Printer Friendly

Synthesis, Crystal Structure and Bioactivity of Copper Complex with bi-[N-(propionic acid)] terephthalal diacythydrazon.

Byline: Fengying Chen, Wangting Wu and Shuiyang He

Summary: A new Cu(II) complex with bi-[N-(propionic acid)] terephthalal diacythydrazon (H4L) was obtained by the reaction of CuCl2*2H2O and H4L in 1:1 pyridine and methanol. According to X-ray diffraction, the product was a binuclear complex, [Cu2L(pyridine)6]*2H2O. Each Cu(II) in the complex is six-coordinated by one N and two O atoms of H4L and three N atoms from pyridine. The coordination polyhedron around Cu(II) can be described as an octahedron with slightly distorted. Inaddition, antibacterial activities of the complex against coliform were investigated. The results showed that the inhibit rates of binuclear complex were 83% against coliform.

Keywords: Binuclear complex, Bioactivity, Coliform, Diacythydrazon.

Introduction

In terms of coordination chemistry, the dicarboxylic acid with aromatic ring can increase the thermal stability and rigidity of the coordination polymer frame structure by coordination with metal ions in many different modes, such as multi-tooth chelating, bridging, and mono-dentate and so on. In this way, it can adjust the distance between the aromatic ring and carboxyl group [1-3]. Addition of acyl groups to dicarboxylic acid can provide potential coordination atoms or super molecular identification points. Therefore, the synthesis of aromatic carboxylic acid ligands is one of the research hotspots in coordination chemistry and supramolecular chemistry [4-6]. Because of aromatic hydrazone ligands have excellent pharmaceutical and physiological activities, it has been widely studied in the field of antibacterial, anticancer and antiviral activities [7-11].

In addition, the metabolic products of aromatic hydrazone were of low toxicity or non - toxicity, which makes it has potential application in the field of medicine and pesticide. In this paper, a new Cu(II) complex with bi-[N-(propionic acid)] terephthalal diacythydrazon (H4L) was synthesized, and the antibacterial activities of the complex against coliform and wheat rust were investigated, respectivly.

Experimental

Materials and Measurements

H4L was prepared according to the literature method [12] in our laboratory. All reagents were commercial grade and were used as received. The X-ray data for the crystals were collected on a Bruker Smart-1000 CCD X-ray single-crystal diffractometer. UV spectra were obtained by a Lambda 40P UV-vis spectrophotometer.

Preparation of the Complex

H4L (2 mmol) were dissolved in 10 mL pyridine to obtain a yellow solution and a solution of CuCl2*2H2O (1 mmol) in 10 mL MeOH water was added with continuous stirring. Then the mixture was refluxed for 2 h then filtrated. After about two weeks at room temperature, dark green prism-shaped single crystals suitable for X-ray diffraction were obtained from mother solution. IR(KBr), /cm-1: as(COO-) 1612, s (COO-) 1343, (C=O) 1650, (C=N) 1523.

Crystal Structure Determination and Refinement

A dark green crystal of the complex was mounted on a Bruker Smart-1000 CCD diffractometer (Germany). Intensities of reflections were measured at 298 K under graphite monochromatized Mo K[alpha] radiation(I>>=0.071073 nm) using the -I scan technique. Empirical absorption correction was applied via SABADS program [13].

The crystal structure of complex was solved by direct method and Fourier-difference synthesis. Data processing was performed via the SAINT processing program [14]. All the non-hydrogen atoms were refined anisotropically. Full matrix least-squares refinement on F2 was performed by means of SHELXL-97 program package [15]. The crystal data and structure refinement parameters can be seen in Table 1.

Table-1: Crystal data and corresponding refinement parameters.

###Empirical formula###C44H40Cu2N10O8

###Formula weight###963.96

###Temperature###298 K

###Wavelength###0.71073 A

###Crystal system /space

###Monocline /P2(1)/c

###group

###a = 15.655(3) A b = 19.723(4) A c =

###Unit cell dimensions###16.436(3) A

###[alpha]= 90o [beta]= 107.63(3)o###I3= 90o

###Volume###4836.4(17) A 3

Z, Calculated density###4 1.373 Mg/m3

Absorption coefficient###0.995 mm-1

###F(000)###2052

###Crystal size###0.32 x 0.28 x 0.14 mm

Theta range for data

###3.15 to 25.10 deg.

