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第31卷第6期 2015年6月 无 机 化 学 学 报 CH1NESE JOURNAL OF IN0RGANIC CHEMISTRY Vol_31 No.6 1076—1084
1,3.二吗啉基丙烷与Hg(1I) ̄Zn(1I)的配合物: 合成、结构与抗茵研究
Goudarziafshar Hamid ・ Yousefi Somaieh Abbasityula Yunes3 Du ̄ek Michal Eigner Vdclav Rezaeivala Majid Ozbek Neslihan ( Department of Chemistry,Faculty of Science,Sayyed Jamaleddinasadabadi University,Asadabad,lran) (2Department of Chemistry,Facuhy of Science,Ilam University,P.O.Box 69315516 Ham,lrc啊1、 (3Department of Chemistry,Lorestan University,Khorramabad,/ran) (4Institute ofPhysics AS CR, .v.i.,Na Slovance 2,182 21 Prague 8,Czech Republic) ( Department of Chemical Engineering,namedan University of Technology,P.O.Box 65155 nam ̄dan,Iran) (6Department ofPrimary Education,Faculty ofEducation,Ahi Evran University,40100 Krsehir,Turkey) 摘要:以1,3-二吗啉基丙烷(DMP)为配体合成了2个配合物:Hg(DMP)C1 (1)和Zn(DMP)C1 (2),并对其结构进行了表征。单晶X一 射线结构分析表明,2个配合物中的金属离子都与2个N原子和2个Cl原子配位,形成扭曲四面体配位结构。配体和配合物对 3种革兰氏阳性菌(5.aureus ATCC 25923,E calis ATCC 23212和S.epidermidis ATCC 34384)和3种革兰氏阴性菌(E coli ATCC 25922, aeruginosa ATCC 27853和 pneumonia ATCC 70063)都具有抗菌活性,且在一定条件下,H Ⅱ)配合物的抗菌活 性超过了作为标准的磺胺异恶唑药物。 关键词:晶体结构;l,3-吗啉基丙烷;抗菌活性;H 配合物;zn(Ⅱ)配合物 中图分类号:0614.24 1;0614.24*3 文献标识码:A 文章编号:1O014861(2O15)06—1076.09 DOI:10.11862/CJIC.2015.164 Complexation of 1,3-Dimorpholinopropane with Hg(Ⅱ)and Zn(1I)Salts: Syntheses,Crystal Structures and Antibacterial Studies
Goudarziafshar Hamid - Yousefi Somaieh Abbasityula Yunes3 Du ̄ek Michal Eigner Vdclav4 Rezaeivala Majid Ozbek Neslihan6 ( Department of Chemistry,Faeuhy of Science,Sayyed Jamaleddinasadabadi University,A sadabad,/ran)  ̄Department ofChemist ̄,Facuhy ofScience,llam University,P.O.Box 69315516//am,,r帆1 (3Department of Chemistry,Lorestan University,Khorramabad,/ran) (4Ittstitute of ysics AS C_R,” i.,Na Slovance 2,182 21 Prague 8,Czech Republic) ( ̄Department ofChemical Engineering,Hamedan University ofTechnology,P.O.Box 65155 Banedan,/ran) (6Department of尸 m0ry Education,Faculty ofEducation,Ahi Evran University,40100 Krsehir,Turkey) Abstract:Two Hg(H)(1)and Zn(II)(2)complexes with general formulation M(DMP)C12 where DMP=I,3一 dimorpholinopropane were synthesized and structurally characterized by physicochemical methods and single crystal X—ray diffraction.An X—ray structural analysis shows that in both complexes Hg and Zn are coordinated by two nitrogen and two chlorine atoms in a form of distorted tetrahedron.The ligand and related complexes have antibacterial activity against three Gram—positive bacteria ls.epidermidis ATCC 25923 E.faecal/s ATCC 23212 and S.epidermidis ATCC 34384),and also against the three Gram.negative bacteria(E col ATCC 25922, aeruginosa 收稿日期:2015.01—26。收修改稿日期:2015.03.30。 Crystallography part was supported by the project(No.14—03276S)of the Czech Science Foundation. 通讯联系人。E-mail:hamid.gafshar@yahoo.
eom 第6期 Goudarziafshar Hamid等:1,3-二吗啉基丙烷与Hg(11) ̄l zn(Ⅱ)的配合物:合成、结构与抗菌研究 1077 ATCC 27853 and K.pneumonia ATCC 70063).The results revealed that in some cases the antibacterial activity of Hg(1J complex exceeded the one of sulfisoxazole used as a standard.CCDC:957542,1;957846,2.
