二个含N-取代水杨基Schiff碱配体的镍配合物的合成和晶体结构

Syntheses and Crystal Structures of Two Nickel Complexes with N-Substituted-Salicyl Ligand

合成了二个N-取代水杨基Schiff碱的Ni(II)配合物[Ni2(dsh)(C5H5N)6]·2C5H5N(H4dsh=1,2-disalicyloylhydrazine)(1)和Ni(spmbh)(C5H5N)(H2spmbh=N-salicylaldehyde-N-(4-methoxybenzoyl)hydrazone)(2)。化合物1:单斜晶系,P21/c空间群,a=1.27474(5)nm,b=1.64631(7)nm,c=1.19959(5)nm,β=103.344(1)°,V=2.4495(2)nm3,Z=2,Dc=1.381g·cm-3,Mr=1018.44,μ=0.826mm-1,F(000)=1060,R=0.0331,wR=0.0733;化合物2:单斜晶系,P21/c空间群,a=1.09674(8)nm,b=0.94644(6)nm,c=1.7257(1)nm,β=91.006(4)°,V=1.7910(2)nm3,Z=4,Dc=1.506g·cm-3,Mr=406.08,μ=1.109mm-1,F(000)=840,R=0.0317,wR=0.0490。具有晶体学中心对称性的双核镍化合物1中,1,2-二水杨酰基肼通过肼基N-N单键桥联二个Ni髤原子,Ni…Ni原子间距为0.46883(4)nm,每个Ni髤原子具有轴向伸长的八面体配位构型。化合物2中,Ni髤原子具有平面正方形的配位构型。

Two nickel complexes, [Ni-2(dsh)(C5H5N)(6)].2C(5)H(5)N (1) and Ni(spmbh)(C5H5N) (2), have been synthesized and characterized, where H(4)dsh and H(2)spmbh are 1,2-disalicyloylhydrazine and N-salicylaidehyde-N'-(4-methoxybenzoyl) hydrazone, respectively. The complex 1 crystallizes in monoclinic space group P2(1)/c with a=1.274 74(5) nm, b=1.646 31(7) nm, c=1.199 59(5)nm, beta=103.344(1)degrees, V=2.449 5(2)nm(3), Z=2, F(000)=1 060, D-c=1.381 g(.)cm(-3), M-r=1 018.44, mu=0.826 mm(-1), R=0.033 1, wR=0.073 3. The complex 2 crystallizes in monoclinic space group P2(1)/c with a=1.096 74(8) nm, b=0.946 44(6) nm, c=1.725 7(1) nm, beta=91.006(4)degrees, V=1.791 0(2) nm(3), Z=4, D-c=1.506 g(.)cm(-3), M-r=406.08, mu=1.109 mm(-1), F (000)=840, R =0.031 7, wR =0.049 0. The two nickel centers in the centrosymmetric binuclear complex molecule 1 are linked by the N-N single bond of the dsh(4-) ligand, Ni...Ni distance being 0.468 83(4) nm. All the 20 non-hydrogen atoms in the dsh(4-) ligand are in the same plane. Every nickel(II) ion in 1 has an elongated octahedral Ni(ONO)(N)(N)(N) coordination. The two phenolate oxygen atoms, two carbonyl oxygen atoms and two diazine nitrogen atoms of one ligand dsh(4-) coordinate to two nickel ions, respectively. The nickel(II) atom in complex 2 is coordinated by three donors (phenolate oxygen, diazine nitrogen and carbonyl oxygen) in ligand spmbh(2-) and one pyridine nitrogen atom, forming a square geometry.