CC BY
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ISSN 2522-1841 (Online) ISSN 0005-2531 (Print)
AZERBAIJAN CHEMICAL JOURNAL № 4 2019
27
UDC 541.49 +546.562
Co(II), Ni(II), Cu(II) COMPLEXES WITH 1-NICOTINOIL-2-(2-HYDROXYBENZYL) HYDRAZINE
P.A.Fatullayeva
M.Nagiyev Institute of Catalysis and Inorganic Chemistry, NAS of Azerbaijan
pfatullayeva@mail. ru Received 17.07.2019
By reduction of 1-nicotinoyl-(2-salicylidene)hydrazone with use NaBH41-nicotinoyl-2-(2-hydroxyben-zyl)hydrazine was obtained. Co(II), Ni(II), Cu(II) complexes with these ligands were synthesized and their structure was studied. It was shown that first ligand behaves as a dianionic tridentate, while second is monoanionic tridentate.
Keywords: hydrazides hydrazones, nicotinic acid, metal complexes Co(II), Ni(II), Cu(II). doi.org/10.32737/0005-2531-2019-4-27-31 Introduction
Metal complexes with nicotinoylhydra-zone-o-hydroxyaryl- aldehydes exhibit antioxidant, antimicrobial [1], antituberculosis activity [2], have catalytic activity in the alcohols oxidation [3], epoxidation of olefins [4] and catalyze the reaction of benzoyl chloride with aryl-boronic acid to form fluorenons [5] ].
Nicotinoilsalicylidenehydrazides are potentially dianionic tetradentate ligands, therefore they are capable to forming various mono-, bi- and polynuclear structures with metal ions.
In the present of time, mononuclear oxo-and dioxovanadium complexes [6, 7], mono-, bi-nuclear dioxomolybdenum complexes [3, 7, 8], po-lynuclear zinc complexes [9], mononuclear complexes of V(IV), Mn(III), Ni(II), Cu(II) [1], Ag(I) [10], Fe(III) [11], Pb(II) [12] and Pd(II) are known [5].
Almost in all these complexes, 1-nicotin-oyl-2-salicylidenehydrazone behaves as a tridentate and mono- or dianionic (depending on the nature of the metal ion) ligand. It is noteworthy, that in most cases the pyridine nitrogen atom does not participate in coordination, however, in some cases it enters into coordination with neighboring metal atoms, forming polymeric structures [9].
An analysis of the literature has shown, that so far there have been no publications in the literature on metal complexes with hydra-zones, reduced on the azomethine bond. At the same time, such ligands can be of interest due to their flexible structure. In this work, we obtained 1-nicotinoy-l -2 (2-hydroxybenzyl)hydr-azine, Co(II), Ni(II), Cu(II) complexes with this ligand and studied their structure and properties.
Experimental part
Nicotinoylhydrazide bought from the firm "Sigma Aldrich"
1-nicotinoyl-(2-salicylidene)hydrazone (I).
10-3 mol (0.137 g) of nicotinoilhydrazide was dissolved in 15 ml of dioxane and there solution of 10-3mol (0.122 g) of salicylic aldehyde in 10 ml methanole was added. The mixture was stirred jn the magnetic stirrer at 400C for 20 minutes. After cooling the solution bright yellow Schiff base I crystals precipitated, which were filtered and dried, m.p. = 2220C.
Cu(II) complex with ligand 1-nicotinoyl-(2-salicylidene)hydrazone (I). 10-3mol (0.241 g) of the hydrazone (I) was dissolved in 10 ml of di-oxane, and there a solution of 10-3mol (0.199 g) of copper(II) acetate in 10 ml of water was added. The mixture was heated at 500C for 20 min, then the solution was filtered. After cooling dark green crystals with a melting point >2500C dropped out.
The Co(II) and Ni(II) complexes were obtained similarly.
