含2-胺基-4,6-二甲基嘧啶配位基之 二價鋅化合物結構探討

Structural characterization of Zn(II) compounds containing 2-amino-4,6-dimethylpyrimidine

林明芳(Ming-Fang Lin)

指導教授 ： 陳志德

中原大學/理學院/化學研究所/碩士(2011年)

https://doi.org/10.6840/CYCU.2011.00212

摘要

摘要
利用金屬起始物二價鋅之鹵化鹽類與配位基2-胺基-4,6-二甲基嘧啶 (L) 反應，可獲得到三種二價鋅的化合物，其分子式如下: [ZnCl2(L)(H2O)] ⋅ 2L, 1, [ZnBr2(L)(CH3OH)] ⋅ L, 2與[ZnI2(CH3OH)2] ⋅ 2L, 3。以上所有錯合物的結構均已利用單晶 X-ray 繞射鑑定之。
化合物1的晶系空間群為Pī, a = 6.9366 (2) Å，b = 9.7762 (3) Å，c = 18.5656 (5) Å，α = 85.882 (1) °，β = 80.008 (1) °，γ = 79.924 (1) °，V = 1219.61 (6) Å3，Z = 2。化合物2的晶系空間群為Pī， a = 7.3311 (1) Å，b = 9.8646 (2) Å，c = 13.8614 (3) Å，α = 98.562(1) °，β = 97.616 (1) °，γ = 96.586 (1) °，V = 973.23 (3) Å3，Z = 2。化合物3的晶系空間群為C2/c，a = 7.2448 (3) Å，b = 21.7882 (10) Å，c =14.8311 (6) Å， β =102.503 (2) °， V = 2285.97 (17) Å3，Z = 4。化合物1每個鋅原子與配位基L的氮原子，水分子的氧原子及兩個氯原子鍵結，形成扭曲的四面體結構。其分子經由 Nam-HCl、C-HCl和Nam-HNpm、O-HNpm作用力的連結形成二維的超分子網狀結構。化合物2中鋅原子與配位基L的氮原子，甲醇分子的氧原子及兩個溴原子形成扭曲四面體結構。分子間經由Nam-HNpm和O-HNpm的氫鍵連結成二維超分子之結構。化合物3中金屬中心與兩個甲醇分子與兩個碘原子鍵結,形成扭曲四面體結構。分子間藉由O-H---Npm、Nam-HNpm與Nam-HI作用力形成二維超分子層狀結構。

關鍵字

氫鍵 ； 2-胺基-4 ； 6-二甲基嘧啶 ； 網狀 ； X-ray鑑定 ； 錯合物 ； 超分子 ； 長鏈 ； 單核金屬化合物 ； 螺旋狀

並列摘要

Abstract
A series of transition metal zinc(II) complexes [ZnCl2(L)(H2O)] ⋅ 2L, 1,[ZnBr2(L)(CH3OH)] ⋅ L, 2 and [ZnI2(CH3OH)2] ⋅ 2L, 3, have been prepared by the reactions of ZnCl2, ZnBr2 and ZnI2, respectively with 2-amino-4,6- dimethylpyrimidine (L). Their structures have been determined by X-ray crystallography.
Crystal data for 1: space group Pī, a = 6.9366 (2) Å, b = 9.7762 (3) Å, c = 18.5656 (5) Å, α = 85.882 (1) °，β = 80.008 (1) °，γ = 79.924 (1) °, V = 1219.61 (6) Å 3 , Z = 2。with final residuals R1 = 0.0355 and wR2 = 0.0867. Crystal data for 2: space group Pī, a = 7.3311 (1) Å, b = 9.8646 (2) Å, c = 13.8614 (3) Å, α = 98.562(1) °，β = 97.616 (1) °，γ = 96.586 (1) °, V = 973.23 (3) Å3 , Z = 2, with final residuals R1 = 0.0362 and wR2 = 0.0886. Crystal data for 3: space group C2/c, a = 7.2448 (3) Å, b = 21.7882 (10) Å, c = 14.8311 (6) Å , β =102.503 (2) °， V = 2285.97 (17) Å3, Z = 4, with final residuals R1 = 0.0343 and wR2 = 0.0690. In complex 1, the zinc metal center adopts tetrahedral geometry and the molecules are linked by Nam-HCl and O-HNpm,C-HCl,Nam-HNpm hydrogen bonds to form a 2-D supramolecular structure. In complex 2, the molecule are linked by Nam-HNpm and O-HNpm hydrogen bonds to form a 2-D supramolecular structure. In complex 3, the metal center is coordinated by two menthol molecules and two iodide anion to form a mononuclear structure and their molecules are linked by O-H---Npm, Nam-HNpm and Nam-HI hydrogen bonds to form a 2-D supramolecular structure.

並列關鍵字

X-ray crystallography ； complexes ； mononuclear ； hydrogen bond

參考文獻

1. Lehn, J. -M. Supramolecular Chemistry, Concepts and Perspectives, VCH,

Weinheim, 1995. (b) Steed, J. W.; Atwood, J. L. Supramolecular chemistry,Wiley, 2000.

3. Yao, W.; Eisenstein, O.; Crabtree, R. H. Inorg . Chim. Acta 1997, 254, 105.

4. Peris, E.; Lee, J. C.; Rambo, J. R.; Eisenstein, O.; Crabtree, R. H. J. Am. Chem. Soc. 1995, 117, 3485.

5. Minghetti, G.; Cinellu, M. A. J. Organome. Chem. 1986, 315, 387.