Synthesis And Characterization Of Organic-Inorganic Hybrid Metal Phosphate

Combining the merits of organic materials and inorganic materials,organic-inorganic hybrid materials have diverse potential applications. The synthesisand preparation of inorganic-organic hybrid compounds is an important part ofmolecular designing in mordern chemistry.In such materials, the inorganic ocide contributes to the increased complexity andhence functionality through incorporation as one component in a multilevel-structuredmaterial where there is a synergistic interaction between the organic and inorganiccomponents.As a subclass of the hybrid materials, organic metal phosphate hybrid materials areof great importance. They are enjoying widespreas interests due to heterogeneouscatalysts, sorbents, ion exchangears as well as their interesting structure features. Thus,designing synthesis the cobalt phosphates material of novel structure and specialfunction is the our chief task.In this paper, we synthesized and chracterized novel phophate using hydrothermalsynthesis in order to study the multiform structure and potentionl appliction oforganic-inorganic hybrid materials. We using hydrothermal synthesis, DETA andethylenediamine as template, synthesized a series of phophate crstals, two of whichhave not been reported and one of which has only been reported powder phase.Thecrystal structure was determined by single crystal X-Ray diffraction. The EDX wasused to identify the chemical composition of the new compounds. The functiongroups contained in those compounds were tested by IR.1. Novel compound (C₂N₂H₁₀)₂[Zn(PO₄)₂]The color of the crystal is corlorless and its shape is rod like. The crystallographicparameters is: orthorhombic space group Pccn, a=17.056(3) , b=8.4219(17) ,c=8.7260(18) , V=1253.4(4) 3, Z=4. The final refinement was based on 1490independent reflections for 88 parameters and converged to RB1B＝0.0287,wRB2B(all data)＝0.0785. All Zn and P atoms adopt tetrahedra coordination. The POB4B tetrahedra shares two of the oxygen atoms with two ZnOB4B tetrahedra. These tetrahedral buildingblocks self assemble into infinite chains propagating following c axis. There is a holealong the b axis and whose diameter is 4.36?. The framework structure of thecompound consists of alternating inorganic and organic layers stacked along [100]direction. The inorganic and organic layers are connected by N－H···O hydrogenbridges. Two organic layers are located between two inorganic layers. The organiclayers are built by diprotonated (C₂H₁₀N₂)²⁺ ions which are approximatelyperpendicular to each other on the bc plane. The inorganic layers are built by theinfinite chains which are parallel to each other along the b axis.2. Novel compound (C₂N₂H₁₀)₆[Na₂Mo₁₂O₃₁(PO₄)(HPO₄)₂(H₂PO₄)₅]·3.5H₂OThe color of the crystal is dark red and its shape is sheet like. The crystallographicparameters is: triclinic space group P-1, a=12.0117(4) , b= 14.5565(5) , c=21.2805(8) ,α= 80.65(0),β= 82.64 (0),γ= 76.26 (0), V= 3550.8(2) 3, Z=2. Thefinal refinement was based on 15682 independent reflections for 88 parameters andconverged to RB1B＝0.0503,wR₂(all data)＝0.1281. The structure comprisedmolybdenum octahedra and phosphorus tetrahedra. The single crystal X-ray analysisreveals that the title compound consists of [Mo₆P₄] hexamers, sodium cations, andlattice water molecules. [Mo₆P₄] unit is made up of six [MoO₆] octahedra and four[POB4B] tetrahedra. The basic [Mo₆P₄] building blocks of the title compound is bondedtogether via octahedral Na⁺Pions to form an centrosymmetric Na[Mo₆P₄]₂ Bdimer. Thesix oxo-bridged molybdenum atoms are coplanar and constitute a six-membered ring.Among four phosphate groups three around the periphery of the ring and one in thecenter. This compound contains two types of tunnels. A small tunnel is surrounded bytwo Na(3) cations and two Na(2) [Mo₆P₄]₂ anions, with a tunnel bore diameter of 6.06A°based on the Na–Na distance. The other tunnel is surrounded by four Na(3) cations,two Na(1)[Mo₆P₄]₂ anions, and two Na(2)[Mo₆P₄]₂ anions; this tunnel is filled withethylenediamine molecules and water molecules, which may be removed by heating.3. Compound (C₂N₂H₁₀)[Zn₂(PO₄)₂]The color of the crystal is corlorless and its shape is square like. Thecrystallographic parameters is: tetragonal space group P42bc, a=14.6850(2)?, b=14.6850(2), c=8.9274(2), V=1925.19(6)3, Z=8. The final refinement wasbased on 2191 independent reflections for 157 parameters and converged to RB1B＝0.0637,wRB2B(all data)＝0.1576. This compound is a three dimensional openframework zinc phosphate. The framework structure which contains three mutuallyperpendicular channel. Each of which contains an eight membered atom windowsparallel to each of the crystallographic axes. The channels in the [001] direction haveregular shaped windows with an O····O distance of 7.34 ?. There are also channels inthe [100] and [010] directions. The windows of these latter channels do not intersectwith each other but they are intersect with those running parallel to [001] giving riseto a 3-dimentional open network. The diprotonated ethylenediamine cations areconnected to the framework by N－H···O hydrogen bonds.Keywords: phosphate, hydrothermal, crystal structure, X-ray...