Synthese And Structures Of The Transition Metal Complexes Derived From Pyridine And The Schiff Bases From Picolinaldehyde N-oxide And Salicylaldehyde

Part One:In the course of synthesizing of the schiff base ,the complex corresponding to the schifT base was not synthesized,but an unexcepted new complex was obtained. Its molecular formula is Mo8O26(ONC3H7)2(C6H8N,)4 2(H2O) And the crystal is monoclinic,space groud P2(1) n with cell parameters a =8.93 10(12)A,b =24.260(3)A,c =13.3510(19)A,ft =104.688 ( 3 ) ,F=2704.2(7)A3,Mr=899.16,5=2,Dc=2.209mgcm, =1.889mm-1,Ff000;=1,Rn =0.0393 . Rl =0.0287,wR2 =0.0688,5 =0.933. =0.886eA'3,=-0.704eA-3. Eight molybdenum atoms in the complex were held together by three kinds of bridge bonds of ju -2, -3 ,fj -4 oxygen atoms,while there was no Mo-Mo bond in the crystal. There are three types of Hydrogen bonds in the crystal,by which it forms a three dimension network structure.Part Two:Two copper Complexes ,CXCNCIOJ,,Cu2(OAc)4(C5H5ClN2),were synthesized in the course of prerparing the schiff Base N isonicotinamidosalicylaidimine. The mam crystallographic date are as follows :Cu(C6H6N2)2(ClO4)2 Mr =478.73 ,Triclinic system ,space group P-L a =7.641(1)A,b =7.987(1)A,c =7.990(1)A,F=0.4317(1)nm Z =1,DC =1.841mgcm =1. 627mm1,F(OOO) =243,7=0.0264,wR2 =0.0641,5=1.102,Pna =0.251eA- pmm =--0.278eA- Cu2(OAc)4(C5H5ClN2)2:Mr =620.38,monoclinic system ,space group. C2 c. a =19.888(3) A,b =9.158(1)A,c =14.241(2)A. F=2.3336(5)nm3,Z=4,DC =1.766mgcm, =2.104mm-,F(OOO) =1256,S = 1.054. Rl =0.0263, -R2 =0.0676. pmiK =0.254eA"3,pmm =-0.27 leA"3 . Because the Jahn-Teller Effect affects on copper ion ,two crystal structure both have distortion in their shapes.Part Three:The method of prepareing picolinaldehyde N-oxide was improved. The time ofthe preparation was shortened and the yield of the product was increased. The schiff base was synthesized from picolinaldehyde N-oxide and a - amino phenylethanone. Its crystal structurew:as determined by X-ray diffraction method. Molecular formula is C14H,3N2O2. And the crystal is monoclinic,space groud P2(0) n with cell parameterses a =8.1496(11)A,b =15.562(2)A,c =9.6460(14)A,v =1166.1(3)A3,z =4,DC =1.374mgcni3,p. =0.094mm', (000) =508,Rl =0.0734,wR2 =0.2256,=0.0276,pmfl,K).529eA-3,p=-0.684eA-3. The crystal was held together by hydrogen bonds,which form a two-dimension sheet structure. And strong n - n sacking interaction exists in the crystal.The coulorless crystal of the schiff Base N isonicotinamidosalicylaidimine was synthesized. And its molecular formula is QjHnNjO,The crystal is monoclinic,space groud P2(1) n with cell parameterses Mr =241.25,a=8.153(1)A,b =15.574(4)A,c=9.554(2)A,p =105.48(1),V= 1169.1(4) A3,z=4,Dc=1.371mgcm"V=0.096rnrn1,f(000) =504,Rua =0.0242,Rl =0.0832,wR2 =0.1158 ,5=0.869,p,,,at=0.548eA-3 ,pn,,,,=-0.142eA" The Crystal has also been determined by UV and IR spectra. There are two forms of the schiff base ,one is of enol ,the other of ketone. When the schiff base is solid ,it 's most of ketone.In the crystal,strongTT - .Tsacking interaction and hydrogen bonds which are intermolecule or intramolecule ones make the crystal have higher stabilities and symmetries.