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Abstract
Metal complexes of Schiff base derived from condensation of o-vanilin (3-methoxysalicylaldehyde) and sulfametrole [N1 -(4-methoxy-1,2,5-
thiadiazole-3-yl)sulfanilamide] (H2 L) are reported and characterized based on elemental analyses, IR, 1 H NMR, solid reflectance, magnetic
moment, molar conductance, mass spectra, UV–vis and thermal analysis (TGA). From the elemental analyses data, the complexes were pro-
posed to have the general formulae [M2 X3 (HL)(H2 O)5 ]·yH2 O (where M = Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II), X = Cl, y = 0–3);
[Fe2 Cl5 (HL)(H2 O)3 ]·2H2 O; [(FeSO4 )2 (H2 L)(H2 O)4 ] and [(UO2 )2 (NO3 )3 (HL)(H2 O)]·2H2 O. The molar conductance data reveal that all the metal
chelates were non-electrolytes. The IR spectra show that, H2 L is coordinated to the metal ions in a tetradentate manner with ON and NO donor sites
of the azomethine-N, phenolic-OH, enolic sulphonamide-OH and thiadiazole-N. From the magnetic and solid reflectance spectra, it is found that
the geometrical structures of these complexes are octahedral. The thermal behaviour of these chelates shows that the hydrated complexes losses
water molecules of hydration in the first step followed immediately by decomposition of the anions and ligand molecules in the subsequent steps.
The activation thermodynamic parameters, such as, E* , H* , S* and G* are calculated from the DrTG curves using Coats–Redfern method. The
synthesized ligand, in comparison to their metal complexes also were screened for their antibacterial activity against bacterial species, Escherichia
coli, Salmonella typhi, Bacillus subtillus, Staphylococcus aureus and Fungi (Aspergillus terreus and Aspergillus flavus). The activity data show
that the metal complexes to be more potent/antimicrobial than the parent Shciff base ligand against one or more microbial species.
© 2006 Elsevier B.V. All rights reserved.
Keywords: Sulphametrole; o-Vanilin; Transition metal complexes; IR; 1 H NMR; Conductance; Solid reflectance; Magnetic moment; Thermal analysis; Biological
activity
1386-1425/$ – see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.saa.2006.04.033
950 G.G. Mohamed, C.M. Sharaby / Spectrochimica Acta Part A 66 (2007) 949–958
(−1 mol−1
used included absolute ethyl alcohol, diethylether, and dimethyl-
formamide (DMF). These solvents were either spectroscopic
9.87
11.12
15.26
13.70
16.32
7.78
13.03
14.88
12.04
cm2 )
Ωm
–
pure from BDH or purified by the recommended methods [4]
and tested for their spectral purity. Hydrogen peroxide, sodium
(B.M.)
chloride, sodium carbonate and sodium hydroxide (A.R.) were
Diam.
Diam.
Diam.
5.39
5.62
5.24
5.20
3.67
2.10
μeff
used. Hydrochloric and nitric acids (MERCK) were used. De-
–
ionized water collected from all glass equipments was usually
used in all preparations.
