 1 2
Chemistry Department, Faculty of Applied Sciences, Umm Al-Qura University, Saudi Arabia
ChemistryDepartment, Faculty of Science, Al-Azhar University, Egypt
3
Chemistry Department, Faculty of Science, Mansoura University, Egypt
_________________________________________________________________________________
ABSTRACT __________________________________________________________________________
Different types of complexes derived from the reactions of N-methylisatin Girard’s T hydrazone, N,N,N-trimethyl-2-[(2z)-2-(1-methyl-2-oxo-1,2-dihydro-3H-indole3-ylidene)
hydrazino]-2-oxo-ethan
ammonium
chloride
(MIGT)
and
N-
methylisatin Girard’s P hydrazone, 1-{2-(2z)-2-[(1-methyl-2-oxo-1,2-dihyrdo-3Hindole-3-ylidene) hydrazino]-2-oxoethyl}pyridinium chloride (MIGP) with Fe3+, Al3+, Sb3+ and Sn2+ salts were synthesized. The isolated complexes were characterized by elemental analyses, molar conductivities, spectral (IR, UV-Vis., 1
H-NMR, mass), magnetic moments and thermal measurements.
The values of
conductance suggest that the complexes are conducting in polar solvents (EtOH, H2O and DMF). The IR spectra suggest that the ligands coordinate in a bidentate and/or tridentate manner via the carbonyl groups of both N-methylisatin and 1
Girards’T and/or P and the (C=N) group. The solvents inside and outside the coordination sphere were determined by weight loss and TGA methods. The octahedral geometry of the complexes is confirmed using spectral, magnetic and DFT method from DMOL3 calculations. The ligands and their metal complexes were tested against different strains of bacteria and fungi. Keywords: Methylisatain complexes, Spectroscopic studies and DFT calculations, Girard’s T and P hydrazone complexes; Biological activity. _______________________________________________________________ *
Corresponding author. Tel.: 00-202-01067446662; Fax: 00-2050-2246781; email: [email protected]
Introduction Girard’s T and P reagents and their derivatives form water-soluble hydrazones, enabling the separation of carbonyl organic substances [1]. These compounds and their derivatives are used in pharmacology [2]. Also, the reagents and their Schiffbases represent an interesting research subject [3].
The biological activity of
complexes is often enhanced; Schiff-bases have also been studied as ligands in coordination chemistry [4-7]. Isatin and its analogs are versatile substrates, which can be used for the synthesis of numerous heterocyclic compounds. Schiff-bases, derived from various heterocycles were reported to possess cytotoxic [8], anticonvulsant [9], antiproliferative [10] activities. A number of Schiff-bases [1114] have been tested for antibacterial [15-18] antifungal [17-19] anticancer [20,21] 2
and herbicidal [22] activities. In continuation of our earlier work, [23] we extend this work to include the hydrazones (MIGT and MIGP) derived from Girard’s T and P reagents with N-methylisatin and their Fe3+, Al3+, Sb3+ and Sn2+ complexes. Also, one of our goals is to make a comparative study with our earlier work [23] and try to know the difference between the hydrazones derived from isatin and methylisatin in the mode of chelation and their effects of biological activity. Experimental Materials and methods All the chemicals, apparatus, methods and procedures used in this investigation are similar to those reported in our previous papers [23]. Synthesis of ligands and metal complexes The ligands were prepared similar to those reported earlier [23] but using methylisatin and Girard’s P and T. All complexes were prepared by refluxing the ligands (1.0 mmol) and anhydrous metal salts FeCl3, AlCl3 and SbCl3 and the hydrated SnCl2.2H2O salt (1.0 mmol) dissolved in EtOH (30 mL) for 2-3 h, except in the Al3+ complexes in which the reflux process continued for 48 h.