###collection

###Limiting indices###-18<=h<=18 -23<=k<=23 -19<=l2sigma(I)]

###R indices (all data)###R1 = 0.0909 wR2 = 0.2275

Bioactivity Experiment

Coliform was used to test the bioactivities of the complex [Cu2L(pyridine)6]*2H2O by turbidimetry/spectrometry method [16] and the growth curves of coliform as well as the inhibitor rate curves in the absence and presence of complex were studied. The LB culture medium was prepared by mixing 2 g peptone, 1 g yeast, 1 g NaCl, and 200 mL H2O at 80, then cool to use. The experiment route was as follows: mixing 10 mL LB culture medium, 10 uL coliform solution, and 1 mL solution of [Cu2L(pyridine)6]*2H2O (0.25%) together a placing them on the rocking bed and cultivated at 37 a measuring OD of the sample every 3 h a calculating inhibitor rate a drawing growth curves of coliform and inhibitor rate curves. The calculate method is following:

inhibitor rate(%) = [OD(CK) - OD(sample)]/OD(CK) x 100%

Note: Here the CK sample is prepare by mixing 10 mL LB culture medium, 10 uL coliform solution, and 1 mL distilled water.

Results and Discussion

Structure of [Cu2L(pyridine)6]*2H2O

The data listed in Table-2 were selected bond lengths and bond angles of [Cu2L(pyridine)6]*2H2O. The molecular structure with atoms labeling and the packing of the molecules in the crystal lattice were shown in Fig. 1 and Fig. 2, respectively.

The structural study reveals that the complex consists of a neutral [Cu2L(pyridine)6] unit and two lattice water molecules. The ligand connects two Cu(II) by trans-linking. The coordination environments of two center copper(II) are very similar, only the data of the bond lengths and bond angles have slightly difference. The center Cu(II) is six-coordinated, bonded to three coordinating atoms [O2N] from the H4L ligand, three nitrogen atoms from pyridine. The coordination polyhedron around Cu(II) can be described as an octahedron with slightly distorted. O(2), O(3), N(3) and N(4) are approximately coplanar for Cu(1) to form the equatorial plane. N(2) and N(1) occupy axial sites for Cu(1) with bond angle N(2)-Cu(1)-N(1) being 177.37(15)Adeg. The equatorial plane was formed by O(4), Cu(2), N(7), O(5) and N(9), while N(10) and N(8) occupy axial sites with bond angle N(8)-Cu(2)-N(10) being 175.28(16)Adeg.

The Cu(1)-N(4) distance is 1.968(4) A and the distance to the pyridine donors N(1), N(2) and N(3) are 2.173(4) A, 2.162(4) A and 2.049(4) A, respectively. Owing to chelating strain, the bond distances N(4)-Cu(1) and N(7)-Cu(2) are shorter than those of pyridine donors.

There are two lattice water in the molecule, which provides potential super identification point for the carboxyl oxygen at both ends of the complex molecule. The adjacent binuclear complexes are linked by the O-H...O hydrogen bond between the carboxyl oxygen and the lattice water oxygen, which assembled the complex into 1-D supramolecular chain along a - axis(Fig.2).

Along the b-axis, There is a weak hydrogen bond O-H...C between the lattice water and the carbon on the pyridine ring and a weak I-I interaction between adjacent pyridine rings. Thus, the two kinds of weak interactions linked the complex to form a 2D supramolecular network along b-axis(Fig.3).

Table-2: Selected bond lengths (A) and bond angles (Adeg).

