含2,4,6-三胺基嘧啶之金屬氯化物之合成與結構鑑定

Synthesis and Structures of Metal Chloride Complexes Containing 2,4,6-Triaminopyrimidine

邱奕龍(Yi-Long Chiou)

指導教授 ： 陳志德

中原大學/理學院/化學研究所/碩士(2009年)

https://doi.org/10.6840/cycu200900802

摘要

中文摘要

本論文主要探討含2,4,6-三胺基嘧啶配位基(tapm)與過渡金屬氯化物的化學研究。經由將分別溶於甲醇中的起始物NiCl2．6H2O、CoCl2．6H2O和ZnCl2，與溶於濃HCl的配位基2,4,6-三胺基嘧啶相互混合，靜置後可獲得下列三種化合物：[NiCl4(H2O)2][H2tapm]2[Cl]2, 1；[CoCl4][H2tapm], 2；[ZnCl4][H2tapm], 3。化合物1 - 3的結構已經由單晶X-ray 繞射儀測得。化合物1：空間群為Pī，a = 8.1251 (11) Å，b = 8.2632 (17) Å，c = 9.1498 (11) Å，α = 86.236(14) °，β = 65.285 (9) °，γ = 72.765 (14) °，V = 531.76 (15) Å3，Z = 1，R1 = 0.0227，wR2 = 0.0641。化合物2：空間群為R3，a = 10.0622 (9) Å，b = 10.0622 (9) Å，c = 9.7212 (16) Å，V = 852.39 (18) Å3，Z = 3，R1 = 0.0229，wR2 = 0.0575。化合物3：空間群為R3，a = 10.0571 (8) Å，b = 10.0571 (8) Å，c = 9.7126 (7) Å，V = 860.77 (11) Å3，Z = 3，R1 = 0.0240，wR2 = 0.0635。化合物1中，質子化的配位基藉由N-H…Cl與N-H…O氫鍵作用力與金屬上配位原子結合，氯離子則藉由N-H…Cl、O-H…Cl氫鍵作用力分別和質子化的配位基與金屬上配位原子結合。化合物2與3為等結構的晶體結構，其鍵結模式都是質子化的配位基藉由N-H…Cl氫鍵作用力與金屬上配位原子結合。化合物1中，金屬陰離子為鎳原子鍵結四個氯原子與兩個水分子，形成六配位八面體結構。另外，在化合物2與3中，金屬陰離子為以鈷或鋅原子為中心鍵結四個氯原子，形成四配位四面體結構。

關鍵字

氫鍵

並列摘要

Abstract

A series of transition metal chloride complexes of the types [NiCl4(H2O)2][H2tapm]2[Cl]2, 1, [CoCl4][H2tapm], 2, and [ZnCl4][H2tapm], 3, have been prepared by the reactions of NiCl2．6H2O, CoCl2．6H2O and ZnCl2 with 2,4,6-triaminopyrimidine (tapm) liginds in HCl solution. The spectroscopic data of 1 ¬¬- 3 has been characterized and the structures of 1 - 3 determined by X-ray crystallography. Crystal data for 1: space group Pī, a = 8.1251 (11) Å, b = 8.2632 (17) Å, c = 9.1498 (11) Å, α = 86.236(14) °, β = 65.285 (9) °, γ = 72.765 (14) °, V = 531.76 (15) Å3, Z = 1, with final residuals R1 = 0.0227 and wR2 = 0.0641. Crystal data for 2: space group R3, a = 10.0622 (9) Å, b = 10.0622 (9) Å, c = 9.7212 (16) Å, V = 852.39 (18) Å3, Z = 3, with final residuals R1 = 0.0229 and wR2 = 0.0575. Crystal data for 3: space group R3, a = 10.0571 (8) Å, b = 10.0571 (8) Å, c = 9.7126 (7) Å, V = 860.77 (11) Å3, Z = 3, with final residuals R1 = 0.0240 and wR2 = 0.0635. In complex 1, protonated ligands are interacted with metal chloride anions through N-H…Cl and N-H…O hydrogen bonds, and chloride ions are interacted with protonated ligands and metal chloride anions through N-H…Cl and O-H…Cl hydrogen bonds. In complexes 2 and 3, protonated ligands are interacted with metal chloride anions through N-H…Cl hydrogen bonds. While the metal center in 1 forms the octahedral geometry, those in 2 and 3 adopt the tetrahedral geometry.

並列關鍵字

hydrogen bond

參考文獻

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參考文獻

1. Jeffrey, G. A. An Introduction to Hydrogen Bonding, Oxford University Press, New York, 1997.