Supramolecular Stuctures from Mononuclear, Binuclear and 2D Net of Copper(II) Complexes with 6-Hydroxypicolinic Acid

First examples of transition metal complexes with HpicOH [Cu(picOH)2(H2O)2] (1), [Cu(picO)(2,2′-bpy)]·2H2O (2), [Cu(picO)(4,4′-bpy)0.5(H2O)]n (3), and [Cu(picO)(bpe)0.5(H2O)]n (4) (HpicOH = 6-hydroxy-picolinic acid; 2,2′-bpy = 2,2′-bipyridine; 4,4′-bpy = 4,4′-bipyridine; bpe = 1,2-bis(4-pyridyl)ethane) have been synthesized and characterized by single-crystal X-ray diffraction. The results show that HpicOH ligand can be in the enol or ketonic form, and adopts different coordination modes under different pH value of the reaction mixture. In complex 1, HpicOH ligand is in the enol form and adopts a bidentate mode. While in complexes 2–4, as the pH rises, HpicOH ligand becomes in the ketonic form and adopts a tridentate mode. The coordination modes in complexes 1–4 have not been reported before. Because of the introduction of the terminal ligands 2,2′-bpy, complex 2 is of binuclear species; whereas in complexes 3 and 4, picO ligands together with bridging ligands 4,4′-bpy and bpe connect CuII ions to form 2D nets with (123)2(12)3 topology.

[1]  A. Fischer,et al.  Synthesis, spectral and magnetic properties and crystal structures of copper(II) pyridinecarboxylates as potential antimicrobial agents , 2007 .

[2]  M. Du,et al.  Metal−Organic Coordination Architectures with Thiazole-Spaced Pyridinecarboxylates: Conformational Polymorphism, Structural Adjustment, and Ligand Flexibility , 2007 .

[3]  X. Bu,et al.  Novel heterometallic 3d-4f metal-azido complex of mixed ligands with unprecedented structure type: synthesis, structure, and magnetic properties. , 2006, Inorganic chemistry.

[4]  H. Nogueira,et al.  Polynuclear Molybdenum and Tungsten Complexes containing 3-Hydroxypicolinic Acid and Europium (III) , 2006 .

[5]  Lin-pei Jin,et al.  Supramolecular architectures from the self-assembly of lanthanide ions with 6-hydroxypicolinic acid and 1,10-phenanthroline , 2005 .

[6]  P. K. Bharadwaj,et al.  Coordination polymers of La(III) as bunched infinite nanotubes and their conversion into an open-framework structure. , 2005, Inorganic chemistry.

[7]  Guo-Yu Yang,et al.  A 3D coordination framework based on linkages of nanosized hydroxo lanthanide clusters and copper centers by isonicotinate ligands. , 2005, Angewandte Chemie.

[8]  Vladislav A. Blatov,et al.  Interpenetrating metal–organic and inorganic 3D networks: a computer-aided systematic investigation. Part I. Analysis of the Cambridge structural database , 2004 .

[9]  Xiang-Jun Zheng,et al.  Syntheses and Structures of the First Examples of Lanthanide Complexes with 6‐Hydroxypicolinic Acid , 2004 .

[10]  Y. Wen,et al.  A novel ligand-unsupported 3D framework polymer of trimeric copper(I) and its NLO property. , 2004, Chemical communications.

[11]  Jack Y. Lu.  Crystal engineering of Cu-containing metal-organic coordination polymers under hydrothermal conditions , 2003 .

[12]  Xiang-Jun Zheng,et al.  Supramolecular formation via hydrogen bonding in the Zn(II), Mn(II)and Cu(II) complexes with 3-hydroxypicolinic acid , 2003 .

[13]  Rute A. S. Ferreira,et al.  Novel lanthanide luminescent materials based on complexes of 3-hydroxypicolinic acid and silica nanoparticles , 2003 .

[14]  J. Cmaidalka,et al.  An Unforeseen Chemical Rearrangement of Pyridinecarboxylate to Oxalate under Hydrothermal Conditions Afforded the First Oxalato and Isonicotinato Mixed-Ligand Guest-Inclusion Coordination Polymer , 2002 .

[15]  Jack Y. Lu,et al.  A simultaneous reduction, substitution, and self-assembly reaction under hydrothermal conditions afforded the first diiodopyridine copper(I) coordination polymer. , 2002, Inorganic chemistry.

[16]  M. Drew,et al.  Polynuclear molybdenum and tungsten complexes of 3-hydroxypicolinic acid and the crystal structures of (nBu4N)2[Mo4O12(picOH)2] and (nHex4N)2[Mo2O6(picOH)2] , 2001 .

[17]  Wenbin Lin,et al.  Synthesis, X-ray Structures, and Magnetic Properties of Copper(II) Pyridinecarboxylate Coordination Networks , 2001 .

[18]  C. Raptopoulou,et al.  Copper(II) complexes with phenoxyalkanoic acids and nitrogen donor heterocyclic ligands: structure and bioactivity. , 2001, Journal of inorganic biochemistry.

[19]  A. P. Shevchenko,et al.  TOPOS3.2: a new version of the program package for multipurpose crystal- chemical analysis , 2000 .

[20]  C. Raptopoulou,et al.  Structurally diverse copper(II)-carboxylato complexes: neutral and ionic mononuclear structures and a novel binuclear structure. , 2000, Inorganic chemistry.

[21]  G. Micera,et al.  Solution speciation and spectral studies on oxovanadium(IV) complexes of pyridinecarboxylic acids , 2000 .

[22]  M. Drew,et al.  Coordination modes of 3-hydroxypicolinic acid: synthesis and crystal structures of palladium(II), platinum(II) and rhenium(V) complexes , 2000 .

[23]  Wenbin Lin,et al.  A Novel Octupolar Metal−Organic NLO Material Based on a Chiral 2D Coordination Network , 1999 .

[24]  Wenbin Lin,et al.  Luminescent Lanthanide Coordination Polymers , 1999 .

[25]  C. Raptopoulou,et al.  CuII-herbicide complexes: structure and bioactivity , 1998 .

[26]  J. D. Preez,et al.  The coordination mode of 3-hydroxypicolinic acid in oxorhenium (V) complexes. Crystal and molecular , 1998 .

[27]  R. Faure,et al.  Spectral and magnetic properties, and biological activity of several coordination compounds of dinegative isoorotato and 2-thiosoorotato ligands. Crystal structure of the tetrameric complex [Cu4(isoorotato2−)4(NH34(H2O2]·4H2O , 1996 .

[28]  George M. Sheldrick,et al.  SADABS, Program for Empirical Absorption Correction of Area Detector Data , 1996 .

[29]  H. Toma,et al.  Spectroscopic and electrochemical studies on (2-hydroxypicolinate)-bis(2,2′-bipyridine)ruthenium(II) and related complexes , 1994 .

[30]  B. Posner,et al.  Insulin mimetic peroxovanadium complexes: preparation and structure of potassium oxodiperoxo(pyridine-2-carboxylato)vanadate(V), K2[VO(O2)2(C5H4NCOO)].2H2O, and potassium oxodiperoxo(3-hydroxypyridine-2-carboxylato)vanadate(V), K2[VO(O2)2(OHC5H3NCOO)].3H2O, and their reactions with cysteine , 1993 .

[31]  R. V. Parish,et al.  Complexes of gold(III) with mononegative bidentate N,O-ligands , 1992 .

[32]  Xiao‐Ming Chen,et al.  Metal-betaine interactions—VI. Crystal and molecular structure of tetrakis(betaine)copper(II) nitrate, [Cu(Me3NCH2COO)4](NO3)2 , 1991 .