###Bond lengths###Bond angles

N(4) - Cu(1)###1.968(4)###N(3)-Cu(1)-N(4)###177.06(16)###N(7)-Cu(2)-N(9)###178.62(16)

N(3) - Cu(1)###2.049(4)###O(3)-Cu(1)-N(4)###77.99(13)###N(7)-Cu(2)-O(4)###77.66(14)

O(3) - Cu(1)###2.075(3)###O(3)-Cu(1)-N(3)###99.57(15)###N(9)-Cu(2)-O(4)###101.94(14)

O(2) - Cu(1)###2.098(3)###O(2)-Cu(1)-N(4)###78.62(14)###N(7)-Cu(2)-O(5)###78.38(14)

N(2) - Cu(1)###2.162(4)###N(3)-Cu(1)-O(2)###103.84(15)###N(9)-Cu(2)-O(5)###102.01(15)

N(1) - Cu(1)###2.173(4)###O(3)-Cu(1)-O(2)###156.59(12)###O(4)-Cu(2)-O(5)###156.04(13)

N(7) - Cu(2)###1.963(4)###N(4)-Cu(1)-N(2)###91.51(16)###N(7)-Cu(2)-N(10)###93.08(16)

N(9) - Cu(2)###2.072(4)###N(3)-Cu(1)-N(2)###90.15(16)###N(9)-Cu(2)-N(10)###88.25(16)

O(4) - Cu(2)###2.095(3)###O(3)-Cu(1)-N(2)###90.49(14)###O(4)-Cu(2)-N(10)###91.18(15)

O(5) - Cu(2)###2.100(3)###O(2)-Cu(1)-N(2)###88.99(15)###O(5)-Cu(2)-N(10)###90.27(15)

N(10)- Cu(2)###2.140(4)###N(4)-Cu(1)-N(1)###91.12(15)###N(7)-Cu(2)-N(8)###90.79(15)

N(8) - Cu(2)###2.143(4)###N(3)-Cu(1)-N(1)###87.23(16)###N(9)-Cu(2)-N(8)###87.86(15)

###O(3)-Cu(1)-N(1)###90.21(14)###O(4)-Cu(2)-N(8)###87.02(14)

###O(2)-Cu(1)-N(1)###91.37(15)###O(5)-Cu(2)-N(8)###93.15(15)

###N(2)-Cu(1)-N(1)###177.37(15)###N(10)-Cu(2)-N(8)###175.28(16)

Bioactivity Experiment

The curves in Figure 4 show that the growth speed of coliform was much slower in the complex than in CK. That is to say, the complex possessed inhibiting activities against coliform. In order to study the inhibitory rates of all the complex, the inhibitory rate curve of the complex was shown in Fig 5. During 0-4 h, the inhibitory rate was increased very quickly, and then the speed increased slowly at 4-8 h; after 8 h, the inhibitory rate was decreased to some extent. The inhibitory rate reached 83% at 8h.

Although the mechanism of antimicrobial action of the compound still needs further investigation, the assay results would provide basic data for the pharmacological research of this type of complex.

Conclusion

A new Cu (II) complex with bi-[N-(propionic acid)] terephthalal diacythydrazon was synthesized in 1:1 pyridine-MeOH mixture solution and characterized by IR, X-ray single crystal diffraction. The crystal complex crystallizes in the monoclinic system with space group P2 (1)/c. The coordination polyhedral around Cu (II) can be described as an octahedron with slightly distorted. The antibacterial activities of the complex against coliform were investigated by turbidimetry/ spectrometry method and the maximum inhibition rate was 83% at 8h.

Acknowledgment

We thank the Foundation of Shangluo University (17SKY027) and the National Natural Science Foundations of China (No. 21873063 ).

References

1. X. M. Chen, G. F. Liu, DoubleStranded Helices and Molecular Zippers Assembled from Single-Stranded Coordination Polymers Directed by Supramolecular Interactions, Chem. Eur. J., 8, 4811 (2002).

2. R. H. Wang, M. C. Hong, D. Q. Yuan, Y. Q. Sun, L. J. Xu, J. H Luo, R. Cao, A. S. C. Chan, The Role of Spacers between Carboxylate Groups in Self-Assembly Process: Syntheses and Characterizations of Two Novel Cadmium(II) Complexes Derived from Mixed Ligands, Eur. J. Inorg. Chem., 2004, 37 (2004).

