含N-丙酰皮考林酰肼的镍和锰配合物的合成及其晶体结构

Syntheses and Crystal Structures of Nickel and Manganese Complexes Containing N-Propionylpicoloylhydrazide

合成了含N-丙酰皮考林酰肼(简写为HL)的镍和锰2个配合物[NiL2](1,C18H20N6NiO4,Mr=443.11)及[MnL2](2,C18H20N6MnO4,Mr=439.34)。2个配合物均属于单斜晶系,空间群P21/c。配合物1的晶体学参数a=12.745(1),b=8.5690(8),c=18.259(2)?b=100.950(3),V=1957.8(4)?,Z=4,F(000)=920,m(MoKa)=1.029mm-1,R=0.0410,wR=0.1069;配合物2的晶体学参数a=12.553(2),b=8.360(1),c=19.074(3)?b=101.329(6),V=1962.7(5)?,Z=4,F(000)=908,m(MoKa)=0.711mm-1,R=0.0637,wR=0.1648。在配合物中,镍(Ⅱ)原子和锰(Ⅱ)原子具有扭曲的N4O2八面体配位构型,晶体通过分子间氢键作用形成一维的无限链状结构。红外光谱表明,配体在形成配合物后,n(C=O)和n(C=N)红移。电子光谱表明存在d-d,-p和d-p的跃迁。

The two title complexes containing L- (HL = N-propionylpicoloylhydrazide) have been synthesized. They are [NiL2] (1, C18H20N6NiO4, Mr = 443.11) and [MnL2] (2, C18H20N6MnO4, Mr = 439.34). They both belong to monoclinic system, space group P21/c, with a = 12.745(1), b = 8.5690(8), c = 18.259(2) ? b = 100.950(3), V = 1957.8(4) ?, Z = 4, Dc = 1.503 g/cm3, F(000) = 920, m(MoKa) = 1.029 mm-1, R = 0.0410, wR = 0.1069 (for 3029 observed reflections with I≥2s(I)) and S = 1.029 for 1; and a = 12.553(2), b = 8.360(1), c = 19.074(3) ? b = 101.329(6), V = 1962.7(5) ?, Z = 4, Dc = 1.478 g/cm3, F(000) = 908, m(MoKa) = 0.711 mm-1, R = 0.0637, wR = 0.1648 (for 2587 observed reflections with I≥2s(I)) and S = 1.034 for 2. In these complexes, the nickel or manganese reveals an aberrant octahedral coordination geometry with a N4O2. In the crystal there exist several intermolecular hydrogen bonds through which one-dimensional structures were formed. n(C = O) and n(CN) are shifted to lower frequencies in IR spectra; p-p* and d-p* charge-transitions are observed in their electronic spectra.