两个含N-皮考林酰肼铁配合物的合成和结构表征

Syntheses and Characterization of Two Iron Complexes with N-Picoloylhydrazide

合成了含 N-乙酰皮考林酰肼 (简写为 Haphz)的铁配合物 [Fe2 ( aphz) 2 ( μ-CH3 O) 2 Cl2 ]· CH3 OH( 1 ,C19H2 6Cl2 Fe2 N6O7,Mr=63 3 .0 6)和含 N -苯甲酰皮考林酰肼 (简写为 Hphphz)的铁配合物 Fe( phphz) Cl2 ( 2 ,C13 H10 Cl2 Fe N3 O2 ,Mr=3 66.99) .2个配合物均属三斜晶系 ,空间群为 P1 .配合物 1 :a=0 .83 3 5 9( 6) nm,b=1 .0 9990 ( 9) nm,c=0 .75 0 5 4( 7) nm,α=91 .41 2 ( 3 )°,β=96.683 ( 3 )°,γ=1 0 7.997( 6)°,V=0 .64869( 9) nm3 ,Z=1 ,F ( 0 0 0 ) =3 2 4,μ( Mo Kα) =1 .3 74mm-1,R=0 .0 3 1 8,w R=0 .0 864;配合物 2 :a=0 .690 3 8( 6) nm,b=0 .9460 7( 9) nm,c=1 .1 85 82 ( 7) nm,α=89.3 83 ( 5 )°,β=81 .5 1 5 ( 2 )°,γ=69.2 1 4( 2 )°,V=0 .71 5 5 ( 1 ) nm3 ,Z=2 ,F( 0 0 0 ) =3 70 ,μ( Mo Kα) =1 .43 3 mm-1,R=0 .0 681 ,w R=0 .1 3 5 2 .配合物 1分子具有晶体学中心对称性 ,2个甲氧基的氧原子桥联 2个 Fe原子 ,形成中心对称的 Fe2 ( μ-O) 2 核心 ,2个 Fe( )原子间距离为 0 .3 1 60 9( 6) nm,每个 Fe原子由 N -乙酰皮考林酰肼的 2个 N原子和 1个 O原子 ,2个桥联甲氧基的 2个 O原子及氯离子形成畸变的八面体配位构型 ,配合物 1晶体通过分子间氢键作用形成?

Two iron complexes with N-acetylpicoloylhydrazide (Haphz) and N-phenylpicoloylhydrazide(Hphphz), [Fe 2(aphz) 2(μ-CH 3OH) 2Cl 2]·CH 3OH(1, C 19H 26Cl 2Fe 2N 6O 7, M r= 633.06) and Fe(phphz)Cl 2(2, C 13H 10Cl 2FeN 3O 2, M r=366.99), were synthesized. Complex 1 belongs to a triclinic system, space group P1, with cell parameters a=0.833 59(6) nm, b=1.099 90(9) nm, c=0.750 54(7) nm, α=91^412(3)°, β=96.683(3)°, γ=107.997(6)°, V=0.648 69(9) nm 3, Z=1, D c=1.621 Mg/m 3, {F(000)}324, μ(Mo Kα)=1.374 mm -1, R=0.031 8 and wR=0.086 4 for 2 547 observed reflections, GOF=1.112. Complex 2 belongs to triclinic system, space group P1 , a=0.690 38(6) nm, {b}0.946 07(9) nm, c=1.185 82(7) nm, α=89.383(5)°, β=81.515(2)°, γ=69.214(2)°, V{0^715 5(1)} nm 3, Z=2, D c=1.704 Mg/m 3, F(000)=370, μ(Mo Kα)=1.433 mm -1, R=0.068 1 and wR=0.135 2 for 1 720 observed reflections, GOF=1.056. The binuclear complex 1 has a crystallographic center. The two methanol oxygen atoms in complex 1 bridges two iron atoms, forming a Fe 2(μ-O) 2 core with crystallographic centrosymmetry and Fe...Fe distance is 0.316 09 nm. The iron atom is octahedrally coordinated by two nitrogen atoms and one oxygen of the N-acetylpicoloylhydrazide ligand, two methanol oxygen atoms and one chloride ion. The neighboring molecules in complex 1 are connected by hydrogen bonding, forming an infinite chain structure. The iron(Ⅲ) ion in complex 2 has a strongly distorted square pyramidal geometry with three donors of the N-phenylpicoloylhydrazide ligand and two chloride ions. The two centrosymmetry-related molecules of complex 2 are connected as a pair by two {N-H...O} hydrogen bonds. In the two title complexes, ν(CO) and ν(C-N) are shifted to lower frequencies in IR spectra; π-π * charge transitions and d-π * charge-transitions are observed in their electronic spectra. The emission lines (λ ex=310 nm) are shifted to higher frequencies in fluorescence spectra.