N,N’-亚乙基双(1-苯基-3-亚氨基-1-丁酮)硫氰酸根合锰(Ⅲ)的合成和晶体结构

Synthesis and Crystal Structure of the Complex Mn(III)(bzacen)(NCS)

合成了N,N”-亚乙基双(1-苯基-3-亚氨基-l-丁酮)硫氰酸根合锰(Ⅲ),Mn(C_(22)H_(22)·N_2O_2)(NCS),M_r=459.44.该配合物晶体的晶体学参数为:三斜晶系,P1空间群,a=1.0702(3),b=1.2342(2),c=0.8999(2)mm,a=93.74(2)°β=97.09(2)°γ=109.07(2)°,V=1.1078(9)nm^3,D_c=1.377g·cm^(-3),Z=2,F(000)=476,μ=6.85cm^(-1)晶体结构用直接法解出,3205个I≥4σ(I)的可观测点用于结构修正,最终R=0.052,R_w=0.067 Mn原子由三个N原子和两个O原子形成扭曲的四角锥配位构型,晶体沿C轴方向存在贯穿整个晶体的空“隧道”.红外光谱和拉曼光谱均表明配体在形成配合物后,vC=N,vC=O和vC=c带均移向低频.vC=N带(2063cm^(-1))表明NCS^-是通过N原子与Mn(Ⅲ)配位.拉曼光谱中,462cm^(-1)和399cm^(-1)分别为Mn—O和Mn—N的振动带.电子光谱表明有d～d~*,π～π~*跃迁和d～π~*荷移跃迁.电极电位测定表明该配合物中Mn(Ⅲ)不易被氧化和还原.

The complex [ N, N' - ethylenebis( 1 - phenyl - 3 - imino - 1 - butanonato] Mn(III) thiocyanate has been synthesized. The title compound Mn( III )(bzacen)(NCS) crystallizes in the triclinic system, space groupP1,with parameters: a = 1. 0702(3)nm, b =1. 2343 (2) nm, c =0.8999(2)nm,α=93.74(2)°,β = 97.09(2)°,γ= 109.07(2)°, V= 1.1078(9)nm3,Dc = 1.377g·cm-3, Z = 2, F (000) = 476, u = 6. 85cm-1. The final R value is 0. 052 for 3205 observedreflections with I>σ4 (7). The coordination geometry around Mn atom is distorted square -pyramidal, the basal plane consisting of two nitrogen atoms and two oxygen atoms from the Schiff base ligand bzacen2- , while axial site is occupied by a nitrogen atom from NCS- group. The packing of the molecules leaves empty channels running through the crystal along the c axis. The shifts of VC = N ,VC=o and vc=cto lower frequencies in IR and Raman spectra indicate that the ligand bzacen2 has been coordinated to Mn atom through its nitrogen and oxygen atoms. The lines observed at 462 cm-1 and 399cm-1 in Raman spectrum are assigned to Mn-O and Mn-Nvibrations, respectively. There are π-π* transition, d ~ π * charge- transfer transitions and d^d* transition in electronic spectrum. The current potential curve in acetontrile reveals that Mn (III) is in stable valence state. The electronic structure was studied by the EHMO calculation.