On the new low-dimensional organic–inorganic hybrid solids Cu4(bipy)4[V4P2O19]·nH2O (n∼ 5) and Cu2(bipy)2[V2P2O12] with linear [V4P2O19]8− and cyclic [V2P2O12]4− oligomers

The new hybrid organic–inorganic copper oxovanadium phosphates of composition Cu4(bipy)4V4O11(PO4)2·nH2O (n ∼ 5) (1) and Cu2(bipy)2V2P2O12 (2) (bipy = 2, 2′-bipyridine) adopting the triclinic symmetry were obtained by soft hydrothermal routes. Both structures present different oxovanadium phosphate anionic units, resulting from the vertex-sharing of PO4 and VO4 tetrahedra, which are coordinated to copper diimine cationic groups to form a 1D framework. The VPO structures are reminiscent of the known connectivity and geometry of polyphosphate anions. For the two compounds, the magnetic copper(II) centres are square pyramidally coordinated with two nitrogen atoms of the neutral diimine ligand and three oxygen atoms of the oxovanadium phosphate subunit. The CuN2O3 pyramids are linked together by oxo-bridges involving PO4 tetrahedra in Cu2(bipy)2V2P2O12 with the closest Cu–Cu distances corresponding to 4.98 A. Edge-sharing of the copper pyramids in Cu4(bipy)4V4O11(PO4)2·nH2O results in the binuclear unit {Cu2O4N4}, with Cu–Cu distances of 3.19 A. Additional links of these dimers by phosphate oxo-bridges result in the formation of rectangular tetramers Cu4 with a copper–copper separation of approximately 4.10 A. Results of thermal analysis and magnetic susceptibility are presented.

[1]  A. Vega,et al.  Magnetic properties of phosphate-bridged copper(II) organic–inorganic hybrid compounds , 2003 .

[2]  J. Verkade,et al.  Organic-organometallic crystal engineering: novel formation of a honeycomb supramolecular architecture of [Re2(mu-OMe)3(CO)6]- anions encapsulating a linear H-bonded chain of [DABCO-H]+ cations. , 2003, Inorganic chemistry.

[3]  P. Maggard,et al.  Synthesis and properties of V6O16CU(C4H4N2)2 x (H2O)(0.22(1)): charge density matching of a metal-segregated layer structure. , 2003, Inorganic chemistry.

[4]  A. Jacobson,et al.  Vanadyl Oxalatophosphate Compounds (C2H10N2)[VO(HPO4)]2(C2O4) and (CH6N3)2[[VO(HPO4)]2(C2O4) and Their Thermal Transformation to (VO)2P2O7 via VOHPO4 , 2001 .

[5]  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.

[6]  S. Feng,et al.  Hydrothermal Syntheses and X-ray Crystal Structures of Three Inorganic−Organic Hybrid Materials in a Copper Vanadium Phosphate Family: CuL(VO2)(PO4) (L = 4,4‘-bipy, 1,10-phen, 2,2‘-bipy) , 2000 .

[7]  S. Feng,et al.  Inorganic/Organic Hybrid Materials: Layered Vanadium Oxides with Interlayer Metal Coordination Complexes , 1999 .

[8]  P. Amorós,et al.  New trends in V–P–O solids , 1999 .

[9]  Christopher J. Warren,et al.  Structure-Directing Role of Organoamine Ligands in the Self-Assembly of Novel Bimetallic Oxides† , 1998 .

[10]  R. Haushalter,et al.  Variations on a One-Dimensional Theme: The Hydrothermal Syntheses of Inorganic/Organic Composite Solids of the Iron Molybdate Family , 1998 .

[11]  R. Haushalter,et al.  Composite Solids Constructed From One‐Dimensional Coordination Polymer Matrices and Molybdenum Oxide Subunits: Polyoxomolybdate Clusters within [{Cu(4,4′‐bpy)}4Mo8O26] and [{Ni(H2O)2(4,4′‐bpy)2}2Mo8O26] and One‐Dimensional Oxide Chains in [{Cu(4,4′‐bpy)}4Mo15O47]·8H2O , 1997 .

[12]  R. Haushalter,et al.  Solid‐State Coordination Chemistry: Hydrothermal Synthesis of Layered Vanadium Oxides with Interlayer Metal Coordination Complexes , 1996 .

[13]  I. D. Brown,et al.  Bond‐valence parameters obtained from a systematic analysis of the Inorganic Crystal Structure Database , 1985 .

[14]  J. Zubieta,et al.  Solid state coordination chemistry of oxovanadium phosphates: hydrothermal syntheses and structures of the network and chain phosphate phases [{Cu(bpy)}2(VO)3(PO4)2(HPO4)2]·2H2O and [{Cu(terpy)}2(VO2)3(PO4)(HPO4)2] , 2000 .

[15]  J. Zubieta,et al.  Hydrothermal synthesis and structural characterization of prototypical organic–inorganic hybrid materials: [{Cu(2,2′-bpy)(H2O)}(VO)(O3PCH2PO3)], [Cu(2,2′-bpy)(VO)(O3PCH2CH2PO3)], and [Cu(2,2′-bpy)(VO)(O3PCH2CH2CH2PO3)]·H2O. Bimetallic phosphonate networks with surface-modifying organic subunits , 2000 .

[16]  C. Sangregorio,et al.  Solid state coordination chemistry: two-dimensional oxides constructed from polyoxomolybdate clusters and copper–organoamine subunits , 1998 .

[17]  J. Zubieta,et al.  A two-dimensional network constructed from hexamolybdate, octamolybdate and [Cu3(4,7-phen)3]3+ clusters: [{Cu3(4,7-phen)3}2{Mo14O45}] , 1998 .