臺灣博碩士論文加值系統

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。

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.

目 錄
摘 要.......................................................................................................................I
Abstract...................................................................................................................II
謝 誌......................................................................................................................Ⅲ
目 錄.....................................................................................................................IV
圖目錄.....................................................................................................................V
表目錄.................................................................................................................VII
簡 介.......................................................................................................................1
實驗部分...............................................................................................................14
X-ray 晶體結構解析............................................................................................17
結果與討論...........................................................................................................39
結 論.....................................................................................................................48
參考文獻...............................................................................................................49

圖目錄
圖(1) 氫鍵模式圖.............................................................................................2
圖(2) 氫鍵鍵角範圍.........................................................................................3
圖(3) 化合物[Ag(NO3)(L)]n 的ORTEP 圖....................................................5
圖(4) 化合物[Ag(NO3)(L)]n 的氫鍵圖...........................................................5
圖(5) 化合物[Ag(ClO4)(L)〃H2O]n ORTEP 圖............................................6
圖(6) 化合物[Ag(ClO4)(L)〃H2O]n 的氫鍵圖................................................6
圖(7) 化合物[Ag4(SO4)2(L)2(H2O)4]n ORTEP 圖..........................................7
圖(8) 化合物[Ag4(SO4)2(L)2(H2O)4]n 的氫鍵圖.............................................7
圖(9) 化合物[Ag(PF6)(L)2] ORTEP 圖............................................................8
圖(10) 化合物[Ag(PF6)(L)2]的氫鍵圖.............................................................8
圖(11) 化合物[Cu4Cl6 (HL)2]的結構圖............................................................9
圖(12) 化合物[Cu4Cl6 (HL)2]的氫鍵圖............................................................9
圖(13) [Cu4Br6][HL]2結構圖............................................................................10
圖(14) 化合物[Cu4Br6][HL]2的氫鍵圖...........................................................10
圖(15) Zn(II)與N,N'-di(4-pyridyl) adipoamide反應....................................12
圖(16)本論文所使用之2-胺基-4,6-二甲基嘧啶配位基結構示意圖.............13
圖(17) 化合物1的ORTEP圖........................................................................40
圖(18) 化合物 1 的氫鍵示意圖.....................................................................41
圖(19) 化合物 2 的ORTEP圖.........................................................................42
圖(20) 化合物 2 的氫鍵示意圖......................................................................43
圖(21) 化合物 3 的ORTEP圖.........................................................................44
圖(22) 化合物 3 的氫鍵示意圖......................................................................45

表目錄
表(1)氫鍵特性表............................................................................................1
表(2)鹵素原子體積......................................................................................11
表(3)一價和二價的金屬鹽類與配位基L及L´(N,N'-di(4-pyridyl)adipoamide)
的反應............................................................................................................13
表(4)化合物 1 的晶體資料.........................................................................18
表(5)化合物 1 的非氫原子座標(×104)及電子分佈係數(Å2×103).............19
表(6)化合物1 的鍵長(Å) ........................................................................20
表(7)化合物1 的鍵角(°) ...............................................................................21
表(8)化合物1 的非氫原子的熱係數(Å2x103) .............................................23
表(9)化合物 1 的氫原子座標(×104)及電子分佈係數(Å2×103) .................24
表(10)化合物2 的晶體資料...........................................................................26
表(11)化合物2 的非氫原子座標(×104)及電子分佈係數(Å2×103)...............27
表(12)化合物2 的鍵長 (Å) ...........................................................................28
表(13)化合物2 的鍵角(°) ..............................................................................29
表(14)化合物2 的非氫原子的熱係數(Å2x103) .............................................31
表(15)化合物2 的氫原子座標(×104)及電子分佈係數(Å2×103)...................32
表(16)化合物3 的晶體資料............................................................................33
表(17)化合物3 的非氫原子座標(×104)及電子分佈係數(Å2×103)...............34
表(18)化合物3 的鍵長 (Å).............................................................................35
表(19)化合物3 的鍵角(°) ...............................................................................36
表(20)化合物3 的非氫原子的熱係數(Å2x103) ........................................37
表(21)化合物3 的氫原子座標(×104)及電子分佈係數(Å2×103) ..............38
表(22)化合物 1 的氫鍵作用力之鍵長及鍵角..........................................41
表(23)化合物 2 的氫鍵作用力之鍵長及鍵角..........................................43
表(24)化合物 3 的氫鍵作用力之鍵長及鍵角..........................................45
表(25)化合物1～3金屬原子與鹵素鍵角比較............................................46
表(26)化合物1～3結構的比較....................................................................47

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