13.78 (13.99)
14.68 (14.22)
14.56 (14.04)
14.92 (15.31)
16.56 (16.07)
16.23 (15.95)
17.07 (17.44)
26.35 (26.74)
2.2. Instruments
–
M
The spectrophotometric measurements in solution were car-
15.62 (15.25)
15.78 (16.11)
ried out using automated spectrophotometer UV–vis Perkin-
8.47 (8.03)
9.03 (8.92)
8.18 (8.33)
9.13 (8.71)
7.78 (8.03)
8.36 (8.58)
7.82 (7.63)
5.50 (5.65)
Elmer Model Lambda 20 ranged from 200 to 900 nm. The molar
conductance of solid complexes in DMF was measured using
Sybron–Barnstead conductometer (Meter-PM.6, E = 3406). Ele-
S
mental microanalyses of the separated solid chelates for C,
13.03 (13.23)
H, N and S were performed in the Microanalytical Center,
6.84 (7.02)
7.73 (7.80)
6.85 (7.04)
7.60 (7.28)
7.42 (8.71)
7.43 (7.03)
7.85 (7.51)
6.39 (6.66)
8.42 (8.63)
Cairo University. The analyses were repeated twice to check
the accuracy of the data. Infrared spectra were recorded on a
Perkin-Elmer FT-IR type 1650 spectrophotometer in wave num-
N
ber region 4000–200 cm−1 . The spectra were recorded as KBr
4.21 (3.84)
3.11 (3.16)
3.80 (3.48)
3.32 (3.04)
3.59 (3.80)
3.76 (3.44)
3.56 (3.92)
3.69 (3.35)
2.64 (3.00)
1.46 (1.86)
discs. The solid reflectance spectra were measured on a Shi-
madzu 3101pc spectrophotometer. The molar magnetic suscep-
tibility was measured on powdered samples using the Faraday
H
method. The diamagnetic corrections were made by Pascal’s
% Found (calcd.)
White (88)
[Cu2 Cl3 (HL)(H2 O)5 ]·3H2 O, C17 H31 Cl3 Cu2 N4 O13 S2
[Fe2 Cl5 (HL)(H2 O)3 ]·2H2 O, C17 H25 Cl5 Fe2 N4 O10 S2
1155 cm−1 (νasym (SO2 )) and (νsym (SO2 )), respectively. In the the metal complexes. These shifts refer to the coordination
complexes, the asymmetric and symmetric modes are shifted through thiadiazole-N atom. The IR bands at 812–850 and
to 1312–1322 and 1115–1137 cm−1 , respectively, upon coordi- 780–796 cm−1 , υ(H2 O) of coordinated water, is an indication
nation to the transition metals [6–9]. The blue shift of the SO2 of the binding of the water molecules to the metal ions. New
stretching vibration to lower frequencies may be attributed to the bands are found in the spectra of the complexes in the regions
transformation of the sulfonamide ( SO2 NH) to give the enol 520–586, which are assigned to υ(M O) stretching vibrations.
form ( SO(OH) N) as a result of complex formation to give The bands at 434–466 have been assigned to υ(M N) mode
more stable six-membered ring [9–12]. [13].
A sharp band due to the υ(C N) stretching vibration Therefore, from the IR spectra, it is concluded that H2 L ligand
of thiadiazole ring appeared at 1570 cm−1 in H2 L ligand. behaves as a uni-negtively tetradentate ligand coordinated to the
This band is shifted to 1231–1274 cm−1 in the spectra of metal ions via the azomethine-N, deprotonated phenolic-O, eno-
G.G. Mohamed, C.M. Sharaby / Spectrochimica Acta Part A 66 (2007) 949–958 953
Table 2
IR spectra (4000–400 cm−1 ) of the H2 L ligand and its metal complexes
Compound ν(NH) ν(OH) ν(SO2 ) ν(SO2 ) ν(CH N) ν(C O) ν(C N) ν(H2 O) ν(M O) ν(M N)
enolic (asym) (sym.) azome- phenolic thiodiaza (coord.)
thine
3.2.4. Magnetic susceptibility and electronic spectra [Cd2 Cl3 (HL)(H2 O)5 ] 3.33 s, coordinated water
4.00 s, 6H, 2 OCH3
measurements
6.00 brs, 1H, OH-enolic
The UV–vis spectra of the ligand and the complexes were (exchangeable with D2 O)
recorded in DMF solution in the wavelength range from 200 to 6.56 d, 2H, ArH’s, J = 8.70 Hz
800 nm. The spectra showed a sharp and intense band at 207 nm 6.97 m, 2H, vanillin-H
which is attributed to –* transition within the benzene ring 7.45 m, 1H, vanillin-H
7.56 d, 2H, ArH’s, J = 8.70 Hz
of the ligand molecule. This band is red shifted to 221–237 nm.