The
resulting solid complexes were filtered off hot, washed with cold EtOH followed by diethyl ether and finally dried in vacuum over P4O10. Biological activity
3
Antibacterial and antifungal activity of the ligands and their complexes were tested using the same procedure described in our previous paper [23]. Molecular modeling We performed cluster calculations using DMOL3 program in Materials Studio package as discussed earlier in our previous paper [23]. Results and discussion The analytical data of the ligands and their complexes are listed in table1. All the compounds are stable in air and light. The isolated compounds are soluble in water, ethanol, DMF and DMSO and insoluble in most organic solvents.
The
molar conductivities of the isolated compounds were carried out in water, DMF and EtOH at 18 ºC. The values reported in table 2 suggest that all the compounds are electrolytic in nature [24] due to the existence of at least one ionizable chloride outside the coordination sphere.
Also, the molecular weight determinations
confirm the proposed formulae of the ligands and complexes (Table 1). Table 1 Analytical data and some physical properties for hydrazone ligands and their metal complexes. Compound No. Empirical formula
L1; MIGT C14H19ClN4O2 (310.82) [Fe(L1)(EtOH)3]Cl4 (611.26)
Color
M.p.
Yield
(OC)
%
Pale yellow
287
75
Golden brown
228
65
4
Analytical data (%)a
C
H
N
Cl
54.0
6.3
18.1
11.5
(54.1)
(6.2)
(18.0)
(11.4)
39.3
6.0
(39.3)
(6.1)
--
M --
22.8
9.5
(23.2)
(9.1)
[Al(L1)Cl2(EtOH)2]Cl2.1.5H2O (563.34)
>300
50
215
67
Pale yellow
273
75
Yellow
285
80
[Fe(L2)Cl(EtOH)2]Cl3 (585.16)
Brownish yellow
220
65
[Al(L2)Cl2(H2O)2]Cl.2H2O (536.21)
Pale yellow
[Sb(L2)(EtOH)3(H2O)]Cl4 (715.16)
Pale yellow
250
67
Yellow
269
75
[Sb(L1)Cl2(H2O)]Cl2.2H2O (592.98)
Deep yellow Pale yellow
[Sn(L1)(EtOH)2(H2O)2]Cl3 (628.61)
L2; MIGP C16H15ClN4O2 (330.80)
[Sn(L2)Cl(H2O)3]Cl2 (574.45)
>30 0
50
Carbide
28.3
9.9
25.1
4.9
(10.0)
(25.2)
(4.8)
4.3
--
24.0
28.3
(23.9)
(28.4)
16.9
33.6
(16.9)
(33.5)
(28.4)
(4.3)
33.6
4.1
(33.5)
(3.7)
58.1
4.6
16.4
10.5
(58.1)
(4.6)
(16.9)
(10.7)
41.1
4.7
(41.1)
(4.7)
Carbide
37.1
6.0
(37.0)
(5.0)
33.6
4.1
(33.5)
(3.7)
--
--
10.6 (10.5) ---
--
24.5
9.3
(24.2)
(9.5)
26.7
5.1
(26.4)
(5.0)
20.0
17.1
(19.8)
(17.0)
18.6
20.5
(18.5)
(20.7)
Table 2 Magnetic moments, electronic spectral bands and molar conductance of the ligands and their metal complexes.
Molar conductance Absorption bands (nm) Compound No.
µeff (BM)
L1; MIGT
--
State
π -π*
5.75
DMF
288, 354
Nujol
265, 328
[Al(L1)Cl2(EtOH)2]Cl2.1.5H2O
Diam.
DMF
270, 324, 353
[Sb(L1)Cl2(H2O)]Cl2.2H2O
Diam.
DMF
310
[Sn(L1)(EtOH)2(H2O)2]Cl3
Diam.
