HPO3 Pseudo Pyramids Research Articles

Consistent zincophosphite 4-ring 'ladder' chain structural motif with isomeric ligands.

The syntheses and crystal structures of four hydro-thermally prepared organo-zinc phosphites, viz. poly[[(2-amino-3-methyl-pyridine)-μ3-phospho-nato-zinc] hemihydrate], {[Zn(HPO3)(C6H8N2)]·0.5H2O} n , (I), poly[(2-amino-4-methyl-pyridine)-μ3-phospho-nato-zinc], [Zn(HPO3)(C6H8N2)] n , (II), poly[(2-amino-5-methyl-pyridine)-μ3-phospho-nato-zinc], [Zn(HPO3)(C6H8N2)] n , (III), and poly[bis-(2-amino-4-methyl-pyridinium) [tetra-μ3-phospho-nato-trizinc] monohydrate], {(C6H9N2)2[Zn3(HPO3)4]·H2O} n , (IV), are described. Compounds (I)-(III) are constructed from vertex-sharing ZnO3N tetra-hedra (the organic mol-ecule acting as a ligand) and HPO3 pseudo pyramids in a 1:1 ratio to generate the same motif of infinite 4-ring 'ladder' chains propagating in the [010], [101] and [100] directions, respectively, whereas (IV) consists of (010) layers of vertex-sharing ZnO4 and HPO3 units in a 3:4 ratio with the protonated organic mol-ecule acting as a template. When an excess of HCl is used in the synthesis, the simple hydrated mol-ecular salt, bis-(2-amino-3-methyl-pyridinium) tetra-chloro-zincate monohydrate, (C6H8N2)2[ZnCl4]·H2O, (V), arises. Com-pounds (I)-(V) feature extensive networks of hydrogen bonds, both classical (N-H⋯O, N-H⋯Cl, O-H⋯O) and non-classical (C-H⋯O, C-H⋯Cl) in nature, which help to consolidate the extended structures.

LiTi(HPO3)2 A New Polyanion Based Anode for Lithium Ion Battery

Lithium titanium (III) phosphite, LiTi(HPO3)2, a new material, has been synthesized under hydrothermal conditions. The solid-state structure of this material was determined from powder X-ray diffraction data in the tetragonal system, space group I 2d. The anionic inorganic skeleton is a 3D-framework structure, which is built up by TiO6 octahedral units linked together via bridging HPO3 pseudo pyramids, giving rise to tunnels along all the three crystallographic directions. IR and Raman spectroscopic studies show the vibrational modes of the (HPO3)2- oxoanions. This three dimensional structure shows interesting electrochemical behavior. The as-synthesized phase exhibits an insertion host for reversible accommodation of Li+ at ̴ 0.7 V and thus can be used as low voltage anode for lithium ion batteries. LiTi(HPO3)2 phosphite reversibly performs with excellent cycling stability and 100% columbic efficiency for 100 cycles at C/2 rate. After rapid cycling at different C-rates, the initial battery capacity has been recovered with a minimal loss of 3.7 %. Reference: F. Cherkaoui El Moursli, A. Lallaoui, Z. Edfouf, I. Saadoune, M. Abd-lefdil, Nouveau matériau d’insertion pour batteries rechargeables, le phosphite de titane (III) et de lithium LiTi(HPO3)2. Patent OMPIC N° 40700. Figure 1

Synthesis and crystal structure of calcium hydrogen phosphite, CaHPO3.

The hydro-thermal synthesis and crystal structure of the simple inorganic compound CaHPO3, which crystallizes in the chiral space group P43212, are reported. The structure is built up from distorted CaO7 capped trigonal prisms and HPO3 pseudo pyramids, which share corners and edges to generate a three-dimensional network.

Template or ligand? Different structural behaviours of aromatic amines in combination with zinco-phosphite networks.