9.78 s, 1H, CH N
The two bands observed at 302 and 345 nm in the free ligand
954 G.G. Mohamed, C.M. Sharaby / Spectrochimica Acta Part A 66 (2007) 949–958
are reasonably accounted for –* and n–* transitions for the try [17]. The electronic spectrum of the Co(II) complex give
phenolic-OH and azomethine moieties, respectively. The blue or three bands at 15,576, 17,467 and 21,930 cm−1 wave num-
red shifts of these bands in the regions 295–305 and 331–365 nm ber regions. The bands observed are assigned to the tran-
with respect to the ligand depend on the type of metal ions coor- sitions 4 T1g (F) → 4 T2g (F) (ν1 ), 4 T1g (F) → 4 A2g (F) (ν2 ) and
4 T (F) → 4 T (P) (ν ), respectively, suggesting that there is an
dinated to the ligand and indicated coordination of phenolic-OH 1g 2g 3
and azomethine moieties to the metal ions. The spectra of the octahedral geometry around Co(II) ion [18–20]. The magnetic
complexes further display a bands in the range 413–495 and susceptibility measurements lie at 5.20 B.M. (normal range for
559–642 nm, which might be assigned to charge transfer transi- octahedral Co(II) complexes is 4.3–5.2 B.M.), is an indicative
tion from the ligand to metal ions (L → M) [12]. of octahedral geometry [21]. The region at 24,390 cm−1 refers
From the diffuse reflectance spectrum it is observed that, the to the charge transfer band.
Fe(III) chelate exhibit a band at 20,942 cm−1 , which may be The Ni(II) complex reported herein has a room temperature
assigned to the 6 A1g → T2g (G) transition in octahedral geometry magnetic moment value of 3.67 B.M.; which is in the normal
of the complexes [14]. The 6 A1g → 5 T1g transition appears to be range observed for octahedral Ni(II) complexes (μeff = 2.9–3.3
split into two bands at 17,467 and 15,174 cm−1 . The observed B.M.) [17]. This indicates that, the complexes of Ni(II) are
magnetic moment of Fe(III) complex is 5.62 B.M. Thus, the six coordinate and probably octahedral [22]. The electronic
complexes formed have the octahedral geometry [15]. The spec- spectrum, in addition to show the –* and n–* bands of
trum shows also a band at 28,531 cm−1 which may attribute to free ligands, displays three bands, in the solid reflectance
ligand to metal charge transfer. The diffuse reflectance spec- spectrum at ν1 : 15,698 cm−1 : 3 A2g → 3 T2g ; ν2 : 17,422 cm−1 :
3 A → 3 T (F) and ν : 20,202 cm−1 : 3 A → 3 T (P). The
trum of the Mn(II) complex shows three bands at 15,873, 21,739 2g 1g 3 2g 1g
and 27,77 cm-1 assignable to 4 T1g → 6 A1g , 4 T2g (G) → 6 A1g and spectrum shows also a band at 23,255 cm-1 which may attribute
4 T (D) → 6 A to ligand to metal charge transfer. The reflectance spectrum of
1g 1g transitions, respectively [16]. The magnetic
moment value is 5.24 B.M. which indicates the presence of Cu(II) chelat consists of a broad, low intensity shoulder band
Mn(II) complex in octahedral structure. centered at 16,537 and 17,467–22,422 cm−1 . The 2 Eg and 2 T2g
The electronic spectrum of the Fe(II) complex displays two states of the octahedral Cu(II) ion (d9 ) split under the influ-
absorption bands at 15,480 and 17,376 cm−1 which are assigned ence of the tetragonal distortion and the distortion can be such
to 5 T2g → 5 Eg transitions [17]. Also the band at 23,255 cm−1 as to cause the three transitions 2 B1g → 2 B2g ; 2 B1g → 2 Eg and
2B → 2A
is assigned to L → M charge transfer. The observed magnetic 1g 1g to remain unresolved in the spectra [23]. It is
moment of 5.39 B.M. is consistent with an octahedral geome- concluded that, all three transitions lie within the single broad
Table 4
Thermogravimetric data of H2 L metal complexes
Complex TG range DTGmax (◦ C) na % Found (calcd.) Assignment Metallic
(◦ C) residue
Mass loss Total mass
loss
envelope centered at the same range previously mentioned. The the removal of the organic part of the ligand leaving metal oxide
magnetic moment of 2.10 B.M. falls within the range normally as a residue. The overall weight loss amounts to 79.58% (calcd.