Reduction of 1-nicotinoyl-(2-salicylide-ne)hydrazone (I). 0.1 mol of 1-nicotinoyl-2-sa-licylidene) hydrazone was suspended in 40 ml of methanol and there added in small portions of 0.15 mol of sodium borohydride with at intensive stirring. After adding the whole amount of NaBH4, stirring was continued for 0.5 hour, then the colorless solution was diluted three times with water and acidified with a solution of HCl (~10%) to pH ~7.5. The dropped out substance was separated on a porous filter, washed by water, dried and recrystallized from mixture ethanol-water 1:1. After drying under vacuum, Tmelt > 2500C.
Cu(II) complex with 1-nicotinoyl-2-(2-hydroxybenzyl) hydrazine (II). 10-3 mol (0.243 g) 1-nicotinoyl-2-(2-hydroxybenzyl)hydrazine(n), dissolved in 30 ml of ethanol, mixed with a methanol solution of 1103mol (0.199 g) of Cu (CH3COOVH2O. After some time, dark blue small crystals dropped out, which was separated and dried. The melting point is > 2500C.
Calculated% C 49.38, H 4.12, O 17.56, N 11.52, Cu 17.42. C^H^O^Cu.
Found, %: C 49.40, H 4.17, O 17.46, N 11.59, Cu 17.32.
The Co(II) and Ni(II) complexes were obtained similarly to the copper complex with using cobalt and nickel tetrahydrate acetate.
Calculated, % : C 50.09, H 4.17, O 17.78, N 11.67, Co 16.37( C15H15O4N3C0).
Found, % : C 50.08, H 4.19, O 17.83, N 11.71, Co 16.42.
Calculated,%: C 50.04, H 4.17, O 17.79, N 11.68, Ni 16.3. C15H15O4N3NL
Found, %: C 50.08, H 4.12, O 17.81, N 11.70, Ni 16.45.
A fine crystalline precipitate of brown and green color, respectively, precipitated from
the resulting solutions, which were separated and dried in vacuum.
Results and discussion
We have synthesized for the first time1-nicotinoyl-2-(2-hydroxybenzyl)hydrazine (II) by reducing of 1-nicotinoyl-(2-salicylidene)hydra-zone (I) with using sodium borohydride and its complexes with Co(II), Ni(II), Cu(II). For comparison the Co(II), Ni(II), Cu(II) complexes without reduced ligand I were received and studied.
The IR spectrum the reduced hydra-zone(II) (Figure 1) contains an intense absorption band at 3360 cm-1, related to stretching vibrations of N-H and also band of vibrations of amide carbonyl group at 1662 cm-1. The absorption band at 1620 cm-1, which is observed in the Schiff base I, is absent in the reduced ligand II. It should be noted the absence in the IR spectrum of the Schiff base of the absorption band of the carbonyl amide group at -1660 cm-1, which undoubtedly is result of strong shift of keto-enol equilibrium towards the formation of the enol form (compound Ib):
Fig.1. IR spectra 1-nicotinoyl-(2-salicyli-dene)hydrazone (I) and 1-nicotinoyl-2-(2-hydroxybenzyl) hydrazine (II) (dashed line).
4000 3S00 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 V, CIT1
Electronic absorption spectra of hydrazine I and reduced hydrazone II (Figure 2) confirm the predominant presence of the enol form in compound I. The long-wavelength absorption band at 360 nm in compound I can be attributed to the C = N-N = C fragment, conjugated with aromatic rings and the band at 300 nm - to absorption due to aromatic rings. In the reduced compound II, the absorption band of the aromatic rings is shifted to the shortwave region and is observed at 280 nm.
The obtained date allows us to accept the structure (IV) for these complexes.
HO
III
A
3 1
200 240 280 320 X, nm
360 400
Fig. 2. Electronic absorption spectra of compounds I and II in ethanol.
The IR spectra of metal complexes (Cu(II), Co(II) and Ni(II)) with hydrazine I contain the absorption band of the azomethine group at 1615-1630 cm-1 and do not contain the absorption band of amide carbonyl at -1660 cm-1. This confirms his participation in coordination with the metal ion in the enolic form. There is also an absorption peak at 3400 cm-1 related to coordinated water.
Thus, the data of elemental analysis and IR spectroscopy suggest the following structure for metal complexes with ligand I (structure III).