The solution-mediated syntheses and crystal structures of catena-poly[bis-(2-amino-3-hy-droxy-pyridinium) [zinc-di-μ-phospho-nato] dihydrate], {(C5H7N2O)[Zn(HPO3)2]·2H2O} n , (I), and poly[(benzene-1,2-di-amine)(μ5-phospho-nato)zinc], [Zn(HPO3)(C6H8N2)] n , (II) are described. The extended structure of (I) features [010] anionic chains of vertex-sharing ZnO4 tetra-hedra and HPO3 pseudopyramids; these chains are characterized by disorder over major [occupancy 0.7962 (13)] and minor [0.2038 (13)] components, which can be superimposed on each other by a nominal translational shift. The 2-amino-3-hy-droxy-pyridinium cations and water mol-ecules of crystallization inter-act with the ZnPO chains by way of numerous O-H⋯O and N-H⋯O hydrogen bonds. The structure of (II) features a direct Zn-N bond to the neutral 1,2-di-amino-benzene species as part of ZnO3N tetra-hedra as well as HPO3 pseudopyramids. The Zn- and P-centred groupings are linked through their O-atom vertices into infinite (010) sheets and the structure is consolidated by N-H⋯O hydrogen bonds and N-H⋯π inter-actions. The crystal of (I) chosen for data collection was found to be an inversion twin in a 0.56 (2):0.44 (2) domain ratio.

New titanium (III) phosphite structure and its application as anode for lithium ion batteries

A new titanium (III) phosphite Ti2(HPO3)3, has been synthesized under hydrothermal conditions. The solid-state structure of this material was solved using single-crystal X-ray diffraction. The anionic inorganic skeleton has a three-dimensional structure, which is built up by TiO6 octahedral units linked together via bridging HPO3 pseudo pyramids, giving rise to tunnels along the three crystallographic axes. This new compound displays a high thermal stability limit of 625 °C. IR and Raman spectroscopies show the vibrational modes of the (HPO3)2−oxoanions. Electrochemical activity of this phase toward reversible insertion of Li ion was studied for the first time by galvanostatic charge-discharge measurements, an insertion host for reversible accommodation of Li+ was observed.

The crystal structure of (C2H9N2)2[Zn3(HPO3)4], a three-dimensional zincophosphite framework containing 16-membered rings templated by the unsymmetrical dimethyl hydrazinium cation.

The solution-mediated synthesis and crystal structure of 1,1-di-methyl-hydrazinium tetra-phoshonoatotrizincate, (C2H9N2)2[Zn3(HPO3)4], are described. The anionic [Zn3(HPO3)4]2- framework is built up from alternating ZnO4 tetra-hedra and HPO3 pseudo-pyramids to generate a three-dimensional 4,3-net encapsulating the C2H9N2+ cations. The organic cations, which are protonated at their central N atoms, occupy pores delineated by large 16-membered polyhedral rings and inter-act with the framework by way of N-H⋯O hydrogen bonds and possible C-H⋯O inter-actions. One of the zinc ions lies on a crystallographic twofold rotation axis and all the other atoms lie on general positions. The crystal studied was found to be rotationally twinned about the [001] axis in reciprocal space in a 0.585 (5):0.415 (5) ratio.

Syntheses and Characterizations of Three Organically Templated Zinc Phosphites with 12-Ring Channels

Three new zinc phosphites, [Hapy]2[Zn3(HPO3)4] (1; apy = 4-aminopyridine), [H2hepip][Zn3(HPO3)4]·(H2O)0.25 (2; hepip = N-(2-hydroxyethyl)piperazine), and [H2tmdab][Zn3(HPO3)4] (3; tmdab = N,N,N′,N′-tetramethyl-1,3-diaminobutane), have been synthesized and characterized by infrared spectroscopy, elemental analysis, thermogravimetric analysis, and powder and single-crystal X-ray diffraction. The frameworks of 1–3 are constructed from 4-connected ZnO4 tetrahedra and 3-connected HPO3 pseudo pyramids with distinct connection mode driven by different organic amine templates. There are 12-membered ring (12-MR) and 8-MR apertures in the (3,4)-connected three-dimensional architecture of 1–3. It is notable that helical chains are observed in the framework of compound 3.