observed for octahedral Cu(II) complexes [24]. A moderately 79.99%).
intense peak observed at 23,364 cm−1 is due to ligand–metal The TGA curves of the Co(II) and Cu(II) chelates show four
charge transfer transition [25]. stages of decomposition within the temperature range of 30–650
The complexes of Zn(II), Cd(II) and UO2 (II) are diamagnetic. and 30–750 ◦ C, respectively. The first stage at 30–100 ◦ C cor-
In analogy with those described for Zn(II) complexes containing responds to the loss of water molecules of hydration. The
N–O donor Schiff bases [26–28] and according to the empirical energy of activation for this dehydration step was 39.02 and
formulae of these complexes, we proposed an octahedral geom- 63.85 kJ mol−1 for Co(II) and Cu(II) complexes, respectively.
etry for these three complexes. While the subsequent (second, third and fourth) stages involve
the loss of 1–3HCl, 3–5H2 O, 1/2H2 , O2 and ligand molecules
4. Thermal analyses (TGA and DrTG) with a mass loss of 76.68% (calcd. 75.99%) and 76.29% (calcd.
75.17%) for Co(II) and Cu(II) complexes, respectively. The
In the present investigation, heating rates were suitably overall weight loss amounts to 80.84% (calcd. 80.66%) and
controlled at 10 ◦ C min−1 under nitrogen atmosphere and the 83.24% (calcd. 81.94%) for Co(II) and Cu(II) chelates, respec-
weight loss was measured from the ambient temperature up to tively.
∼
=1000 ◦ C. The data are listed in Table 4. The weight losses for On the other hand [(FeSO4 )2 (H2 L)(H2 O)4 ] chelate exhibits
each chelate were calculated within the corresponding tempera- four decomposition steps. The first step in the temperature
ture ranges. The different thermodynamic parameters are listed range 30–250 ◦ C (mass loss = 8.92%; calcd. for 4H2 O; 9.03%)
in Table 5. may accounted for the loss of water molecules of coordi-
The thermogram of [Fe2 Cl5 (HL)(H2 O)3 ]·2H2 O chelate nation. The energy of activation for these steps was 53.25
shows four decomposition steps within the temperature range and 82.37 kJ mol−1 for the first and second steps, respec-
30–700 ◦ C. The first two steps of decomposition within the tively. As shown in Table 4, the mass losses of the remain-
temperature range 30–250 ◦ C correspond to the loss of water ing decomposition steps amount to 52.60% (calcd. 52.82%).
molecules of hydration, 5HCl, 1/2H2 and 1.5O2 gases with a They correspond to the removal of H2 L molecules leaving
mass loss of 33.70% (calcd. 33.46%). The energy of activation FeSO4 as a residue. The energy of activation for these steps
was 44.40 and 78.24 kJ mol−1 for the first and second steps, was 132.4 and 176.9 kJ mol−1 for the third and fourth steps,
respectively. The subsequent steps (250–700 ◦ C) correspond to respectively.
Table 5
Thermodynamic data of the thermal decomposition of H2 L metal complexes
Complex Decomp. E* A (s−1 ) S* H* G*
temperature (kJ mol−1 ) (J K−1 mol−1 ) (kJ mol−1 ) (kJ mol−1 )
(◦ C)
[Ni2 Cl3 (HL)(H2 O)5 ] complex was thermally decomposed vation energies were 75.98 and 137.4 kJ mol−1 for the second
in three decomposition steps within the temperature range of and third steps, respectively.
