Juneja, H D

Kharche, V W

Munshi, K N

English

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IndianJ~urnalof ChemistryVol.27A, March 1988,pp.222-224Synthetic& StructuralStudiesonthePolymericComplexesofT4rephthaloyl-bis-(N-phenylhydroxamicAcid) (TPHA) &Sebacyl-bis-(N-phenylhydroxamicAcid) (SPHA) withCo(n),Ni(n),Cu(n)& Zn(n)K N MUNSHI*, V W KHARCHEt & H D JUNEJADepartmentof Chemistry,NagpurUniversity,Campus,Nagpur440010Received9March 1987;revised16July 1987;rerevisedandaccepted7September1987i Polymeric complexes of terephthaloyl-bis-(N-phenylhydroxarnicacid) (TPHA) and sebacyl-bis-(N-p'enylhydroxamicacid)(SPHA) withCo(II), Ni(II), Cu(II) andZn(II) havebeenpreparedbythereactionof thecorre-sIJOndingligandswithtransitionmetalionsin dimethyIformarnidemedium.Polymersformedhavebeencharacterisedbytheirelementalanalysis.Thermalstabilitiesof thepolymershavebeeninvestigatedbycarryingoutdifferentialther-m/lIanalysisandthermogravimetricanalysis.The structuresof thepolymericcomplexesareassignedon thebasisof~ir reflectanceandinfraredspectralandmagneticsusceptibilitydata.Hydrotamicacidsareanimportantclassof reagentsandfohn complexeswithvariousmetalionsl-4.Intheprel,sentpaper,preparationof terephthaloyl-bis-(N- hdnylhydroxamicacid) (lPHA) and sebacyl-bis-(NJphenylhydroxamicacid) (SPHA) and theirpolym~ricomplexeswithCo(II), Ni(II), Cu(II) andZn(II) ~avebeenreportedfor thefirsttime.Besidesthesyqthesisandexaminationof theirthermalsta-bility,~resentwork describesstructuralcharacteri-sation~fthesepolymericcomplexeson thebasisofeleme,*alanalysis,infraredandreflectancespectraandm1gneticsusceptibilitymeasurements.Mater¥dsandMethodsAll ~e chemicalsusedasstartingmaterialsin thesynthe~isof ligands and coordinationpolymerswereol chemicallypurequality.If required,thesewerefo/therpurifiedbystandardprocedures.Prepar~tionof ligandsTerephthaloyl-bis-(N-phenylhydroxamic acid)(lPHA!) and sebacyl-bis-(N-p enylhydrox micac-id) (SPl!A) werepreparedby themodifiedmethodof Priy~darshiniandTandon5basedon theSchot-ten-Ba~ann reaction. N-Phenylhydroxylamine(0.25 Aft),ethanol(50ml),sodiumbicarb nate(0.5M) an4distilledwater(25ml)weretakenin a 250mlbeaker.To this, ciddichlorid (0.1M) dissolvedin die~ylether(100ml)wasaddedoveraperiodof45minlwithconstantstirring.A granularsolidsepa-ratedwhichwasfilteredandtrituratedwithsaturat-ed solJtion of sodiumbicarbonateto removeanyacidic impurities.The productswere obtainedin-~tPrt-sent!address:ChemistryDepartment,SindhuMahavidyal-aya,Nag~ur,222low yields(60 to 70%)andwerecrystallizedwithdifficulty from dimethylformamide(DMF) (m.p.SPHA 1520andlPHA 232°).lPHA meltedwithdecomposition.lPHA [Found:C, 68.55;H, 4.81;N,7.80;Calc. for CZOH1604Nz:C,.68.96;H, 4.80;N,7.81%].SPHA [Found:C, 67.60;H, 7.39;N, 7.30;Calc.for CZZHZ804Nz:C, 68.76;H, 7.29;N, 7.29%].PreparationofpolymersThe ligand(0.01M), metalacetate(0.01M), andDMF (50ml)wereheatedon awaterbathfor 2 hr.The insolublepolymersformedwerefilteredandthroughlywashedseveraltimeswithdimethylform-amideandethanoltill freefromunreactedreactants.The polymerswereobtainedasamorphouspow-dersandwerefoundtobeinsolubleinalmostallthecommonorganicsolvents.The elementalanalysesandproposedcompositionsfor thesepolymersaregiveninTable1.Carbon,hydrogenand nitrogenwereestimatedusuingaColeman'sanalyser.IR spectrawererecordedon a specordIR-75 in-strumentin the range4000-400em- 1usingnujolmull.A singlebeamCarl-ZeissUSU-2-p-spectropho-tometerwasusedfor recordingreflectancespectraof polymersandmagnesiumcarbonatewasusedasa referencesample.A DTA apparatusfabricatedatlIT, Bombay was used for recordingdifferentialthermogramsof thepolymers.The heatingratewasmaintainedat 7°/min.A Stanton-Redcrofthermo-gravimetricbalancewith an automaticrecorder(BARC, India)wasusedfor thermogravimetrican-alysis.The analysiswascarriedout in air with 100mgOf a sampletakenin a platinumcrucible.TheMUNSHI etaL:POLYMERIC COMPLEXES OF CoIn), Ni(n),Cu(n)&Zn(II)Table I-Elemental Analyses and Decomposition Temperatures of Ligands and PolymersProposedcompositionFound(Calc.),%Colour!left.(Dec.Temp.,0c)(B.M.)CHNM[Co(a)]"58.653.566.7814.40Brown3.91(290)( .98)( . 