摘要或動機

在本實驗中，我們合成了三個新的鋅的幾何異構物：trans-facial-[Zn(dipica)₂]Cl₂.CH₃OH(dipica=dipicolylamine，C₁₂H₁₃N₃，雙(2吡啶甲基)胺)trans-facial-[Zn(dien)₂]Cl₂(dien=diethylenetriamine，C₄H₁₄N₃，二乙基三胺)及反式-[Zn(demn)₂Cl₂](demn=N,N’-dimethylethylenediamineC₄H₁₂N₂，N,N'-二甲基乙二胺)。本實驗的特色皆在室溫下反應，採用擴散法培養晶體。trans-facial-[Zn(dipica)₂2]Cl₂.CH₃OH晶體為三斜晶系，晶格常數a=8.8269(6)Å, b=8.9908(6)Å, c=10.0292(6)Å,α=76.715(1)^。,β=81.232(1)^。,γ=67.753(1)^。;其空間群為P1，可信度R=0.025,Rw=0.0697。六配位的陽離子，其結構為扭曲八面體，兩個含氮三牙基(dipica)trans-facial配位，赤道面(ZnN(1)N(2)N(1A)N(2A))由兩個含吡啶環之氮(N(1)、N(1A))及兩個飽和胺之氮(N(2)、N(2A))所組成。主軸為兩個吡啶環之氮所組成。兩個含氮三牙基(dipica)與鋅的咬合角皆為84.5^。。trans-facial-[Zn(dien)₂]Cl₂晶體為單斜晶系，晶格常數為a=11.3050(3)Å,b=10.9264(3)Å, c=12.6147(3)Å,β=92.884(1)^。;其空間群為P2₁/c，可信度R=0.0191，Rw=0.0484。六配位的離子，其結構為扭曲八面體，兩個含氮三牙基(dien)與鋅的咬合角為156°、157°。反式-[Zn(dmen)₂Cl₂]晶體為單斜晶系，晶格常數 a=10.3397(4)Å,b=8.5916(4)Å,c=7.9774(3)Å,β=100.520(1)°;其空間群為C2/m，可信度R=0.0266，Rw=0.0686。其結構為八面體，鋅原子四個氮原子組成赤道面(ZnN(1)N(1A)N(1B)N(1C))，兩個氯原子位於此平面的兩側。兩個含氮雙牙基(dmen)與鋅的咬合角皆為83.0(1)Å。



In this study, we have synthesized three new geometrical isomers of zinc(II)complexes:
trans-facial-bis(dipicolylamine)zinc(II)chloride-mathanol(1/2)(trans-fac-[Zn(dipica)₂]Cl₂.2CH₃OH),
trans-facial-bis(ethylenetriamine)zinc(II)chloride(trans-fac[Zn(dien)₂]Cl₂)and trans-bis(N,
N'-dimethylethylenetriamine)zinc(II)chloride(trans-[Zn(dmen)₂]Cl₂). The crystals
suitable for X-ray diffraction were obtained by slow diffusion of ether to solution
of the products. There molecular strctures determined by X-ray diffraction. The
complex trans-fac-[Zn(dipica)₂]Cl₂.2CH₃OH crystallizes in the triclinic space group
P 1 with a=8.8269(6)Å, b=8.9908(6)Å, c=10.0292(6)Å,α=76.715(1)^。,β=81.232(1)^。,γ=
67.753(1)^。, for Z=1. The R value is 0.0259 for 3286 significant reflections. In
the hexacoordinate cation, the two tridentate dipicolylamine ligands are trans-facially
coordinated with two pyridine nitrogens and two secondary amine nitrogens situated
on four positions in a basal plane(ZnN(1)N(2)N(1A)N(2A)). The remaining two pyridine
nitrogens constitute the axis in a distorted octahedra structure. Colorless trans-fac-[Zn(dien)₂]Cl₂

crystallizes the monoclinic space group P2₁/c with a=11.3050(3)Å, b=10.9264(3)Å,
c =12.6147(3)Å,β=92.884(1)^。,and Z=1. The R value is 0.0191 for 3285 significant
reflections. The zinc(II) atom has distorted octahedra coordination, in which the
ligands are bound in a trans-facial configuration. Colorless trans-[Zn(dmen)₂Cl₂]
crystallizes the monoclinic space group C2/m with a=10.3397(4)Å, b= 8.5916(4)Å,
c=7.9774(3)Å,β=100.520(1)^。, and Z=2. The R value is 0.0266 for 856 significant reflections.
The zinc(II)atom of trans-[Zn(dmen)₂Cl₂]is six coordinate with 4 nitrogens of bidentate
dmen forming a basal plane(ZnN(1)N(1B)N(1A)N(1C)),and two chlorines on the axial
sites completing an octahedra structure.