臺灣博碩士論文加值系統

本論文主旨在於探討2-胺基嘧啶(2-aminopyrimidine)和2-胺基-4-甲基嘧啶(2-amino-4-methylpyrimidine)與鋅金屬鹽類所合成之晶體結構，與其中所包含的弱作用力，以及其對於堆疊模式的影響。利用配位基與二價鋅鹽類反應，可得到下列八種化合物: [ZnCl2(L1)2] (L1 = 2-Aminopyrimidine), 1; [ZnBr2(L1)2], 2; [ZnI2(L1)2], 3; [ZnBr(OH)(L1)]n, 4; [Zn(NO3)(OH)(L1)]n, 5; [ZnCl2(L2)2] (L2 = 2-Amino-4-methylpyrimidine), 6; [ZnBr2(L2)2], 7; [ZnI2(L2)2], 8。以上八種化合物的構造均已利用X-ray鑑定之。
經由X-ray 所鑑定出的結構可得知，化合物為1 – 3相同構形，化合物6 – 8亦為相同構形。上述化合物皆以鋅金屬離子為中心配位上兩個有機配位基及兩個陰離子形成四面體構型的構型。分子和分子之間包含有C–H---X, N–H---X, N–H---N, 及π – π stacking 等作用力，而形成二維網狀結構。
化合物 4和 5為相同構形，鋅金屬中心配位上一個有機配位基及一個陰離子和兩個氧原子所形成四面體構型的構型。化合物形成一維的高分子鏈狀結構。鏈與鏈之間以C–H---O, O–H---O, N–H---N, 及π – π stacking 等作用力連結，而形成二維及三維高分子結構。

The syntheses and structures of a series of zinc compounds [ZnCl2(L1)2] (L1 = 2-Aminopyrimidine), 1; [ZnBr2(L1)2], 2; [ZnI2(L1)2], 3; [ZnBr(OH)(L1)]n, 4; [Zn(NO3)(OH)(L1)]n, 5; [ZnCl2(L2)2] (L2 = 2-Amino-4-methylpyrimidine), 6; [ZnBr2(L2)2], 7; [ZnI2(L2)2], 8, are reported. All compounds have been structurally characterized by X-ray crystallography.
Compounds 1 - 3 are same configuration as well as compounds 6 - 8, which consist of a central zinc(II) metal centers coordinated by two organic ligands and two anions, forming a tetrahedral geometry. The C–H---X, N–H---X, N–H---N, and π – π stacking interactions were found in the structures, which link the molecules to form 2D structures.
Compounds 4 and 5 form polymeric 1D structures, which consist of central zinc(II) metal centers coordinated by one organic ligands, one anions, and two oxygen atoms, forming a tetrahedral geometry. The C–H---O, O–H---O, N–H---N, and π – π stacking interactions were found in the structures, which link the molecules to form 2D or 3D polymer structures.

中文摘要-I
Abstract-II
謝誌-III
Contents-IV
Table contents-V
Figure contents-VI
Appendix table contents-XI
Introduction-1
Experimental-11
X-ray crystallography-16
Results and discussions-28
Structural Comparisons-58
Conclusions-60
References-61
Appendix-65



Table Contents
Table 1. Crystal data and structure refinement for 1…….……...… 18
Table 2. Crystal data and structure refinement for 2………............ 19
Table 3. Crystal data and structure refinement for 3………..….…. 20
Table 4. Crystal data and structure refinement for 4……………… 22
Table 5. Crystal data and structure refinement for 5……………… 23
Table 6. Crystal data and structure refinement for 6…………........ 25
Table 7. Crystal data and structure refinement for 7………….…... 26
Table 8. Crystal data and structure refinement for 8………….…... 27
Table 9. Selected bond distances (Å) and angles (°) for 1………....28
Table 10. Selected bond distances (Å) and angles (°) for 2…………35
Table 11. Selected bond distances (Å) and angles (°) for 3…………37
Table 12. Selected bond distances (Å) and angles (°) for 4…..……. 42
Table 13. Selected bond distances (Å) and angles (°) for 5…….….. 45
Table 14. Selected bond distances (Å) and angles (°) for 6………... 48
Table 15. Selected bond distances (Å) and angles (°) for 7………... 51
Table 16. Selected bond distances (Å) and angles (°) for 8………... 54
Table 17. Comparisons of compound 1 - 3 and 6 - 8…….…..….…. 59
Table 18. Atomic volume of the halide atom…………….…........... 59