Hydrothermal synthesis of a new zinc phosphite (C5H7N2)2·[Zn3(HPO3)4] with intersecting 8- and 12-ring channels

Using 4-aminopyridine as the structure-directing agent(SDA), a new open-framework zinc phosphite, (C5H7N2)2·[Zn3(HPO3)4](ZnHPO-CJ70), was synthesized under hydrothermal condition. Single-crystal X-ray diffraction analysis reveals that ZnHPO-CJ70 is constructed by the strictly alternating ZnO4 tetrahedra and HPO3 pseudo-pyramids, with their vertexes linked to generate a three-dimensional(3D) open framework with intersecting 8- and 12-ring channels. Further characterizations of ZnHPO-CJ70 were performed by means of X-ray powder diffraction(XRD), elemental analysis(ICP, CHN), infrared spectroscopy(IR) and thermogravimetric(TG) analyses. The results of luminescent test shows that ZnHPO-CJ70 exhibits strong fluorescence emissions in the solid state at room temperature.

(C5H6N)4[Be6(HPO3)8]·H2O: A low-density open-framework beryllium phosphite with multidirectional 12-ring channels

Employing the common pyridine (=py) solvent as the source of structure-directing agents (SDAs), a novel three-dimensional open-framework beryllium phosphite (Hpy)4[Be6(HPO3)8]·H2O (1), has been solvothermally synthesized and structurally characterized by IR, elemental analysis, thermogravimetric analysis, powder and single-crystal X-ray diffractions. It crystallizes in the orthorhombic system, space group Pbca (No. 61), a = 20.0034(4) Å, b = 20.2188(4) Å, c = 20.9731(3) Å, V = 8482.5(3) Å3, and Z = 8. The alternating connection of BeO4 tetrahedra and HPO3 pseudopyramids give rise to a (3, 4)-connected network with multidirectional intersecting 12-ring channels. The compound possesses a low density and a new {4.8.10}{42.6.8.10.12}{42.6}3{42.8.102.12}{43.62.8} topology.

Syntheses and characterizations of zinc phosphites with new templates generated by N-alkylation transformations

Two new organically templated zinc phosphites, [tmpip]0.5[Zn2(HPO3)2(H2PO3)] (1) and [dmdabco][Zn3(HPO3)4]·(H2O) (2), have been synthesized under solvothermal conditions, where tmpip=N,N,N′,N′-tetramethyl-piperazinium and dmdabco=N,N′-dimethyl-1,4-diazabicyclo[2,2,2]octane. Note that the templating agents tmpip2+ and dmdabco2+ originated from in situ N-methylation transformations between CH3OH solvent and corresponding cyclic aliphatic amine precursors, i.e. piperazine, 1-methylpiperazine or 1,4-dimethylpiperazine in 1, and 1,4-diazabicyclo[2,2,2]octane in 2. Distinct from conventional Eschweiler–Clarke methylation with excess formic acid and formaldehyde, such direct methylation transformation from methanol molecules is unique. Compound 1 consists of ZnO4 tetrahedra, HPO3 and HPO2(OH) pseudopyramids, exhibiting a complex double layered structure with 12-ring windows. Compound 2 is constructed from strictly alternating ZnO4 tetrahedra and HPO3 pseudopyramids, and possesses a (3,4)-connected interrupted architecture with intersecting 8- and 12-ring channels.

Construction of two novel indium phosphites with (3,6)- and (3,5)-connected frameworks: Synthesis, structure and characterization

Two novel anionic indium phosphites, formulated as [H3O][In(HPO3)2] (1) and [C4H12N2][In2(HPO3)3(C2O4)] (2), were prepared under hydrothermal conditions by using piperazine (PIP) as a structure-directing agent (SDA). Single-crystal X-ray diffraction analysis reveals that compounds 1 and 2 crystallize in the hexagonal space group P63mc (No. 186) and orthorhombic space group Cmcm (No. 63), respectively. Compound 1, constructed from InO6 octahedra and HPO3 pseudo-pyramids, exhibits a rare (3,6)-connected layer structure with kgd (Kagome dual) topology. Compound 2, on the other hand, features a 3D phosphite-oxalate hybrid structure with intersecting 8- and 12-MRs channels. From a topological perspective 2 can be regarded as a (3, 5)-connected binodal net with the Schläfli symbol (42.6)(42.65.83).