4)6 88(14.48)[Ni(a)(HzO)z]"5 004 1523Yellow304 210.323 6Cu(a)]n768 8Yell ish1. 86325 3green[Zn(a)]".125 62White(270)63 97782o b75 15Lightpink755.30b)( lz]"62 4Lightgr n3. 92(56 5)522.80D rty e8378 9( 1)( . 6)9Zn59 93345(a=TPHA,b=SPHA)I•heatingratewasmaintainedat 3°C/min.Magneticsusceptibilitiesof polymerswere determinedbyGouy'smethod.ResultsandDiscussionAn IR bandaround2800cm- 1hasbeenassignedto0- H stretchingvibrationin thistypeof hydrox-amicacids6•In thepresentcasethisbandappearsat3170cm-1 in SPHA andlPHA ligands.Bandsap-pearingat 1615and 1595cm-1 in SPHA maybeduetotheresonatingstructuresofN - N-( - C =0)-OH moiety.In thecaseofTPHA it appearsat1600cm-1•An intensebandappearingat 3275cm-1 isdueto freeN - H stretchingwhereasthebandap-pearingat895in SPHA and890cm-1 in lPHA isassignedtoN - 0stretchingvibration.The hydroxamicacidsgenerallyformfivemem-beredchelateswithmetalionscoordinatingthrough)N - 0and>C =0oxygens.As is anticipated,thebanddueto 0-H groupdisappearsin polymers.The banddueto carbonylgroupis shiftedtowardslowerfrequencysideindi-catingtheformationof C =0-+M coordinatebond.The N - 0bandin polymeris foundto havebeenshiftedslightlyto higherfrequencyside with in-creasein its intensity.Mediumbandsappearinginthe regionof 520 to 565 cm-1 are assignedtoM - 0bondingin polymers7•Reflectancespectra ndmagneticpropertiesA band appearingaround 18.69kK in Co(II)-lPHA and around18.60kK in Co(II)-SPHA po-lymersmaybeassignedto4Az-+41;.(P) transitionintetrahedralfields.Magneticdataof Co(II)-lPHA and -SPHA po-lymersalso supportthe tetrahedralgeometryofthesecomplexes.A bandappearingat 25.64kK inNi(II)-SPHA andat 28.00kK in Ni(II)-TPHA p0-lymerisdueto 3Azg-+31;.J P) transition.The magne-tic momentvalue also confirms the octahedralgeometryof thecomplexes.Broad bandsaround 15.38kK and 12.66kKin Cu(II) polymers of SPHA occur due tot4.,dxz-+dx2 - y and dZ2-+dx2 - y transitionsrespect-ively9.•••In lPHA-Cu(II) polymer,however,onlyonebandis observedaround15.88kK whichmaybe duetot4.,dxz-+dx2 _ y transition.Thus,inboththecases,thesquareplanargeometryis predicted10.ThermalstudiesofpolymersCo(II) and Cu(ll) complexesof lPHA show alargeexothermin therange310-4QO°C(390-520°Cfor SPHA complexes)while the rangefor Ni(ll),Zn(ll) complex is 310°-340°C(360"-500°CforSPHA complexes).In additionto this,Co(ll) andCu(II) complexesof lPHA showa sharpexothermat - 230°C(250°Cfor SPHA complexes)whileforNi(ll) complexit occurs at - 300°C (310°CforSPHA complex).Zn(ll)-lPHA complexshowsnosuchsharpexotherm.It hasbeenobservedin the caseof Co(Il) andCu(II) polymersthatthissharpexothermis not as-sociatedwithmasslossin TGA. In Ni(n) polymer223INDIAN J. CHEM., VOL. 27A, MARCH 1988{: Ph Ph H24I I 0O-N N-O II I ----- MO=C-'CH I -c=o~1\ 280H(1) 2 nthisex?thermis almostmergedwith thelargeex-otherm.Dec~mpositiontemperatureof thepolymersaregivenill Table1.224On thebasisof abovestudies,structures(I) and(IT)areproposedfor Ni-SPHA andNi-TPHA po-lymersrespectively.In caseof Co(ll), Cu(IT)andZn(ll) complexesof SPHA andTPHA waterof co-ordinationisabsent..References1 DasJ & ShomeS C,Anal chimActa.24(1961)37.2 LuitwickG D & RyanD E, Can/ Chern,32 (1954)949.3 RyanDE &ArmourCA, Can/Chern, 3S (1965)-1454.4 RyanDE & LutwickGD, Can/Chern, 31(1953)9.5 PriyadarshiniU & Tandon S G, / chemEngg Data, 12(1967)143.6 ShuklaJ P,AgrawalY K & KuchyaK P, / IndianchemSoc,51(1954)437.7 Nakamoto,Infraredspectraof inorganicand coordinationcompounds(JohnWiley,NewYork), 1970,270.8 LeverA B P, Inorganicelectronicspectroscoy(Elsevier,NewYork), 1968,323.9 WentworthR A D, InorgChern,5 (1966)496.10 Lever A B P, Inorganicelectronicspectroscopy(Elsevier,NewYork), 1968,356..•...It.

Synthetic & Structural Studies on the Polymeric Complexes of Terephthaloyl-bis-(N-phenylhydroxamic Acid) (TPHA) & Sebacyl-bis(N-phenylhydroxamic Acid) (SPHA) with Co(II), Ni(II), Cu(II) & Zn(II)

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Synthetic & Structural Studies on the Polymeric Complexes of Terephthaloyl-bis-(N-phenylhydroxamic Acid) (TPHA) & Sebacyl-bis(N-phenylhydroxamic Acid) (SPHA) with Co(II), Ni(II), Cu(II) & Zn(II)

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