Figure Contents
Fig. 1. Examples of Ag - Ag contacts, which are unsupported
by bridging ligands…………………………………......2
Fig. 2. Molecular structures of the bis-chelate complex
[Ag(5,5’-dicyano-2,2’-bipyridine)2]BF4….…………….3
Fig. 3. Ag(I) with simple aromatic hydrocarbons lead to a
Ag(I) - π interaction…………........................................3
Fig. 4. Base pairing in DNA by hydrogen bonding………..…..4
Fig. 5. (a) Face-to-face (b) off-set (c) face-to-edge…………… 5
Fig. 6. Coulombic self-assembly between the quaternary
ammonium group………………………………..……..5
Fig. 7. The anion bridging in AgNO3 and
2-aminomethylpyridinedipropionitrile (2-AMPDPN)…6
Fig. 8. The halogen-halogen interactions……………............... 7
Fig. 9. (a) D-H---XM ,(b) D-H---X2M and (c) D-H---X3M
(D = hydrogen bond donor, e.g. C, N, O)………………8
Fig. 10. The Cl---Br interactions between molecular chains…… 8
Fig. 11. (a) Negative and positive electrostatic potentials of
halocarbons. (b) Anisotropic atomic charge distribution
around halogens………………………………………...9
Fig. 12. Charge transfer involves movement of electrons……… 9
Fig. 13. An ORTEP showing the molecular structure of
compound 1 ……………………………………………28
Fig. 14. A packing diagram showing the C-H---Cl and N-H---Cl
hydrogen bonding among the molecules……………….29
Fig. 15. (a) A packing diagram showing the N-H---N hydrogen
bonding among the molecules for compound 1; (b) the
wave-like chain of compound 1…………………...…...30
Fig. 16. A view showing the π – π stacking among the
molecules……………………………………………….30
Fig. 17. (a) A view of packing diagram for compound 1; (b) the
ABAB molecular packing of 2D layers……………..…31
Fig. 18. An ORTEP showing the molecular structure of
compound 2 ……………………………………………32
Fig. 19. A packing diagram showing the C-H---Br hydrogen
bonding among the molecules………………………….33
Fig. 20. A dimer structure formed by C-H---Br hydrogen
bonding…………………………………………………34
Fig. 21. The N-H---N interactions between molecular zigzag
chain of compound 2…………………………………...34
Fig. 22. A packing diagram showing the 2-D hydrogen bonded
net………………………………………………………35
Fig. 23. A view showing the π – π stacking among the
molecules…………………………………………….....35
Fig. 24. (a) A view of packing diagram for compound 2; (b) the
ABAB molecular packing of 2D layers………………..36
Fig. 25. An ORTEP showing the molecular structure of
compound 3 ……………………………………………37
Fig. 26. A packing diagram showing the C-H---I hydrogen
bonding among the molecules………………………….38
Fig. 27. A dimer structure formed by C-H---I hydrogen
bonding…………………………………………………39
Fig. 28. The N-H---N interactions between molecular zigzag
chain of compound 3…………………………………...39
Fig. 29. A packing diagram showing the 2-D hydrogen bonded
net………………………………………………………40
Fig. 30. A view showing the π – π stacking among the
molecules…………………………………………….....40
Fig. 31. (a) A view of packing diagram for compound 2; (b) the
ABAB molecular packing of 2D layers………………..41
Fig. 32. An ORTEP showing the molecular structure of
compound 4 ……………………………………………42
Fig. 33. A view showing the 1-D polymer chain of compound
4………………………………………………………...43
Fig. 34. A view showing the π – π stacking among the
molecules…………………………………………….....44
Fig. 35. The N-H---N interactions between molecular polymer
chain of compound 4…………………………………...44
Fig. 36. An ORTEP showing the molecular structure of
compound 5 ……………………………………………45
Fig. 37. A view showing the 1-D polymer chain of compound
5………………………………………………………...46
Fig. 38. A view showing the π – π stacking and N-H---N among
the molecules………………………...............................47
Fig. 39. A packing diagram showing the 3-D structure……….... 47
Fig. 40. An ORTEP showing the molecular structure of
compound 6 ……………………………………………48
Fig. 41. A dimer structure formed by C-H---Cl hydrogen
bonding……………………………………………..…..49
Fig. 42. The N-H---N interactions between molecular zigzag
chain of compound 6…………………………………...50
Fig. 43. A packing diagram showing the 2-D hydrogen bonded
net………………………………………………………50
Fig. 44. An ORTEP showing the molecular structure of
compound 7 ……………………………………………51
Fig. 45. A packing diagram showing the C-H---Br hydrogen
bonding among the molecules………………………….52
Fig. 46. The N-H---N interactions between molecular zigzag
chain of compound 7…………………………………...53
Fig. 47. A packing diagram showing the 3-D hydrogen bonded
net………………………………………………………53
Fig. 48. An ORTEP showing the molecular structure of
compound 8 ……………………………………………54
Fig. 49. A packing diagram showing the C-H---I hydrogen
bonding among the molecules………………………….55
Fig. 50. (a) The N-H---N interactions between molecular
helical chain of compound 8; (b) View of the 1-D
hydrogen bonded helical chain running along the c
axis…………………………………...............................56
Fig. 51. A packing diagram showing the 3-D hydrogen bonded
net....................................................................................57
Fig. 52. Shows two types conformations of syn and anti for the
bound L1 or L2 ligands………………………………...58

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