【作者】 邓记华；

【导师】 梁宏； 于青；

【作者基本信息】 广西师范大学 ， 无机化学， 2006， 硕士

【摘要】 为了研究和讨论N-氧化吡啶甲醛类Schiff碱及其配合物的结构与性质关系,本文从N-氧化吡啶-2-甲醛出发,得到了三个配合物,并解析了它们的晶体结构。另外从吡啶-3-甲醛和吡啶-2-甲醛出发,得到了六个配合物,并测定了它们的晶体结构。第一章:以N-氧化吡啶-2-甲醛缩水杨酰腙和高氯酸钴为原料,用溶液法得到配合物C29H28ClCoN7O11(1)。晶体属三斜晶系,空间群为P-1。晶胞参数:a = 8.1716(17)A,b = 14.136(3) A,c = 14.644(3) A,α= 111.881(3)°,β= 90.534(3)°,γ= 92.854(4)°,V = 1567.1(6) A3,Z = 2,Dc = 1.579 Mg/m3。中心金属离子Co(II)为六配位畸变的八面体结构,Co(II)离子与2个配体中N(C=N),O(N→O),O(C=O)的原子配位。配合物通过氢键形成三维网状结构。第二章:以N-氧化吡啶-2-甲醛缩氨基硫脲与硝酸镍为原料,用溶液法得到配合物C14H18N10NiO9S2(2)。晶体属正交晶系,空间群为Pca2(1)。晶胞参数:a = 20.728(2)A,b = 20.728(2) A,c = 11.7113(12) A,V = 2307.6(4) A3,Z = 4,Dc = 1.707 Mg/m3。中心金属离子Ni(II)为六配位的拉长的八面体结构,Ni(II)与2个配体中N(C=N),O(N→O),S(C=S)的原子配位。分子间通过配阳离子、结晶水和抗阴离子(NO3-)之间形成氢键,使配合物分子组装成三维网状结构。生物活性表明:配体对金黄色葡萄球菌和大肠杆菌无效果,配合物2对金黄色葡萄球菌、大肠杆菌、肺炎链球菌、乙型溶血性链球菌和炭疽杆菌均无效果。N-氧化吡啶-2-甲醛缩氨基硫脲与高氯酸钴在水热条件下,得到配合物C14H16ClCoN8O7S2(3)。晶体属三斜晶系,空间群为P-1。晶胞参数:a = 6.893(5)A,b = 11.671(8) A,c = 14.254(10) A,α= 93.457(10)o,β= 103.624(10)°,γ= 94.567(10)°,V = 1107.2(14) A3,Z = 2,Dc = 1.700 Mg/m3。中心金属离子Co(III)为六配位的压缩的八面体结构,Co(III)与2个配体中N(C=N),O(N→O),S(C=S)的原子配位,分子间通过配阳离子、结晶水和抗阴离子(ClO4-)之间形成氢键,使配合物分子组装成三维网状结构。生物活性表明配合物3对大肠杆菌无效果,对金黄色葡萄球菌有很好的抑制效果,对乙型溶血性链球菌、白色葡萄球菌有较好的抑制效果,而对肺炎链球菌有良好的抑制效果,其MIC值分别为0.30μg·mL-1、501.67μg·mL-1、501.67μg·mL-1、250.83μg·mL-1。第三章:以氯化镍、醋酸镉、醋酸锰和吡啶-2-甲醛缩水杨酰腙为原料,用溶液法获得了Ni(II)、Cd(II)、Mn(II)的配合物单晶。C26H19N6NiO4(4)晶体属于单斜晶系,空间群为P2(1)/n,晶胞参数:a = 12.549(3) A,b = 17.788(5) A,c = 13.292(4) A,β= 115.310(5)°,V = 2682.1(12) A3,Z = 4,Dc = 1.333 Mg/m3。中心金属离子Ni(II)与两个吡啶环上的N原子、亚胺基上的N原子和羰基上的O原子配位,形成六配位的拉长的八面体结构,配合物通过分子间氢键和分子内氢键形成二聚体。C26H20CdN6O4(5)晶体属于单斜晶系,空间群为P2(1)/n,晶胞参数:a = 11.6648(10) A,b = 30.270(3) A,c = 21.764(2) A,β= 101.616(2)°,V = 7527.5(12) A3,Z = 12,Dc = 1.569 Mg/m3。中心金属离子Cd(II)与两个吡啶环上的N原子、亚胺基上的N原子和羰基上的O原子配位,形成六配位的拉长的八面体结构。生物活性表明:配合物5对金黄色葡萄球菌有抑制效果,其MIC值为525.83μg·mL-1,而对大肠杆菌无效果。配合物在波长λem = 560 nm (λex = 449.8 nm)处有最大发射,Cd(II)具有d10电子构型,因而没有因为d-d跃迁而产生对光的吸收,配合物5的发光可以认为属于LLCT发射。C26H21MnN6O4。50(6)晶体属于单斜晶系,空间群为P-1,晶胞参数:a = 18.56(2) A,b = 25.03(3) A,c = 11.515(18) A,β= 103.49(4)°,V = 5202(12) A3,Z = 8,Dc = 1.390 Mg/m3。中心金属离子Mn(II)与两个吡啶环上的N原子、亚胺基上的N原子和羰基上的O原子配位,形成六配位的拉长的八面体结构。C30H20Cd3N10O4S4(7)晶体属于单斜晶系,空间群为C2/c,晶胞参数:a = 20.088(6) A,b = 11.327(3) A,c = 17.659(4) A,β= 119.216(3)°,V = 3507.0(15) A3,Z = 4,Dc = 1.989 Mg/m3。中心金属离子Cd(II)(1)为五配位的四方锥,Cd(II)(2)为六配位拉长的八面体。在配合物7中配体L3脱酚羟基上的氢以负一价阴离子的形式参与配位,通过μ1,3-SCN-和配体桥连成二维配位聚合物。