含水杨醛缩对硝基苯甲酰腙的钒酰配合物和钴配合物的合成和晶体结构  

Syntheses and Structures of Oxovanadium(V) and Cobalt(III) Complexes with Salicylaldehyde p-Nitrobenzoylhydrazone

作　　者：吴琼洁[1] 刘世雄[1] 

机构地区：[1]福州大学中心实验室,福州350002

出　　处：《Chinese Journal of Structural Chemistry》2004年第10期1177-1182,共6页结构化学（英文）

基　　金：福建省自然科学基金资助项目(E0110010)

摘　　要：本文合成了含水杨醛缩对硝基苯甲酰腙(简写为H2L)的钒酰配合物VOL(CH3OH)(CH3O)(1,C16H16N3O7V,Mr=413.26)和钴配合物[CoL(C5H5N)3]NO3C5H5N(2,C34H29N8O7Co,Mr=720.58)。配合物1属单斜晶系,空间群为P21/c,a=7.3253(3),b=18.8237(9),c=12.9014(5)?b=91.672(1),V=1778.2(1)3,Z=4,F(000)=848,m(MoKa)=0.603mm1,R=0.0470,wR=0.1312。配合物2属单斜晶系,空间群为P21/c,a=11.4196(8),b=17.157(1),c=17.081(1)?b=96.8233(9),V=3323.0(4)3,Z=4,F(000)=1488,m(MoKa)=0.578mm1,R=0.0455,wR=0.1311。在配合物1中,钒(V)原子由周围的酰氧基原子、配体L2的3个配位原子,去质子化甲醇的甲氧基原子和配位甲醇的氧原子配位,形成畸变的VO(ONO)(O)(O)八面体配位构型。晶体内每2个分子间通过氢键作用缔合成中心对称的分子对,OH…N氢键键长为2.861(4)?键角163.20。晶体中存在着弱p-p共轭作用。在配合物2中,钴(Ⅲ)原子由1个L2的3个配位原子和3个配位吡啶分子的3个氮原子配位,呈N4O2八面体配位构型。The two title compounds containing the same ligand H2L (H2L = salicylaldehyde p-nitrobenzoylhydrazone), VOL(CH3OH)(CH3O) 1 (C16H16N3O7V, M-r = 413.26) and [CoL(C5H5N)(3)](NO3C5H5N)-N-.-C-. 2 (C34H29N8O7Co, M-r = 720.58) have been synthesized and characterized. Complex 1 belongs to monoclinic, space group P2(1)/c with a = 7.3253(3), b = 18.8237(9), c = 12.9014(5) Angstrom, beta = 91.672(1)degrees, V = 1778.2(1) Angstrom(3), Z = 4, F(000) = 848, mu(MoKalpha) = 0.603 mm(-1), R = 0.0470 and wR = 0.1312. Complex 2 is of monoclinic, space group P2(1)/c with a = 11.4196(8), b = 17.157(1), c = 17.081(1) Angstrom, beta = 96.8233(9)degrees, V = 3323.0(4) Angstrom(3), Z = 4, F(000) = 1488, mu(MoKalpha) = 0.578 mm(-1), R = 0.0455 and wR = 0.1311. The vanadium atom in 1 has a distorted octahedral VO(OON)(O)(O) coordination with a normal V=O bond of 1.583(3) Angstrom. Two oxygen and one nitrogen atoms of the tridentate hydrazone ligand L2-, and one oxygen atom of the deprotonated methanol CH3O- are coordinated to the vanadium(V) atoms, forming an equatorial plane. The axial position trans to the oxo group is occupied by the oxygen atom of the neutral methanol CH3OH. Every two molecules related by centrosymmetric operation in 1 are connected by pairs through intermolecular hydrogen bonds. The hydrogen bond length of (ON)-N-... is 2.861(4) Angstrom and bond angle of O-(HN)-N-... is 163.20degrees. Each two facial benzene rings form dimers via partial pi-pi stacking in the pairs. The cobalt atom in 2 is octahedrally coordinated by three ONO donors in L2- and three nitrogen atoms in three pyridine molecules.

关 键 词：水杨醛缩对硝基苯甲酰腙 钒酰配合物 钴配合物 合成 晶体结构 

分 类 号：O641.4[理学—物理化学]