Syntheses and Crystal Structures of Complexes Zinc and Copper(Ⅱ) Nitrates with 1,10-Dioxa-4,7,13,16-tetraazacyclooctadecane

Abstract

Abstract: Two new complexes zinc and copper (Ⅱ) nitrates with 1,10-dioxa-4,7,13,16-tetraazacyclooctadecane (L) were synthesized. Cu(L)(NO₃)₂ crystalizes in orthorhombic, space group Pbca, a=1.574 4(6) nm, b=1.267 6(4) nm, c=1.898 3(6) nm, Z=8, V=3.789(2) nm³; Zn(L)(NO₃)₂ crystalizes in orthorhombic system, space group Pnna, a=1.613 56(10) nm, b=1.328 71(11) nm, c=0.862 60(5) nm, Z=4, V=1.849 4(2) nm³. Structure refinement converged to R₁=0.043 1, wR₂=0.090 4 for Cu(L)(NO₃)₂ and R₁=0.071 8, wR₂=0.195 0 for Zn(L)(NO₃)₂, respectively. Copper(Ⅱ) and zinc ions are coordinated to four nitrogen and two oxygen atoms from the azacrown ether moiety, but not to the nitrate anions. The coordination numbers for both copper(Ⅱ) and zinc ions are six. These complexes have also been characterized by IR, 1H NMR and EPR spectroscopies. The cyclic voltammogram shows that Cu(L)(NO₃)₂ undergoes a reversible reduction, Cu(Ⅱ)→Cu(Ⅰ) in acetonitrile in the range of -1.0～0 V, E 1/2=-0.56 V and an irreversible reduction, Cu(Ⅰ)→Cu(0) in the range of -1.6～0 V, E_1/2=-1.20 V.

Key words: Dioxa-tetraazacrown ether, Zinc and copper(Ⅱ) complexes, Crystal structure

CLC Number:

O614

TrendMD:

GUO Xue-Yan, ZHU Wen-Xiang, YAN Xi, WANG Ru-Ji, LI Yong. Syntheses and Crystal Structures of Complexes Zinc and Copper(Ⅱ) Nitrates with 1,10-Dioxa-4,7,13,16-tetraazacyclooctadecane[J]. Chem. J. Chinese Universities, 2002, 23(10): 1842.

References

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