第四章:以吡啶-3-甲醛缩氨基脲与醋酸镉为原料,用溶液法得到配合C11H17CdN4O7(8),晶体属单斜晶系,空间群为P2(1)/c,晶胞参数:a = 8.2505(12) A,b = 19.858(3) A,c = 10.4917(15) A,β= 106.639(2)°,V = 1647.0(4) A3,Z = 4,Dc = 1.366 Mg/m3。Cd(II)离子配位数为七,其周围分别被一个配体分子中的吡啶氮原子和另一个配体中的酰肼氧原子,两个醋酸根和一个H2O分子所包围,醋酸根与Cd(II)离子双齿螯合配位,这种结构单元的无限延伸使整个分子呈现出一维链状结构。生物活性表明配合物8对金黄色葡萄球菌有很好的抑制效果,而对大肠杆菌均有良好的抑制效果,其MIC值分别为0.55μg·mL-1和281.9μg·mL-1。第五章:以高氯酸钴、硫氰酸铵和吡啶-3-甲醛缩水杨酰腙为原料,用溶液法得到配合物C28H30CoN8O8S2(9)。晶体属单斜晶系,空间群为P2(1)/n,晶胞参数:a = 13.1482(19) A,b = 30.757(4) A,c = 8.1333(12) A,β= 94.378(3)°,V = 3279.5(8) A3,Z = 4,Dc = 1.478 Mg/m3。中心金属离子Co(II)为六配位的畸变八面体几何构型,与配体中吡啶环上的N原子和硫氰根上的N原子以及H2O配位,配合物通过氢键形成二维网状结构。生物活性表明配合物9对金黄色葡萄球菌和大肠杆菌有较好的抑制效果,而对乙型溶血性链球菌、肺炎链球菌和白色葡萄球菌都有很好的抑制效果,其MIC值分别为387.5、775、0.84、0.84、0.84μg·mL-1。更多还原

【Abstract】 In order to investigate the relationship between the structure and property of the pyridinehydrazone and its complexs,nine complexs had been synthesized and their crystal structures had been characterized.Chapter One: The complex C29H28ClCoN7O11(1) is obtained by the reaction of L1 (2-pyridinecarboxaldehyde N-oxide reacts with salicylhydrazide) and Co(ClO4)·6H2O, It belongs to triclinic crystal system,space group p-1,with cell parameters: a = 8.1716(17)?,b = 14.136(3) ?,c = 14.644(3) ?,α= 111.881(3)°,β= 90.534(3)°,γ= 92.854(4)°,V = 1567.1(6) ?3,Z = 2,Dc = 1.579 Mg/m3. In complex 1,the centeral metal ion Co(II) adopts six-coordinated distorted octahedron geometry.L1 is coordinated to Co(II) via the oxygen(N→O),nitrogen(C=N) and oxygen(C=O) atoms,the complex forms two-dimensional network by intermolecule hydrogen bonds.Chapter Two: The complex C14H18N10NiO9S2(2) is obtained by the reaction of L2 (2-pyridinecarboxaldehyde N-oxide reacts with thiosemicarbazide) and Ni(NO3)·6H2O, It belongs to orthorhombic crystal system,space group Pca2(1),with cell parameters:a = 20.728(2)?,b = 20.728(2) ?,c = 11.7113(12) ?,V = 2307.6(4) ?3,Z = 4,Dc = 1.707 Mg/m3. In complex 2,the centeral metal ion Ni(II) adopts six-coordinated distorted octahedron geometry.L2 is coordinated to Ni(II)via the oxygen(N→O),nitrogen(C=N) and sulfur(C=S) atoms,there are a large number of hydrogen bond involving the cations,water molecules and nitrate counter-ions,which result in formation three-dimensional network structure.The antimicrobial activities of the extracts were evaluated by MIC against five bacteria (Escherichia coli, Staphylococcus aureus, Streptococcus pneumoniae,β-hemolytic