DMF
258,322
--
DMF
304
L2; MIGP
d-d
H2O
DMF
EtOH
92.4
56.5
37.9
441.3
197.7
175.8
256.8
95.8
88.2
--
279.2
106.9
76.4
--
369.1
127.5
97.8
--
127.0
67.9
42.8
transitions
DMF [Fe(L1)(EtOH)3]Cl4
n- π*
(Ω-1 cm2 mol-1)
5
432, 458, 498 424. 460 386, 438 412, 452, 494 360, 400, 470 427, 453, 500 340, 410,
-538 522 --
[Fe(L2)Cl(EtOH)2]Cl3
5.71
DMF
--
[Al(L2)Cl2(H2O)2]Cl2.2H2O
Diam.
Nujol
288
[Sb(L2)(EtOH)3(H2O)]Cl4
Diam.
DMF
268
[Sn(L2)Cl(H2O)3]Cl2
Diam.
Nujol
288
450, 570 434, 464 348, 398, 445 349, 429, 473 350, 388, 438
592
329.1
132.3
143.5
--
145.9
55.8
47.9
--
394.8
134.2
137.3
--
235.6
96.4
151.7
Molecular modeling Molecular modeling of ligand MIGT and its metal complexes The molecular structures along with atom numbering of MIGT are shown in Figure 1. The molecular structures of the metal complexes are shown in Figure S 1. Analysis of the data (S 2-4) including comparison between the bond lengths and bond angles and some energetic data of the ligand and its metal complexes; one can conclude the following remarks: • The intra-molecular hydrogen bond length is 1.825 Å where the bond angle is 139.866o. • The C(8)-O(10), C(9)-N(11) and C(13)-O(14) bond lengths of the ligand become slightly longer or smaller in complexes as the coordination takes place via these groups. • In the case of Al3+ and Sn2+ the stretching of the bonds (C=O)GT and (C=O)mi is attributed to the formation of hydrogen bonds with the coordinated groups (EtOH or water), respectively. 6
• The bond angles of the hydrazone moiety of MIGT are altered somewhat upon coordination; the largest change affects N(7)-C(8)-O(10), C(9)-C(8)O(10), C(9)-N(11)-N(12), N(12)-C(13)-O(14) and O(14)-C(13)-C(15) in complexes structures. • The previous angles are reduced or increased on complex formation due to participating in the coordination sphere.
(a)
(b)
(c)
(d)
7
(ei) (eii) Fig. 1. Molecular structures of (a) MIGT (b) electron density (c) HOMO (d) LUMO (e) the
intra-molecular hydrogen bond (i) length and (ii) angle. Molecular modeling of MIGP and its metal complexes The molecular structures along with atom numbering of the ligand (Fig. 2) while its metal complexes are shown in S 5. Analysis of the data (S 6-8) includes comparison between the bond lengths and bond angles and some energetic data of the ligand and its metal complexes, one can conclude the following remarks: • There is an intra-molecular hydrogen bond (H- O16). The bond length of the hydrogen bond is 1.918 Å where 134.560o is the bond angle. • The C(8)-O(16), C(9)-N(10) , N(10)-N(11) and C(8)-O(15) bond lengths of the ligand were changed in numbering to C(8)-O(11), C(9)-N(10), N(10)N(12) and C(13)-O(14) for Sb3+, and C(8)-O(15), C(9)-N(26), N(26)-N(10) and C(11)-O(12) for the Sn2+ complexes. • These bond lengths of the ligand become slightly longer in complexes as the coordination takes place via these groups. 8
• The C(8)-O(16) bond distance in all complexes becomes longer due to the formation of the M-O bond which makes the C-O bond weaker. • The bond angles of the hydrazone moiety of MIGP are altered somewhat upon coordination; the largest change affects N(7)-C(8)-O(16), C(9)-C(8)O(16), C(9)-N(10)-N(11), N(11)-C(12)-O(13) and O(13)-C(12)-C(14) in complexes structures as these sites participate in the coordination sphere. • The lower HOMO energy values show that molecules donating electron ability is the weaker. On the contrary, the higher HOMO energy implies that the molecule is a good electron donor. LUMO energy presents the ability of a molecule-receiving electron [25].
