The Solid State Synthesis of Metal Pyridonate Complexes and the Crystal Structure of Cu_2(C_5H_4No)_4(dmso)_2

金屬吡啶酮錯合物之固態合成及［Cu_2(C_5H_4NO)_4(dmso)_2］之結晶構造

廖彥銓(Show-Kei Yeh) ； 葉秀貴(Der-Shin Liaw) ； 彭旭明(Shie-Ming Peng)

《中央研究院化學研究所集刊》 34期 (1987/03) Pp. 49-56

https://doi.org/10.6522/BICAS.1987.34.8

摘要

第一列過渡金屬後半週期各元素之醋酸鹽與啶吡酮（2-羧基吡啶）在鹼性溶放下，未能成功合成任何一種吡啶酮錯合物。鈷、銅之醋酸鹽在固態反應條件下可生成穩定之錯合物，其中銅之錯合物可溶於二甲亞碸，再結晶可得六角形晶體。經x-光繞射解析結構，空間羣屬P2_1/n，a=9.452(2)，b=9.183(1)，c=15.849(3)Å，β=101.34(2)°, Z=2; 172個變數，696個繞射點之誤差指數R_1=0.041, R_2=0.039。這雙核錯合物由四個雙牙吡啶酮所配位（Cu-N: 2.01(1)Å，Cu-O: 1.95(1)Å），而二甲亞碸配位於軸端（Cu-O: 2.26(1)Å）形成扭曲之八面體。二銅原子問之距離為2.587(4)Å。

並列摘要

The reactions of M (OAc)_2．nH_2O (M=Fe, Co, Ni, Cu) with a-pyridone (2-hydroxypyridine) in basic solution failed to yield any pyridonate complex and the solid state reactions led to the formation of air-stable complexes of cobalt and copper. The copper complex has been recrystallized from dmso solution to form Cu_2(C_5H_4NO)_4, (dmso)_2, 1, which has been studied by X-ray structure analysis. The black green crystals of 1 conform to monoclinic space group P2_1/n with a=9.452(2)Å, b=9.183(1)Å, c=15.849(3)Å, and /β=101.34(2)°, Z=2. Final consistency indices of R_1=0.041 and R_2=0.039 were obtained from the refinement on 696 observed reflections and 172 variables. The structure consists of binuclear metal complex containing two equivalent copper atoms in distorted octahedral environment, bridged by four α-pyridonate ligands, which act as bidentate bimetallic ligands (Cu-N: 2.01(1)Å, Cu-O: 1.95(1)Å). The distorted octahedral coordination around Cu is completed by the oxygen atom of the dmso molecule (Cu-O: 2.26(1)Å) and by the second copper atom (Cu-Cu: 2.587(4)Å).