2,2'-二吡啶胺Ni~Ⅱ、Mn~Ⅱ配合物的合成、结构及热稳定性研究
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摘要
利用NaNCO(异氰酸钠),Dipy(Dipy=2,2'-二吡啶基胺),NiSO_4·6H_2O或MnSO_4自由组装,得到2个结构新颖的配合物[Ni(Dipy)_2(NCO)_2](1)、[Mn(Dipy)_2(NCO)_2](2),对其进行元素分析、红外光谱、TGA(热重分析)、PXRD(X-射线粉末衍射)等表征。X-射线单晶衍射检测表明,配合物1属于单斜晶系,空间群为P21/n,晶胞参数为a=1.06202(10)nm,b=1.60978(15)nm,c=1.30856(13)nm,β=96.632(2)°,V=2.2222(4)nm3,Z=4;配合物2属于单斜晶系,空间群为C2/c,晶胞参数为a=0.85272(4)nm,b=1.65974(7)nm,c=1.57540(7)nm,β=101.8690(10)°,V=2.18198(17)nm3,Z=4。在配合物1、2中,每个金属离子与两个配体(Dipy)及两个阴离子NCO-配位,形成一个以金属离子为中心的六配位八面体构型,然而中心金属离子的半径、电子云分布不同致使配合物1、2的空间排布不同。
Two novel complex [Ni( Dipy)_2( NCO)_2]( 1) and [Mn( Dipy)_2( NCO)_2]( 2) were obtained using Na NCO、2,2'-Dipyridylamine、Ni SO4·6H_2O or Mn SO4 in water and alcohol. The products were characterized by elemental analysis,IR,thermogravimetric analysis( TGA) and X-ray powder diffraction( PXRD). The X-ray diffraction analysis show that complex 1 crystallizes in monoclinic system with space group P21/ n and cell parameter a =1. 06202( 10) nm,b = 1. 60978( 15) nm,c = 1. 30856( 13) nm,β = 96. 632( 2) °,V = 2. 2222( 4)nm3,Z =4. The complex 2 belongs to monoclinic system with space group C2/c and cell parameter a =0.85272( 4) nm,b =1.65974( 7) nm,c =1. 57540( 7) nm,β =101. 8690( 10) °,V =2. 18198( 17) nm3,Z =4. In the complex 1 and 2,each metal ion coordinates with two ligands( Dipy) and two anionic NCO-,forming a sixcoordinated and distorted octahedron which the metal ion located at the center,whereas the central metal ion radius and electron cloud distribution different causing the complex 1 and 2 spatial arrangement of different.
Two novel complex [Ni( Dipy)_2( NCO)_2]( 1) and [Mn( Dipy)_2( NCO)_2]( 2) were obtained using Na NCO、2,2'-Dipyridylamine、Ni SO4·6H_2O or Mn SO4 in water and alcohol. The products were characterized by elemental analysis,IR,thermogravimetric analysis( TGA) and X-ray powder diffraction( PXRD). The X-ray diffraction analysis show that complex 1 crystallizes in monoclinic system with space group P21/ n and cell parameter a =1. 06202( 10) nm,b = 1. 60978( 15) nm,c = 1. 30856( 13) nm,β = 96. 632( 2) °,V = 2. 2222( 4)nm3,Z =4. The complex 2 belongs to monoclinic system with space group C2/c and cell parameter a =0.85272( 4) nm,b =1.65974( 7) nm,c =1. 57540( 7) nm,β =101. 8690( 10) °,V =2. 18198( 17) nm3,Z =4. In the complex 1 and 2,each metal ion coordinates with two ligands( Dipy) and two anionic NCO-,forming a sixcoordinated and distorted octahedron which the metal ion located at the center,whereas the central metal ion radius and electron cloud distribution different causing the complex 1 and 2 spatial arrangement of different.
引文
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[20]余荣华,林家皇,倪青玲,等.新型不对称双席夫碱化合物的合成及其晶体结构[J].合成化学,2016,24(1):35-38.
[21]罗亚楠,姜慧莹,刘旭影,等.配合物{[Co(5-氨基-8-羟基喹啉)2]·H2O}n的合成及结构研究[J].分子科学学报,2016,32(1):78-82.
[2]Zhang Y N,Liu P,Wang Y Y,et al.Syntheses and Crystal Structures of a Series of Zn(II)/Cd(II)Coordination Polymers Constructed from a Flexible 6,6'-Dithiodinicotinic Acid[J].Cryst.Growth Des.,2011,11(5):1531-1541.
[3]Hou L,Liu B,Jia L N,et al.Two New(3,6)-Connected Frameworks Based on an Unsymmetrical Tritopic Pyridyldicarboxylate Ligand and Co2Dimer:Structures,Magnetic,and Sorption Properties[J].Cryst.Growth Des.,2013,13(2):701-707.
