含四氮杂大环的双(O,O'-二(2-苯乙基)二硫代磷酸根)合镍(II)或铜(II)配合物的合成和晶体结构  

Syntheses and Crystal Structures of Bis (O,O'-di(2-phenylethyl)dithiophosphate) Nickel(II) or Copper(II) Complexes Containing Tetraazamacrocycle Ligand

作　　者：谢斌[1] 李可彬[1] 邹立科[1] 毛治华[2] 洪洲[2] 

机构地区：[1]四川理工学院基础科学系,自贡643033 [2]四川大学分析测试中心,成都610043

出　　处：《Chinese Journal of Structural Chemistry》2004年第3期324-331,共8页结构化学（英文）

摘　　要：合成了含四氮杂大环hmta(hmta = meso-5,7,7,12,14,14-六甲基-1,4,8,11-四氮杂环十四烷 )和O,O-二(2-苯乙基)二硫代磷酸根的配合物 [Ni(hmta){SSP(OCH2CH2Ph)2}2] 1和 [Cu(hmta){SSP(OCH2CH2Ph)2}2] 2 , 并测定了它们的晶体结构。配合物1属单斜晶系,空间群为P21/c,晶胞参数为: C48H72N4O4P2S4Ni, a = 9.827(3), b = 19.430(6), c = 13.932(3) ? b = 99.99(2), Mr = 1017.99, V = 2620(1) 3, Z = 2, Dc = 1.285 g/cm3, = 0.635 mm-1, F(000) = 1076, 最终的偏离因子为R = 0.0434, wR = 0.1078, 相应的可观测反射数为2306; 配合物2属单斜晶系, 空间群为P21/c, 晶胞参数为: C48H72N4O4P2S4CuO25, a = 9.730(4), b = 19.513(4), c = 14.031(3) ? b = 99.97(3), Mr = 1022.82, V = 2624 (1) 3, Z = 2, Dc = 1.295 g/cm3, = 0.681 mm-1, F(000) = 1086, 最终的偏离因子为R = 0.0465, wR = 0.1222, 相应的可观测反射数为2492。结构测定表明:两配合物中的配体 (PhCH2CH2O)2PS2-均为单齿配体,金属离子与硫和氮形成了六配位的拉长的八面体配合物,配合物分子具有中心对称性; 同时晶胞中配合物的两配体之间形成了2种N-H贩稴氢键。Two complexes [M(hmta){SSP(OCH2CH2Ph)2}2] (hmta = meso-(5,7,7,12,14,14-hexamethyl- 1,4,8,11-tetraazacyclotetradecane), and M = Ni 1 or Cu 2) have been synthesized and characterized by elemental analysis, molar conductivity, IR spectra, electronic spectra and room magnetic moment. Their crystal structures have been determined by single-crystal X-ray diffraction method. Crystal data for 1: monoclinic, space group P21/c with a = 9.827(3), b = 19.430(6), c = 13.932(3) ? b = 99.99(2), Mr = 1017.99, V = 2620(1) ?, Z = 4, Dc = 1.285 g/cm3, ?= 0.635 mm-1, F(000) = 1076, the final R = 0.0434 and wR = 0.1078 for 2306 observed reflections (I > 2s(I)); and for 2: monoclinic, space group P21/c with a = 9.730(4), b = 19.513(4), c = 14.031(3) ? b = 99.97(3), Mr = 1022.82, V = 2624(1) 3, Z = 4, Dc = 1.295 g/cm3, ?= 0.681 mm-1, F(000) = 1086, the final R = 0.0465 and wR = 0.1222 for 2492 observed reflections (I > 2s(I)). The structure determination shows: the ligand (PhCH2CH2O)2PSS- is a monodentate ligand coordinating to nickel or copper ion which has a formal six-coordination number. Two complexes exist as a centrosymmetric lengthened octa- hedron geometry. There are two NH…S hydrogen bonds between tetraazamacrocycle hmta and (PhCH2CH2O) 2PSS- ligand in the complexes.

关 键 词：四氮杂大环 O O’—二(2—苯乙基)二硫代磷酸 铜配合物 镍配合物 合成 晶体结构 润滑油 抗氧剂 

分 类 号：O627[理学—有机化学]