3. R. H. Wang, Y. F. Zhou, Y. Q. Sun, D. Q. Yuan, L. Han, B. Y. Ben, B. L. Wu, M. C. Hong, Syntheses and Crystal Structures of Copper(II) Coordination Polymers Comprising Discrete Helical Chains, Cryst. Growth Des., 5, 251 (2005).

4. N. L. Rosi, J. Eckert, M. Eddaoudi, D. T. Vodak, J. Kim, M. O. Keeffe, O. M. Yaghi, Hydrogen storage in microporous metal-organic frameworks, Science, 300, 1127(2003).

5. H. K. Chae, D. Y. Siberio-Perez, J. Kim, Y. Go, M. Eddaoudi, A. J. Matzger, M. O. Keeffe, O. M. Yaghi, A route to high surface area, porosity and inclusion of large molecules in crystals, Nature, 427, 523 (2004).

6. N. N. R. Rao, S. Natarajan, R. Vaidhyanathan, Metal Carboxylates with Open Architectures, Angew. Chem. Int. Ed. 43, 1466 (2004).

7. M. Math, N. Sharma, C. L. Sharma, Studies on Some Organotin (IV) Complexes of Semicarbazones and Thiosemicarbazones, Synth. React. Inorg. Met-Org. Chem., 19, 339 (1989).

8. D. R. Willianms, Metals, ligands, and cancer, Chem. Rev., 72, 203 (1972).

9. L. Zhang, B. H. Zhang, N. Tang, Synthesis, Characterization and Antibacterial Activity of the Transition Metal Complexes of (1-formylferrocene)-3,5-dibenzyloxybenzoyl hydrazone, Synth. React. Inorg. Met-Org. Chem., 37, 263 (2007).

10. T. A. Khattab, H. E. Gaffer, S. A. Aly, T. M. Klapotke, Synthesis, Solvatochromism, Antibacterial Activity and Dyeing Performance of Tricyanofuran-Hydrazone Analogues Chemistry select, 1, 6805 (2016).

11. A. Syamal, M. R. Maurya, Coordination chemistry of schiff base complexes of molybdenum, Coord. Chem. Rev., 95, 183 (1989).

12. CHEN Feng-ying, WU Wang-ting, LI Heng-xin, HE Shui-yang, WEN Zhen-yi, LI Jia-xing, Molecular Structure and Properties of a Novel Acylhydrazone (C14H14O6N4)*HCON (CH3)2*2H2O, Chem. Res. Chin. U., 28, 524 (2012).

13. G. M. Sheldrick, SADABS, University of Gottingen, Gottingen, (1996).

14. W. I. Madison, SMART and SAINT, Siemens Analytical X-Ray Instruments, Inc., (1996).

15. G. M. Sheldrick, SHELXTL-97, A Program for Refining Crystal Structures, Version 5.10, Bruker AXS Inc., Madison, WI-53719, USA, (1997).

16. F. Y. Chen, S. Y. He, Studies on Lanthanide(III) Ternary Mixed-Ligand Complexes with N-(2-Propionic Acid)-Salicyloyl Hydrazone and Isonicotinic Acid: Synthesis, Characterization, and Antibacterial Activities, Synth. React. Inorg. Met-Org. Chem., 38, 642 (2008).
COPYRIGHT 2019 Knowledge Bylanes
No portion of this article can be reproduced without the express written permission from the copyright holder.
Copyright 2019 Gale, Cengage Learning. All rights reserved.

Article Details
Printer friendly Cite/link Email Feedback
Author:Chen, Fengying; Wu, Wangting; He, Shuiyang
Publication:Journal of the Chemical Society of Pakistan
Article Type:Technical report
Date:Jun 30, 2019
Words:2481
Previous Article:Optimization of Production Parameters of Tobacco Seed Oil Methyl Ester using Multi-Response Taguchi Method and MANOVA.
Next Article:Phytochemical Isolation and Biological Activities of Corydalis adiantifolia from Baltistan.
Topics:

Terms of use | Privacy policy | Copyright © 2021 Farlex, Inc. | Feedback | For webmasters |