30–800 ◦ C. The first decomposition step with an estimated mass The TGA curve of the UO2 (II) chelate represent four decom-
loss of 26.68% (calcd. mass loss = 27.03%) within the tempera- position steps as shown in Table 4. The first step of decom-
ture range 30–140 ◦ C, may be attributed to the liberation of the position within the temperature range 30–130 ◦ C corresponds
3HCl and C2 H3 NOS. The activation energy was 22.95 kJ mol−1 . to the loss of hydrated water molecules with a mass loss of
The remaining decomposition steps (two steps) found within 2.82% (calcd. for 2H2 O; 3.00%). The energy of activation for
the temperature range 140–800 ◦ C with an estimated mass loss this dehydration step was 51.18 kJ mol−1 . The remaining steps
of 41.14% (calcd. mass loss = 40.57%) which are reasonably of decomposition within the temperature range 130–1000 ◦ C
accounted for by the removal of H2 L ligand as gases. The acti- correspond to the removal of H2 L ligand as gases with an
Table 6
Antimicrobial activity of H2 L and corresponding metal complexes
Samples Concentration Test organisms
(mg/mL)
Escherichia Salmonella Staphylococcus Bacillus Aspergillus Aspergillus
coli typhi aureus subtillus terreus flavus
1 ++ ++ + ++ + +
H2 L 2.5 ++ +++ ++ ++ + +
5 +++ +++ ++ ++ + +
1 + ++ + ++ 0 +
[Fe2 Cl5 (HL)(H2 O)3 ]·2H2 O 2.5 ++ +++ ++ ++ 0 +
5 ++ +++ ++ ++ + +
1 + + + + + +
[(FeSO4 )2 (H2 L)(H2 O)4 ] 2.5 + + + + + +
5 + ++ ++ ++ + +
1 + + + ++ + +
[Co2 Cl3 (HL)(H2 O)5 ]·2H2 O 2.5 ++ ++ + ++ ++ ++
5 ++ +++ ++ +++ ++ ++
1 + + ++ + + +
[Ni2 Cl3 (HL)(H2 O)5 ] 2.5 + + ++ + + +
5 + ++ ++ + + +
1 + ++ + + + +
[Cu2 Cl3 (HL)(H2 O)5 ]·3H2 O 2.5 ++ +++ + + + +
5 ++ +++ + + + +
1 ++ +++ + ++ + 0
[Zn2 Cl3 (HL)(H2 O)5 ] 2.5 +++ +++ + ++ + 0
5 +++ +++ ++ ++ + +
1 ++ +++ + ++ + +
[Cd2 Cl3 (HL)(H2 O)5 ] 2.5 +++ +++ + ++ + +
5 +++ +++ ++ ++ ++ ++
1 ++ + + + 0 +
[(UO2 )2 (HL)(NO3 )3 (H2 O)]·2H2 O 2.5 ++ + + + + +
5 +++ ++ + + + +
1 ++ +++ ++ ++ +++ +++
St. 2.5 +++ +++ ++ +++ +++ +++
5 +++ +++ +++ +++ +++ +++
St., reference standard; chloramphenicol was used as a standard antibacterial agent and grisofluvine was used as a standard antifungal agent. The test was done using
the diffusion agar technique. Inhibition values = 0.1–0.5 cm beyond control = +; inhibition values = 0.6–1.0 cm beyond control = ++; inhibition values = 1.1–1.5 cm
beyond control = +++; inhibition values > 1.5 cm beyond control = ++++; 0 = not detected. Well diameter 1 cm (100 l of each conc. was tested).
958 G.G. Mohamed, C.M. Sharaby / Spectrochimica Acta Part A 66 (2007) 949–958
cluded that H2 L behaves as a uninegatively tetradentate ligand [3] P. Nagpal, R.V. Singh, Appl. Organometal. Chem. (2004) 221.
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