Unprecedented coordination modes for PDC (pyridine-2,5-dicarboxylate) in polymorphic 3D heterobimetallic compounds α- and β-[MNa2(PDC)2(H2O)4], with M = Ni, Co

Four 3D coordination polymers have been hydrothermally synthesized using PDC (PDC = pyridine-2,5-dicarboxylate), and subsequently characterised. The four compounds are heterobimetallic, their formula being [MNa2(PDC)2(H2O)4], with M = Ni, Co. Two polymorphous compounds having the formula [NiNa2(PDC)2(H2O)4] have been obtained: polymorph α is monoclinic, and β is triclinic. Similarly, two phases have been characterised for the [CoNa2(PDC)2(H2O)4] formula, which are isostructural with the nickel compounds. All the studied compounds are 3D by covalent bonding. The four of them exhibit sodium octahedral chains whose extension allows the presence of perpendicular nickel octahedral chains for the monoclinic phases (α polymorphs). However, for the triclinic phases (β polymorphs) the connections between nickel ions just extend to trimers. The interest of these compounds lies on several aspects: two new coordination modes have been detected for PDC and all compounds exhibit a novel 3D complex multi-nodal topology. Density functional calculations have been carried out to analyse the crystallographic and chemical relationships between these phases.

[1]  T. Trindade,et al.  Three-Dimensional Lanthanide−Organic Frameworks Based on Di-, Tetra-, and Hexameric Clusters , 2009 .

[2]  T. Maji,et al.  Structural Flexibility and Selective Guest Accommodation in Two CuII Metal–Organic Coordination Frameworks , 2009 .

[3]  F. Tuna,et al.  A trinuclear copper(II) complex with 2,5-pyridine-dicarboxylato bridges - [Cu3(2,5-pydc)2(Me5dien)2(H2O)2(BF4)2] · H2O: Synthesis, crystal structure and magnetic properties , 2009 .

[4]  Daqiang Yuan,et al.  Intricate 3D lanthanide-organic frameworks with mixed nodes nets , 2009 .

[5]  Song Gao,et al.  Cobalt-lanthanide coordination polymers constructed with metalloligands: a ferromagnetic coupled quasi-1D Dy3+ chain showing slow relaxation. , 2008, Chemistry.

[6]  Deqing Zhang,et al.  In situ hydrothermal decarboxylation for unprecedented three-dimensional lanthanide–organic frameworks , 2008 .

[7]  E. Castellano,et al.  Structure and thermal reactivity of Zn(II) salts of isocinchomeronic acid (2,5-pyridinedicarboxylic acid) , 2008 .

[8]  M. Kurmoo,et al.  Hydrothermal syntheses, structures and magnetic properties of coordination frameworks of divalent transition metals , 2008 .

[9]  C. Stern,et al.  Cation-anion interactions and polar structures in the solid state. , 2007, Journal of the American Chemical Society.

[10]  L. A. Gerrard,et al.  Bimetallic Metal-Organic Frameworks Containing the (M = Cu, Pd, Pt; x = 4, 5) Building Block – Synthesis, Structure, and Magnetic Properties† , 2007 .

[11]  Ting‐Shen Kuo,et al.  Versatile 2,5-Pyridinedicarboxylate in Linking Transition-Metal Atoms into 1D and 2D Coordination Polymers and Concomitant Polymorphs , 2007 .

[12]  Yun-xia Che,et al.  A noninterpenetrating 3D coordination network with rare (4,6)-connected (4·53·62)2(42·56·64·83) topology , 2007 .

[13]  Robert C. Thompson,et al.  Coordination polymers incorporating copper(II) and manganese(II) centers bridged by pyridinedicarboxylate ligands: Structure and magnetism , 2005 .

[14]  David Casanova,et al.  Shape maps and polyhedral interconversion paths in transition metal chemistry , 2005 .

[15]  Xiaofeng Zhang,et al.  Synthesis, structural characterization and magnetic property of metal 2,5-pyridine dicarboxylate complex , 2005 .

[16]  S. M. Humphrey,et al.  Multiple areas of magnetic bistability in the topological ferrimagnet [Co3(NC5H3(CO2)2-2,5)2(mu3-OH)2(OH2)2]. , 2004, Journal of the American Chemical Society.

[17]  Song Gao,et al.  Crystal structure and magnetic properties of a new three-dimensional coordination polymer constructed from (4,4) layers based on dimeric iron(II) subunits , 2003 .

[18]  Santiago Alvarez,et al.  Continuous symmetry maps and shape classification. The case of six-coordinated metal compounds , 2002 .

[19]  E. Lachowski,et al.  Hydrothermal Synthesis and Characterisation of M(pdc)·3H2O (pdc=2,5-pyridinedicarboxylate); M=Co, Ni, CoxNiy (x=0.4–0.6, y=0.6–0.4) , 1998 .

[20]  Giovanni Luca Cascarano,et al.  Completion and refinement of crystal structures with SIR92 , 1993 .

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

[22]  Wang Yinghua.  Lorentz–polarization factor for correction of diffraction-line profiles , 1987 .