[4]Zhang Y B,Zhang W X,Feng F Y,et al.A Highly Connected Porous Coordination Polymer with Unusual Channel Structure and Sorption Properties[J].Angew.Chem.Int.Ed.,2009,48(29):5287-5290.
[5]Ji C C,Qin L,Li Y Z,et al.Effect of Different Imidazole Ancillary Ligands on Supramolecular Architectures of a Series of Zn(II)and Cd(II)Complexes with a Bent Dicarboxylate Ligand[J].Cryst.Growth Des.,2011,11(2):480-487.
[6]赵国良,沈金杯,咸会朵.由癸二酸柔性配体构筑的包裹水分子的多孔过渡金属配合物的合成及与DNA作用[J].中国科学:化学,2012,(7):983-994
[7]刘海燕,黄守磊,赫丽杰,等.二维网状配合物[Cd(HL)(tbb)(H2O)]·2H2O的合成、晶体结构及荧光性质[J].化学试剂,2014,36(1):73-75.
[8]Lehn J M.Supramolecular Chemistry[M].Wiley-VCH,Weiheim,1995.
[9]马海瑞.两种新型吡啶胺类配体的设计、合成及其构筑超分子配合物的研究[D].兰州:西北大学,2005.
[10]Rosana P S,Otaciro R N,Ricardo C S,et al.Structure and Magnetism of a Binuclear Cu II Pyrophosphate:Ttransition to a 3D Magnetic Behaviour Studied by Single Crystal EPR[J].Dalton Trans.,2015,44:4732-4743.
[11]Tangoulis V,Lalia-Kantouri M,Gdaniec M,et al.New Type of Single Chain Magnet:Pseudo-One-Dimensional Chain of High-Spin Co(II)Exhibiting Ferromagnetic Intrachain Interactions[J].Inorg.Chem.,2013,52(11):6559-6569.
[12]Stephanie P,Ryan J R,Debbie L,et al.Interpreting Effects of Structure Variations Induced by Temperature and Pressure on Luminescence Spectra of Platinum(II)Bis(Dithiocarbamate)Compounds[J].Inorg.Chem.,2015,54(8):3728-3735.
[13]Chaveng P,Brian W S,Allan H W,et al.Structural Aspects of Some 2:1 Dipyridylamine Complexes of Some Copper(II)Salts:An Interesting New Polymorph of the Binuclear Carbonate/Perchlorate Tetrahydrate Adduct[J].Inorg.Chim.Acta,2009,362(1):19-26.
[14]Sujittra Y,Jaturong P,Unchulee S,et al.Crystal Structures,Spectro-Structural Correlation and Structural Pathways of Eight[Cu(Dpyam)2(NCO)][Y]Complexes(Dpyam=Di-2-Pyridylamine),Y=Br-,CF3SO-3,BF-4·dpyam,Cl-·4H2O,NO-3,PF-6,Cl O-4and BPh-4[J].Polyhedron,2007,26(4):871-882.
[15]Doyel B,Golam M,Hoong-Kun F,et al.The Mn(II)-2,2'-Dipyridylamine-Pseudohalide System:Synthesis,Crystal Structure and Luminescence Behaviour of[Mn(dpa)2(X)2]·H2O and[Mn(dpa)2(X)(OH2)]Cl O4(dpa=2,2'-dipyridylamine;X=N-3,NCO-)[J].Polyhedron,2005,24(6):747-758.
[16]Rosa C,Berta C,Ana B L,et al.Exploration of the Solid State Metallosupramolecular Chemistry of Mononuclear Nickel(II)Complexes withα-Hydroxycarboxylates and 2,2'-Dipyridylamine[J].Polyhedron,2015,85(8):124-130.
[17]Sheldrick G M.SHELXS-97,Programs Zur Losung Von Kristallstrukturen[M].Gottingen:University of Grttingen,1997:509-771.
[18]Sheldrick G M.SHELXS-97,Program for X-ray Crystal Structure Refinement[M].Grttingen:University of Grttingen,1997:208-311.
[19]Janiak C.A Critical Account onπ-πStacking in Metal Complexes with Aromatic Nitrogen-containing Ligands[J].J.Chem.Soc.,Dalton Trans.,2000,3885-3896.
[20]余荣华,林家皇,倪青玲,等.新型不对称双席夫碱化合物的合成及其晶体结构[J].合成化学,2016,24(1):35-38.
[21]罗亚楠,姜慧莹,刘旭影,等.配合物{[Co(5-氨基-8-羟基喹啉)2]·H2O}n的合成及结构研究[J].分子科学学报,2016,32(1):78-82.