(a)
(b)
9
(c)
(d)
(ei)
(eii)
Fig. 2. Molecular structures of (a) MIGP (b) electron density (c) HOMO (d) LUMO (e) the intra-molecular hydrogen bond (i) length and (ii) angle. IR and 1H-NMR spectra of ligands and their metal complexes The IR spectrum of MIGT (Fig. 3) shows a band at 3016 cm-1 assigned to υ(NH)GT vibration [26]. The bands observed at 1708, 1674, 1525 and 993 cm-1 are attributed to υ(C=O)mi, υ(C=O)GT [27], υ(C=N)hy and the hydrazinic υ(N-N) [28] vibrations, respectively.
The bands in the 3492-3323 cm–1 region support the
existence of intra-molecular hydrogen bond. All the band assignments are recorded in table 3.
10
Fig. 3. IR spectrum of MIGT. Table 3 Significant IR spectral bands (cm-1) of the ligands and their metal complexes. Compound No.
υ(NH)hy
υ(C=O)mi
υ(C=O)hy
υ(C=N)
υ(M-N)
υ(M-O)
L1; MIGT
3224
1708
1689
1525
--
--
[Fe(L1)(EtOH)3]Cl4
3207
1722
1683
1533
403
523
[Al(L )Cl2(EtOH)2]Cl2.1.5H2O
3210
1719
1684
1560
398
525
[Sb(L1)Cl2(H2O)]Cl2.2H2O
3201
1714
1686
1518
398
515
[Sn(L1)(EtOH)2(H2O)2]Cl3
3232
1708
1679
1545
448
538
L2; MIGP
3226
1724
1688
1578
--
--
[Fe(L2)Cl(EtOH)2]Cl3
3215
1719
1677
1587
426
539
[Al(L2)Cl2(H2O)2]Cl2.2H2O
3146
1727
1681
1524
398
532
[Sb(L )(EtOH)3(H2O)]Cl4
3218
1709
1689
1542
401
505
[Sn(L2)Cl(H2O)3]Cl2
3183
1701
1691
1527
491
628
1
2
11
The 1H-NMR spectrum of MIGT (Fig. 4) shows a weak singlet signal at δ 12.68 ppm downfield of TMS. This signal is assigned to (NH)GT proton. The multiple signals at δ 7.20–7.64 ppm are attributed to the aromatic C-H of the bisubstituted ring [29]. The signal of the methylene group (CH2) appears at δ 4.99 ppm. The signal at δ 3.38 ppm corresponds to the protons of the aliphatic (CH3)3 [26] where the methyl group of the methylisatin ring is observed at δ 2.51 ppm.
Fig. 4. 1H-NMR spectrum of MIGT. The IR spectrum of MIGP (Fig. 5) shows a medium broad band at 3226 cm-1. This band is due to ν(NH)GP vibration. The strong band and its shoulder at 1688 and 1724 cm-1 are attributed to ν(C=O)GP and ν(C=O)mi vibrations, respectively. The 12
shoulder band at 1578 cm-1 is assigned to ν(C=N)imine vibration. The bands at 680 and 416 cm-1 are attributed to the pyridine ring in plane and out of plane deformation . The weak band at 972 cm-1 is attributed to ν(N-N) vibration. The broad band in the 3461–3405 cm-1 regions is taken as an evidence for the involvement of the NH proton in the formation of intra-molecular hydrogen bonding [30].
Fig. 5. IR spectrum of MIGP. The 1H-NMR spectrum of the ligand (MIGP; Fig. 6) shows a signal at δ 12.8 ppm, downfield relative to TMS, which disappears upon deuteration. This signal is
13
assigned to the (NH)GP proton . The multiple signals at δ 7.21-7.63 ppm are attributed to the aromatic protons. The pyridine protons are represented by the multiple signals at δ8.2-9.1 ppm. The signal due to CH2 protons appears at 6.2 ppm . The methyl protons of the methylisatin ring appear as a singlet signal at δ3.4 ppm.