streptococcus and Anthrax bacillus). The test results indicate that the complex shows no activity. The complex C14H16ClCoN8O7S2(3) is obtained by the reaction of L2 and Ni(NO3)·6H2O, It belongs to triclinic crystal system,space group P-1,with cell parameters:a = 6.893(5) ?,b = 11.671(8) ?,c = 14.254(10) ?,α= 93.457(10)o,β= 103.624(10)°,γ= 94.567(10)°,V = 1107.2(14) ?3,Z = 2,Dc = 1.700 Mg/m3. In complex 3,the centeral metal ion Co(III) adopts six-coordinated distorted octahedron geometry . L2 is coordinated to Co(III) via the oxygen(N→O),nitrogen(C=N) and sulfur(C=S) atoms,there are a large number of hydrogen bond involving the cations,water molecules and perchlorate counter-ions,which result in formation two-dimensional network structure.The antimicrobial activities of the extracts were evaluated by MIC against five bacteria (Escherichia coli,Staphylococcus aureus,Streptococcus pneumoniae,β-hemolytic streptococcus and Staphylococcus whiteus, The test results indicate that the complex shows strong activity.Chapter Three:The complex C26H19N6NiO4 (4) is obtained by the reaction of NiCl2·6H2O and L3 (2-pyridinecarboxaldehyde reacts with salicylhydrazide),It belongs to monoclinic crystal system,space group P2(1)/n,with cell parameters:a = 12.549(3) ?,b = 17.788(5) ?,c = 13.292(4) ?,β= 115.310(5)°,V = 2682.1(12) ?3,Z = 4,Dc = 1.333 Mg/m3.The centeral metal ion Ni(II) is six coordinated by two ligand anions,formed a distorted octahedron geometry. The complex forms dimer by intermolecule hydrogen bond. The complex C26H20CdN6O4(5) is obtained by the reaction of Cd(CH3COO)2·2H2O and L3,It belongs to monoclinic crystal system,space group P2(1)/n,with cell parameters:a = 11.6648(10) ?,b = 30.270(3) ?,c = 21.764(2) ?,β= 101.616(2)°,V = 7527.5(12) ?3,Z = 12,Dc = 1.569 Mg/m3.Cd(II) ion is six coordinated by two ligand anions,formed a distorted octahedron geometry. The antimicrobial activities of the extracts were evaluated by MIC against two bacteria (Escherichia coli,Staphylococcus aureus),The test results indicate that the complex shows weak activity.The complex C26H21MnN6O4.50(6) is obtained by the reaction of Mn(CH3COO)2·2H2O and L3,It belongs to monclinic crystal system,space group P-1,with cell parameters:a = 18.56(2) ?,b = 25.03(3) ?,c = 11.515(18) ?,β= 103.49(4)°,V = 5202(12) ?3,Z = 8,Dc = 1.390 Mg/m3.Mn(II) ion is six coordinated by two ligand anions,formed a