In the IR spectra of a nickel (II) complex with a reduced ligand II, the amide carbonyl band observed in the starting ligand at 1666 cm-1 shifts towards lower frequencies. The presence of this band and its shift during complexation indicate its participation in coordination in the keto-form. This, in turn, is evidence that the ligand in this case is monoanionic. In addition, the IR spectrum of this complex contains absorption bands of the carboxylate group at 1580 and 1420 cm-1.
nh-ch2-I
Ni —
I
O-O
\ /
O
IV
M= Co(II),Ni(II), Cu(II)
Thus, it has been shown that nicotinoyl-hydrazone of salicylic aldehyde can be reduced to the corresponding nicotinoil 2-hydroxyben-zyl hydrazide. Studies have also shown the different nature of coordination of 1-nicotinoyl-2-salicylidenehydrazone and its reduced analogue 1-nicotinoyl-2-(2-hydroxybenzyl)hydrazine. If in the first case the ligand behaves as dianionic tri-dentate, in the second case it is monoanionic tridentate.
A number of works are known in which it has been shown that carbohydrate hydrazides, hydrazones carboxylic acids possess bactericidal and fungicidal properties [1, 2].
However, hydrazones and their complexes reduced by the azomethine group have not been studied yet in this respect. We have shown the bactericidal and fungicidal properties of 1-ni-cotinoyl-2-(2-hydroxybenzyl)hydrazine (II) and its Co(II) complex (see table).
It can been seen from table, that 1-ni-cotinoyl-2-(2-hydroxybenzyl)hydrazine (II) showed the high fungicidal and bactericidal activity. The Co(II) complex showed only bactericidal activity.
Antimicrobial properties of 1-nicotinoyl-2-(2-hydroxybenzyl) hydrazine (II) and its Co(II) complex
Conc, at % The diameter of the zone of inhibition, cm
Chemical formula Bacterium in the environment of MPA (meat-peptide agar) agar mushrooms
1 0.5 2.0-2.2 1.6-1.8 1.0-1.2 0.8-1.0
0.25 1.4 -1.4 + +
1.0 \ /T^V^A / 1.8-2.0 + + +
0.5 \,_/ II i \ // N-' O- Co-O—-' 1.6-1.6 + + +
0.25 O,O CH3_C 1.2 -1.3 + + +
+ - the absence of activity
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1-NÍKOTÍNOÍL-2-(2-HÍDROKSÍBENZÍL)HÍDRAZÍNÍN Co(II), Ni(II), Cu(II) KOMPLEKSLORÍ
P.A.Fatullayeva
1-nikotinoil-2(caliciliden)hidrazonun(I) NaBH4 vasitaci ila reduksiyasi yolu ila 1-nikotinoil-2-hidroksibenzil)hidrazin alinmiíjdir. Bu liqandla Co(II), Ni(II), Cu(II) komplekslari sintez olunmu§ va onlarin quruluíju óyranilmiíjdir Góstarilmi§dir ki, 1-nikotinoil-2-(caliciliden) hidrazon (I) ozünü dianion tridentat liqand kimi, 1-nikotinoil-2-(2-hidroksibenzil)hidrazin(II) ozunu monoanion tridentat liqand kimi aparir.
Agar sozlar: nikotin tur§usunun hidrazidbri, hidrazonlarin reduksiyasi, metal komplekslari.
КОМПЛЕКСЫ Co(II), Ni(II), Cu(II) С 1-НИКОТИНОИЛ-2-(2-ГИДРОКСИБЕНЗИЛ) ГИДРАЗИНА
П.А.Фатуллаева
Восстановлением 1-никотиноил-(2-салицилиден)гидразона c помощью NaBH4 получен 1-никотиноил-2-(2-гидроксибензил)гидразин. Синтезированы комплексы Co(II), Ni(II), Cu(II) с этими лигандами и изучено их строение. Показано, что первый ведет себя как дианионный тридентатный, в то время как второй - моноанионный тридентатный лиганд.
Ключевые слова: гидразиды HUKomunoeou кислоты, восстановление гидразонов, комплексы металлов.
