含N-乙酰皮考啉肼的锌和钒配合物的晶体结构及其激光倍频性质

Syntheses and Crystal Structures of Zinc, Vanadium and Nickel Complexes Containing N-acetylpicoloylhydrazide

合成了N 乙酰皮考啉酰肼 (HL)与锌和钒的配合物 [ZnL2 ]·H2 O(1 ,C16 H2 0 N6 O5Zn)和VⅤ O2 L(2 ,C8H8N3O4 V)。2个配合物晶体均属于单斜晶系。配合物 1的晶胞中每个不对称单元存在 2个晶体学独立的配合物分子 ,每个锌 (Ⅱ )原子与 2个N 乙酰皮考啉酰肼的 4个氮原子和 2个氧原子形成严重扭曲的N4 O2 八面体配位构型 ,配合物通过分子间氢键作用形成一维的无限链状结构。在配合物 2中 ,钒 (Ⅴ )原子具有畸变的N2 O3四角锥配位构型 ,晶体内每 2个分子通过分子间氢键作用形成缔合分子对。红外光谱表明 ,配体形成配合物后 ,σ(CO )和σ(CN )红移。电子光谱表明 ,存在d d 和π π 跃迁。配合物 1对于λ=0 1 0 6nm激光倍频系数I2ω/I2ω(KDP) 为 0 85。量子化学从头算方法计算结果证实配合物

Two title complexes ·H 2O(1, C 16H 20N 6O 5Zn) and VO 2L (2, C 8H 8N 3O 4V; HL= N-acetylpicoloylhydrazide) have been synthesized. Their crystal data were determined for complex 1 space group C c, a=3.083 2(1) nm, b=0.759 31(3) nm, c=1.837 07(8) nm, β=116.918(2)°, V= 3.834 8(3) nm 3, Z=8, F(000)=1 824,μ=1.32 mm -1, R=0.034 0, for 3 177 observed reflections(I≥2σ(I)); for complex 2 space group C 2/c, a=1.012 2(3) nm, b=1.244 5(4) nm, c=1.694 1(5) nm, β=105.587(7)°, V=2.056(1) nm 3, Z=8, F(000)=1 056, μ=0.967 mm -1, R=0.057 7 for 1 268 observed reflections(I≥2σ(I)). The Zinc(II) ion in complex 1 is coordinated with two pyridine nitrogen atoms, two diazine nitrogen atoms and two carbonyl oxygen atoms from two tridentate ligands, forming a distorted octahedral of N 4O 2. The vanadium atom in complex 2 is bound to two terminal oxygen atoms and one tridentate donor ligand in a distorted square pyramidal arrangement. There is an one-dimensional chain structure through the intermolecular hydrogen bonds and intramolecular hydrogen bonds in complex 1. Every two molecules in the crystal of complex 2 are linked by pairs through the intermolecular hydrogen bonds. The second harmonic generation I 2ω of complex 1 is 0.85 time as that of KDP.