- 作者: 彭旭明; 王瑜; 陳春貴; 李珍薇; 廖德鑫
- 作者服務機構: Department of Chemistry, National Taiwan University, Taipei, Taiwan, R.O.C.
- 中文摘要: Crystal and molecular structures of the planar neutral ligand, C/sub 26/H/sub 16/N/sub 8/, and the four isomorphous five-coordinated metal complexes, [M(C/sub 26/H/sub 14/N/sub 8/-(H/sub 2/O)], M=Mn(II), Co(II), Cu(II), Zn(II), have been determined from three-dimensional X-ray diffraction data. The free ligand hpH/sub 2/, C/sub 26/H/sub 16/N/sub 8/, belongs to the P 2/sub 1//c space group with Z=2, a=4.142(3), b=23.736(6), c=10.338(3)A, .beta.=94.66(6).degree.. The metal complexes monohydrate Mhp.bcdot.H/sub 2/O all belong to the orthorhombic Pcab space group with Z=8. The dimensions are roughly 8.8*19.3*23.7 A/sup 3/. In each structure, the macrocyclic ligand has an almost planar conformation which differs from the saddle shaped ligand hydrate (hpH/sub 2/.bcdot.H/sub 2/O) and the nickel complex [Nihp]/sub 5)/. The distances from the center of the macrocyclic ring to the nitrogen atom of the free ligand are 1.907(6) and 2.245(6)A. The coordination geometry in these four complexes is square pyramidal with a water molecule as an axial ligand. The bond distances of M(II)-O(H/sub 2/O), M(II)-N1 (imine), M(II)-N3 (pyridine) are:2.19(1), 2.00(2), 2.27(2)A respectively for the manganese complex; 2.08(1), 1.97(1), 2.23(1)A for the cobalt complex; 2.33(1), 1.92(1), 2.18(1)A for the copper complex; 2.110(5), 1.964(6), 2.252(6)A for the zinc complex. The variation of metal-ligand distances can be correlated to the metal d orbital occupancy. A comparison with similar ligands will be presented.
- 英文摘要: --
- 中文關鍵字: Crystal structure; hemiporphyrazine; macrocyclic ligand and manganese, cobalt, copper, zinc complexes.
- 英文關鍵字: Crystal structure; hemiporphyrazine; macrocyclic ligand and manganese, cobalt, copper, zinc complexes.