Fig. 6. 1H-NMR spectrum of MIGP.
14
A careful comparison of the IR spectra of the free ligands and their metal complexes reveals that the ligands coordinate to the metal ions without deprotonation.
Also, they coordinate to the metal ions in a bidentate and/or
tridentate manners through the carbonyl and the azomethine groups. The bands in the 382–492 and 503–526 cm-1 regions are assigned to ν(M–N) [31-33] and ν(M– O) [34-36] vibrations, respectively, which are absent in the free ligand. Mass Spectra The mass spectrum of MIGT (Fig. 7) shows the molecular ion peak at m/z = 311.05 which agree with the molecular formula C14H19ClN4O2; 310.82. Also, the spectrum shows numerous peaks corresponding to the various fragments and their intensity gives an idea on the stability of the fragments. The decomposition steps for the ligand are shown in S 9.
15
Fig. 7. Mass spectrum of MIGT. The mass spectrum of the Sn2+ complex derived from MIGT (Fig. 8) shows the molecular ion peak at m/z = 628.65 (Calcd.: 628.61) which agree with the molecular formulae C18H35Cl3N4O6Sn Scheme (S 10) shows the proposed fragmentation route of the complex.
16
Fig. 8. Mass spectrum of [Sn(L1)(EtOH)2(H2O)2]Cl3. The mass spectrum of MIGP (Fig. 9) shows the molecular ion peak at m/z = 331.4 which agree with the molecular formula, C16H17ClN4O2; 330.80. Also, the mass spectrum shows numerous peaks corresponding to various fragments and their intensity gives an idea on the stability of the fragments. Scheme (S 11) shows the proposed path of the decomposition steps for the ligand (L2; MIGP).
17
Fig. 9. Mass spectrum of MIGP.
The mass spectrum of Sb3+ complex (Fig. 10) shows the molecular ion peak at m/z=715.05, which agree with the molecular formulae C22H35Cl4N4O6Sb; 715.16. Scheme (S 12) shows the proposed fragmentation pattern of the complex.
18
Fig. 10. Mass spectrum of [Sb(L2)(EtOH)3(H2O)]Cl4.
Magnetic moments and electronic spectra of the ligands and their metal complexes The electronic spectra of the ligands show absorption bands at 354 and 340 nm (Table 2). These bands correspond to the transition from the azomethine groups in ligands of the type MIGT and MIGP, respectively. The presence of this band confirms the existence of the ligand in the hydrazo form [37]. The value of magnetic moments for the Fe3+ complexes are µ eff = 5.75 and 5.71 BM indicating a high-spin configuration where the unpaired spin complex has more stable arrangement than the low-spin [38,39]. The electronic spectra of the other complexes show bands due to π→π* and n→π* transitions which are shifted to lower or to higher wavenumber due to the 19
coordination of the ligand to the metal ions through these groups. The complexes are diamagnetic in nature in accordance with the d0 or d10 configuration. Thermogravimetric analysis TGA data of the metal complexes was used as a probe to proof the amounts of solvents (H2O or EtOH) in the coordination sphere or in the crystalline form. The TGA thermogram of the Fe3+ [Fe(L1)(EtOH)3]Cl4 complex, shows three stages of decomposition (S 13). The first step lies in the 206-383 ºC range and represents the loss of the coordinated EtOH molecules and the chloride ions (Found: 44.49 %; Calcd.: 45.81 %). The second step is found in the 384-545 ºC