distorted octahedron geometry.The complex C30H20Cd3N10O4S4(7) is obtained by the reaction of Cd(CH3COO)2·2H2O,NH4SCN and L3,It belongs to monoclinic crystal system,space group C2/c,with cell parameters:a = 20.088(6) ?,b = 11.327(3) ?,c = 17.659(4) ?,β= 119.216(3)°,V = 3507.0(15) ?3,Z = 4,Dc = 1.989 Mg/m3. Cd(1) ion is five coordinated by one ligand anions and SCN-,formed a distorted tetragonal pyramid geometry,Cd(2) ion is six coordinated by oxygen of the ligand and SCN- formed a distorted octahedron.geometry.The two-dimensional coordination polymers are formed through the SCN- bridging ligand.Chapter Four : The complex C11H17CdN4O7(8) is obtained by the reaction of Cd(CH3COO)2·2H2O and L4 (3-pyridinecarboxaldehyde reacts with semicarbazide),It belongs to monoclinic crystal system,space group P2(1)/c,with cell parameters:a = 8.2505(12) ?,b = 19.858(3) ?,c = 10.4917(15) ?,β= 106.639(2)°,V = 1647.0(4) ?3,Z = 4,Dc = 1.366 Mg/m3. In the complex 8,Cd(II) ion is seven coordinated with NO6 enviroment,two oxygen atoms from C=O of the ligand and water molecule respectively,four oxygen atoms from two acetate groups and one nitrogen atom from pyridyl ring of the ligand.The complex forms a one dimensional polymer of infinite length connecting.The antimicrobial activities of the extracts were evaluated by MIC against two bacteria (Escherichia coli,Staphylococcus aureus),The test results indicate that the complex shows strong activity.Chapter Five : The complex C28H30CoN8O8S2(9) is obtained by the reaction of Co(ClO4)2·6H2O,NH4CNS and L5 (3-pyridinecarboxaldehyde reacts with salicylhydrazide),It belongs to monoclinic crystal system,space group P2(1)/n,with cell parameters:a = 13.1482(19) ?,b = 30.757(4) ?,c = 8.1333(12) ?,β= 94.378(3)°,V = 3279.5(8) ?3,Z = 4,Dc = 1.478 Mg/m3. The crystal structure adopts distorted octahedron geometry with six coordination number,the Co(II) center surrounded by two nitrogen atoms from pyridyl ring of the ligand, two nitrogen atoms from thiocyanate and two oxygen from two water molecules . Two-dimensional network is formed via abundant intermolecular hydrogen bonds.The antimicrobial activities of the extracts were evaluated by MIC against five bacteria (Escherichia coli , Staphylococcus aureus , Streptococcus pneumoniae ,β-hemolytic streptococcus and Staphylococcus white). The test results indicate that the complex shows strong activity.更多还原