Topological description of a 3D self-catenated nickel hybrid vanadate Ni(bpe)(VO3)2. Thermal stability, spectroscopic and magnetic properties

The three-dimensional Ni(bpe)(VO3)2 hybrid compound, where bpe is 1,2-di(4-pyridyl)ethene, (C12H10N2), has been synthesized using mild hydrothermal conditions under autogeneous pressure at 140 °C during five days, obtaining green emerald prismatic single-crystals suitable for X-ray structure determination. The compound crystallizes in the orthorhombic system, space groupPbcn, with a = 14.9066(5), b = 7.6269(2) and c = 26.9624(10) A, Z = 8, and R1 = 0.0373 for 4149 observed reflections. Single-crystal X-ray diffraction reveals that the crystal structure is composed of a 3D self-catenated 10-connected uninodal net constructed from 36-hxl like {NiV2O6} inorganic sheets linked through bpe ligands. The thermal evolution of the crystal parameters shows three different tendencies during the heating process: (i) initial contraction, (ii) thermal expansion, (iii) structural collapse due to the thermal instability of the organic ligand. The IR spectrum shows the vibrational modes of the bpe organic molecules and those of the (VO4)3− tetrahedral oxoanions. Diffuse reflectance electronic absorption spectroscopy shows the characteristic bands of the Ni(II) d8-high spin cation in slightly distorted octahedral geometry. From the positions of the bands in the electronic spectrum the Dq (940 cm−1) and Racah, B (930 cm−1) and C (3350 cm−1), parameters have been calculated. Magnetic measurements indicate the existence of antiferromagnetic interactions between the Ni(II) centres of the dinuclear units, with a value of the J/k = −59.4, with g = 2.076.

[1]  William A. Goddard,et al.  Metal−Organic Frameworks Provide Large Negative Thermal Expansion Behavior , 2007 .

[2]  T. Rojo,et al.  Hydrothermal synthesis and crystal structure of the Ni2(C4H4N2)(V4O12)(H2O)2 and Ni3(C4H4N2)3(V8O23) inorganic–organic hybrid compounds. Thermal, spectroscopic and magnetic studies of the hydrated phase , 2007 .

[3]  Song Gao,et al.  Chiral magnetic metal-organic frameworks of dimetal subunits: magnetism tuning by mixed-metal compositions of the solid solutions. , 2006, Inorganic chemistry.

[4]  Cameron J Kepert,et al.  Advanced functional properties in nanoporous coordination framework materials. , 2006, Chemical communications.

[5]  Michael O'Keeffe,et al.  Crystal nets as graphs: Terminology and definitions , 2005 .

[6]  R. Doedens,et al.  Inorganic−Organic Hybrid Materials Containing Porous Frameworks: Synthesis, Characterization, and Magnetic Properties of the Open Framework Solids [{Co(4,4‘-Bipy)}V2O6] and [{Co2(4,4‘-Bipy)3(H2O)2}V4O12]·2H2O , 2004 .

[7]  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 .

[8]  Susumu Kitagawa,et al.  Functional porous coordination polymers. , 2004, Angewandte Chemie.

[9]  S. Mitra,et al.  A novel dinuclear nickel (II) complex: spectroscopic and magnetic studies , 2004 .

[10]  Davide M. Proserpio,et al.  POLYCATENATION, POLYTHREADING AND POLYKNOTTING IN COORDINATION NETWORK CHEMISTRY , 2003 .

[11]  L. Lezama,et al.  Water displacement by cyanogold complexes in binuclear nickel(II) compounds based on bridging oxalate. Synthesis, structural diversity, magnetic properties, and DFT calculations. , 2003, Inorganic chemistry.

[12]  J. Zubieta,et al.  Hydrothermal syntheses and structural characterizations of organic-inorganic hybrid materials of the M(II)-ligand/vanadium oxide system (M(II) = Cu(II) and Zn(II); ligand = 2,2'-bipyridine and 2,2':6',2"-terpyridine). , 2001, Inorganic chemistry.

[13]  J. Zubieta,et al.  Hydrothermal synthesis of organic-inorganic hybrid materials: network structures of the bimetallic oxides [M(Hdpa)2V4O12] (M = Co, Ni, dpa = 4,4'-dipyridylamine). , 2001, Inorganic chemistry.

[14]  B. Lin,et al.  Hydrothermal syntheses, structures and magnetic properties of coordination cation metavanadates, Cu(tn)2(VO3)2 and Ni(NH3)2(VO3)2 , 2000 .

[15]  B. Lin,et al.  Hydrothermal synthesis and characterization of metavanadate containing spiral chain: Ni(en)3(VO3)2 , 2000 .

[16]  P. Zavalij,et al.  Structural chemistry of vanadium oxides with open frameworks. , 1999, Acta crystallographica. Section B, Structural science.

[17]  J. Zubieta,et al.  Organic-Inorganic Hybrid Materials: From "Simple" Coordination Polymers to Organodiamine-Templated Molybdenum Oxides. , 1999, Angewandte Chemie.

[18]  D. Riou,et al.  Hydrothermal Synthesis and Structure Determination of 1,4-Diaminobutane Metavanadate , 1996 .

[19]  R. Haushalter,et al.  One-Dimensional Vanadium Oxide Chains Containing Covalently Bound Copper Coordination Complexes: Hydrothermal Synthesis and Characterization of Cu(H2N(CH2)2NH2)[V2O6], Cu(C10H8N2)[V2O6], and Cu(C10H8N2)2[V2O6] , 1996 .

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

[21]  E. Muetterties,et al.  Idealized polytopal forms. Description of real molecules referenced to idealized polygons or polyhedra in geometric reaction path form , 1974 .

[22]  Y. Tanabe,et al.  On the Absorption Spectra of Complex Ions II , 1954 .

[23]  Michael O'Keeffe,et al.  Three-periodic nets and tilings: regular and quasiregular nets. , 2003, Acta crystallographica. Section A, Foundations of crystallography.

[24]  J. Zubieta,et al.  A two-dimensional organic–inorganic material constructed from copper-dipyridylamine and vanadate chains: [Cu(dpa)VO3]† , 1999 .

[25]  Juan Faus,et al.  ABILITY OF TEREPHTHALATE (TA) TO MEDIATE EXCHANGE COUPLING IN TA-BRIDGED COPPER(II), NICKEL(II), COBALT(II) AND MANGANESE(II) DINUCLEAR COMPLEXES , 1997 .

[26]  K. K. Nanda,et al.  Linear dependence of spin exchange coupling constant on bridge angle in phenoxy-bridged dinickel(II) complexes , 1994 .