Synthesis, Characterization And Crystal Structure Of The Complexes With Some Carboxylic Acids

Coordination polymers have attracted much interest due to their unique properties in magnetism, catalyst, NLO, superconduct, thermal stability which resulted from 2D or 3D structures. Many coordination polymers were made up of rigid ligands, such as 4,4,-bipy, pyrazine, terephthalic acid. These coordination polymers have many potential applications in host-guest interaction, molecular recognition, and so on. Relatively, complexes based on flexible ligand are less reported. But rigid ligands have less diversity in conformation that flexible ligands in the process of complex for mation, while flexible ligand can meet the coordination requiremeet of different metal geometry . In this thesis ,ten coordination complexs have been synthesized with Zn(II), Cd(II),Cu(II),Ag(I) ions and the three flexible ligands: [3-carboxyl-1,5-benzdioxyaceticacid (CBDOAH3)], [2-methyl-1,3-diacetoxylbenzimidazole(DAMB)], [4-(2-hydroxylbenzylimidogen)benzoic acid(HBIBA)]. [Zn3(CBDOA)₂(H₂O)10]·2CH3OH(I); [Cd3(CBDOA)₂(H₂O)]_n (II); [Cd3(CBDOA)₂(H₂O)4]_n(III); [Ag6(CBDOA)₂(C6H12N4)3]_n(IV); [Zn3(CBDOA)₂(H₂O)6]_n(V); [Zn(MDAB)₂(H₂O)4]·4 H₂O(VI); [M(mdab)Cl]_n(M=Zn(VII),Cd(VIII),Cu(IX)); [Cu(hbiba)(py)]_nAnDMF(X)The crystal structures of these coordination complexs have been characterized by X-ray single crystal diffraction.This thesis is divided into four sections.The first part introduces briefly complexes based on carboxylate ligands and discuss the difference between rigid and flexible ligands in the construction of metal-organic complexes.In the second part, the ligand of [3-carboxyl-1,5-phendioxyaceticacid (CBDOAH3) and its five complexes(I-V) with Zn(II), Cd(II), Ag(I) have been synthesized . Complex(I) crystalizes in triclinic crystal system, space group P-1, unit cell parameter: a=7.2569(11)A,b=9.0562(14)A,c=13.401(2)A,α=79.598(2)°,β=82.995(3)°,γ=74.362(2)°. In complex(I) three nuclears are observed,in which there are two kind of Zn(II). Both of Zn(II) have six coordination numbers,which form a octahedral configuration.The hydrogen bonding interactions andπ…πstacking interactions extend the complex(I) into a three-dimensional architecture. Complex(II) crystalizes in triclinic crystal system,space group P-1, unit cell parameter:a=7.8771(11)A,b=11.3542(16)A,c=11.6732(16)A,α=116.704(2)°,β=104.177(2)°,γ=93.534(2)°. In complex(II) the 2D double-layer structure is observed,in which there are two kind of Cd(II). One tyle of Cd(II) which is located in the interval of the two layers is six coordination numbers,which form a octahedral configuration.The other which is located in the two layers is five coordination numbers,which form a diprick configuration. Theπ…πstacking interactions extend the complex(II) into a three-dimensional architecture.Complex(III) crystalizes in triclinic crystal system, space group P-1, unit cell parameter:a= 7.6503(10)A, b= 9.9373(13)A,c= 10.1128(13)A,α=63.504(2)°,β= 82.022(2)°,γ= 69.502(2)°. In complex(III) the 3D structure is observed, in which there are three kind of Cd(II). One tyle of Cd1(II) and Cd2(II) is six coordination numbers,which form a octahedral configuration. The other is seven coordination numbers,which form a triprism configuration . The three oxygen atoms(O2,O8,O18) extend the complex(II) into a three-dimensional architecture. Complex(IV) crystalizes in monoclinic crystal system, space group C2/c, unit cell parameter: a= 16.847(2)A, b=24.7042(15)A, c=26.7670(17)A,α=90°,β=104.037(3)°,γ=90°. Complex(V) crystalizes in monoclinic crystal system, space group P21/n, unit cell parameter: a=8.0458(9)A, b=14.2074(16)A, c=12.1692(13)A,α=90°,β=90.261(2)°,γ=90°. In complex(V) the 2D double-layer structure is observed,in which there are two kind of Zn(II). One tyle of Zn(II) is six coordination numbers,which form a octahedral configuration.The other is four coordination numbers,which form a tetrahedron configuration.The oxygen atoms(O5) extend the complex(V) into a three-dimensional architecture.In the third part, the ligand of 2-methyl-1,3-diacetoxylbenzimidazole(DAMB) and its five complexes(VI-IX) with Zn(II), Cd(II), Cu(II) have been synthesized . Complex(VI) crystalizes in monoclinic crystal system, space group P21/n ,unit cell parameter:a=7.2749(9)A, b=21.265(3)A, c=9.7794(12)A,α=90A,β=104.467(2)A,γ=90A. In complex(VI) one nuclear are observed,in which the Zn(II) has six coordination numbers,which form a octahedral configuration.The hydrogen bonding interactions andπ…πstacking interactions extend the complex(VI) into a three-dimensional architecture. The complex (VII-IX) crystalizes in monoclinic crystal system, space group P21/n, unit cell parameter: complex(VII) a=7.1285(17)A, b=13.301(3)A, c=12.804(3)A,α=90°,β=90.540(4)°,γ=90°; complex(VIII) a=7.2418(9)A, b=13.4867(17)A, c=12.9531(16)A,α=90°,β=90.229(2)°,γ=90°; complex (IX) a=7.0088(11)A, b=13.341(2)A, c=12.7924(19)A,α=90°,β=90.548(3)°,γ=90°. The 2D structure is observed in complex (VII-IX).In the fourth part , the ligand of 4-(2-hydroxylbenzylimidogen)benzoic acid(HBIBA) and its complex(X) with Cu(II) has been synthesized . Complex(X) crystalizes in triclinic crystal system,space group P-1, unit cell parameter: a=8.9547(13)A, b=10.6215(15)A,c=11.3899(16)A,α=80.393(2)°,β=86.408(2)°,γ=80.138(2)°. In complex(X) the 1D double-chain structure is observed,in which the Cu(II)is five coordination numbers,which form a foursquare prick configuration. Theπ…πstacking interactions extend the complex(X) into a two-dimensional architecture.