Key words:crystal structure;1,3・dimorpholinopropane;antibacterial activity;H Ⅱ)complex;Zn(11)complex Morpholine is a strong alkali,which can be considered as a kind of secondary aliphatic amine. However,the incorporation of nitrogen into the six— member ring exposes the lone electron pair on nitrogen and makes the molecule a good nucleophile[1]. Morpholine and its derivatives are used extensively in many chemical reactions and its alkyl and aryl deriva— tives are very important in chemical and pharmaceu— tical industries 5J.Heterocyclic ring systems with mor— pholine nucleus have aroused great interest in recent years due to their biological activities嘲.Morpholine derivatives were reported to possess antimicrobial activity[7 and inflammatory activities in albino rats【砌. Morpholine derivatives exhibit anthelmintic and insecticidal activityl11】_N—substituted morpholines are used in the treatment of inflammatory diseases,asthma and migraine【 .N-substituted morpholines are also reported to show activity like antiemetics,platelet aggregation inhibitors and bronchodialatorst .Studies on the energetic of N・-substituted morpholine deriva-・ fives are highly important in order to understand the biological activities and designing new drugs. In continuation of our recent work on synthesis of the morpholine complexes we report in this paper the synthesis and crystal structures of Hg(1)and Zn(1) complexes of 1,3一dimorpholinopropane(DMP)ligand. Also,the antibacterial activity of the 1,3一dimorpholin— opropane ligand and its metal complexes is reported against three Gram—positive species .epidermidis,S. aurell ̄,E.faecalis)and three Gram—negative species (E coli, aeru ̄ino3a,K.pneumonia)of bacterial strains by the disc diflusion and micro dilution methods. 1 Experimental 1.1 Chemicals All chemicals and salts of transition metals were of analytical grade(Sigma,Aldrich)and used as supplied.Solvents were distilled before use. 1-2 Physical measurements IR spectra of the ligand and complexes over the region of 400~4 000 am一 were recorded using a Perkin Elmer spectrum (Version 10.01.001 FT.IR spectrometer with solid KBr pellets. H NMR and 0C NMR spectra were recorded on a BRUKER AC 400 MHz spectrometer using TMS as an internal standard in DMSO.d6 solvent.Mass spectral data were obtained on Agilent Technology(HP).Elemental analyses were performed on a Vario ELⅢCHNS system. 1.3 Synthesis 1.3.I Synthesis of 1,3-dimorpholinopropane(DMP) The ligand was prepared according to the literature method 阍.1,3-dibromopropane(4.69 g,25 mmo1)in absolute ethanol(40 mE)was added drop wise to the mixture of potassium carbonate(6.9 1 g,50 mmo1)and morpholine(4.35 g,50 mmo1)in absolute ethanol(30 mE).The contents were refluxed for about 48 h at 80 oC.The solution was then reduced to 20 mL by rotary evaporation and the product was extracted with chloroform.The product formed as a yellow Liquid, Yield:0.092 g,(43%). H NMR(CDC13,400 MHz):6 1.3-1.7(m,一CH2-,2H);2.1-2.4(d,N—CH2,12H);3.47- 3.61(d,0一CH2,8H); C NMR(CDC13,400 MHz):6 65.4(d),55.4(c),52.2(b),22.1(a);IR(KBr,am ): 2 954 and 2 853(C—H);1 457(一CH2一);1 120(C—N);1 071 and 916(C—O). 1.3.2 Syntheses of the complexes Both complexes were synthesized by the branch tube method .1,3一dimorpholinopropane(DMP)(1 mmol,0.214 was placed in one arm of a branched tube and metal salts(1 mmo1)in the other.Ethanol was then carefully added to fill both arms,the tube sealed and the ligand containing arm immersed in an oil bath at 60 oC,while the other was left at ambient temperature.After one week,the colorless crystals were collected in the cooler arm.They were filtered off,washed with ether,and dried in air.For compl