range due to the loss of five CH3 groups, CO2 and N2 with experimental mass loss 24.83 % which is close to the theoretical value 24.08 %). The third stage lies in the 546-756 ºC range is attributed to the loss of C7H4N (Found: 16.66 %; Calcd.: 16.71 %). The residual part of the complex was found to be FeN and one carbon atom with a mass of 14.0 % where the calculated value is 13.39 %. The TGA curve of the Al3+ complex, [Al(L2)Cl2(H2O)2]Cl2.2H2O, shows four stages of decomposition as shown in S 14. The first step lies in the 38-191ºC range corresponds to the loss of two molecules of water of hydration, two molecules of water (coordinated) and the CH3 group (Found: 17.27 %; Calcd.: 16.25 %). The second step is found in the 191-296 ºC range attributes to the loss of 2Cl2 + O2 (observed mass loss 32.03 %; theoretical value 21.41 %). The third 20
step corresponds to the loss of one chloride atom and C5H5 is observed in the 296452 ºC range (Found: 12.87 % ; Calcd.:12.14 % ). The fourth step is found in the 452-642 ºC range attributes to the loss of one chloride atom and C2H3N2. The observed mass loss of this step is 10.48 % (Calcd.: 10.27 %). Finally, the observed residue corresponds the loss of C8H4N and AlN (Found: 27.35 %; Calcd.: 28.93%). Antibacterial and antifungal activity The ligand MIGT reveals a moderate inhibition activity against Salmonella typhimurium on increasing concentration; where MIGP shows no inhibition activity towards any of the used strains of bacteria and fungi (Table 4). The Fe3+ complexes, [Fe(L1)(EtOH)3]Cl4 and
[Fe(L2)Cl(EtOH)2]Cl3, reveal a moderate
inhibition activity towards the Gram (-ve) bacteria Salmonella typhimurium. The Sb3+ complex, [Sb(L2)(EtOH)3(H2O)]Cl4 possess a moderate activity against the Gram (+ve) bacteria; Bacillus subtilis. The other complexes reveal a low and/or no activity towards the entire tested microorganism. The results are shown in table 4.
Table 4 Antibacterial and antifungal activity of the ligands and their metal complexes.
Sample
Conc.
Zone diameter (mm)
21
mg/ml Gram (+ve) bacteria
Gram (-ve) bacteria
Staphylococcus Bacillus
L1; MIGT
0.5
[Fe(L1)(EtOH)3]Cl4
0.5
[Al(L1)Cl2(EtOH)2]Cl2.1.5H2O
0.5
[Sb(L1)Cl2(H2O)]Cl2.2H2O
0.5
[Sn(L1)(EtOH)2(H2O)2]Cl3
0.5
L2; MIGP
0.5
[Fe(L2)Cl(EtOH)2]Cl3
0.5
[Al(L2)Cl2(H2O)2]Cl2.2H2O
0.5
[Sb(L2)(EtOH)3(H2O)]Cl4
0.5
[Sn(L2)Cl(H2O)3]Cl2
0.5
Control
1 1 1 1 1 1 1 1 1 1 0.5 1
Yeast and fungi
Salmonella Escherichia Candida
Aspergillus
aureus
subtilis
typhimurium
coli
albicans
fumigatus
2L 4L
2L
8L 13 I
-
2L
-
2L
-
8L 14 I
2L 4L
-
-
2L
2L 4L
7L 10 L
-
-
3L 5L
4L 6L
-
5L 8L
-
2L
-
3L 5L
3L
4L 7L
3L
-
2L 4L
-
2L
2L
2L
4L 6L
-
-
2L
10 I 18 I
2L 5L
4L 8L
2L
2L
2L 4L
7L 10 L
-
-
3L 5L
4L 6L
14 I 18 I
5L 8L
-
4L 9L
-
3L 5L
3L
4L 7L
3L
-
2L 4L
26 35
25 35
28 36
27 38
28 35
26 37
CONCLUSION
Acknowledgment The authors are thankful to Dr. Z.D. Al-Shafey, Chemistry Department, Faculty of Science, Al-Azhar University, Egypt for supporting during the progress of this work.
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27
GRAPHICAL ABSTRACT
Molecular structures of L2
28
HIGH LIGHTS
•Methylisatin Girard’s T and P hydrazones.
• Biological activity of the ligands and complexes. • Fe3+, Al3+, Sb3+ and Sn2+ complexes. • DFT calculations.
29