Hydrothermal synthesis of three-dimensional open-framework beryllium phosphites with 3,4-connected networks

Two new beryllium phosphites, H2en·Be3(HPO3)4 (1) and H2pda·Be3(HPO3)4 (2), have been synthesized under hydrothermal conditions. Single-crystal structural analyses reveal that both compounds have three-dimensional inorganic frameworks constructed from strictly alternating BeO4 tetrahedra and HPO3 pseudo pyramids. The structure of compound 1 can be described as a pillared layered structure with 12-ring channels. The structure of compound 2 has an interesting sqp topology if Be3(HPO3)4 clusters are regarded as 5-connected nodes in the network.

Synthesis and characterization of a new open-framework zinc phosphite (4,4′-(C5H4N)2(CH2)3)·[Zn3(HPO3)4

Employing 4,4′-trimethylenedipyridine as a template, a new two-dimensional zinc phosphite (4,4′-(C5H4N)2(CH2)3)· [Zn3(HPO3)4] has been prepared at room temperature and characterized by single-crystal X-ray diffraction, FTIR, elemental analysis, powder X-ray diffraction, and thermogravimetric analysis. The compound crystallizes in the monoclinic space group P21/c, with cell parameters, a = 9.3309(19) A, b = 14.798(3) A, c = 33.637(7) A, β = 91.11(3)°, V = 4643.8(16) nm3 and Z = 4. The connectivity of the ZnO4 tetrahedra and HPO3 pseudo pyramids results in infinite corner-sharing 4-membered ring chains as second building units which are further linked by Zn-O-P bonds to form a 2-D layer that with interesting 8-membered ring channels along the [100] direction. The diprotonated 4,4′-trimethylenedipyridine molecules sit in the middle of the layers along the [100] direction and interact with the framework via hydrogen bonds.

An Open-framework Strontium Phosphate Containing a Novel 412 Cages

A novel strontium phosphite open-framework H2[Sr6(HPO3)7] (denoted as ZZ-2, ZZ = Zhen Zhu) was hydrothermally synthesized by using isophorondiamine (IPDA) as the trial structure-directing agent. Single crystal structure refinement discloses that ZZ-2 crystallizes in the trigonal space group R-3 with the cell parameters of a = 16.410(2) Å, b =16.410(2) Å, c = 6.8651(14) Å, ? = 114.61(5)°, ? = 90°, V = 1601.0(5) Å3, Z = 3. The structure of ZZ-2 is constructed by eight coordinated SrO8 and HPO3 pseudo pyramids. A novel 412 cages existed in the structure with a proton located in the center of the cage. the P-H bonds stretch in all cages, hydrogen proton at the center of the cage to balance framework.

Structural Transformation of Three‐Dimensional Bimetallic Phosphites Containing Corner‐Sharing 4‐Ring Chains

AbstractTwo open‐framework bimetallic phosphites, [C6H18N2][Co0.3Zn2.7 (HPO3)4] (1) and [C2H8N]2[Co0.3Zn2.7(HPO3)4] (2) were synthesized and characterized. The inorganic frameworks of the two compounds are constructed from strictly alternating MO4 (M = Zn, Co)tetrahedra and HPO3 pseudo pyramids, forming three‐dimensional networks with 8‐ring and 12‐ring channels for 1 and 16‐ring channels for 2. The anionic frameworks of the two compounds can be easily transformed to a neutral framework structure with 16‐ring channels at room temperature.

Synthesis and Characterization of [(C2H8NO)2Zn5(HPO3)6(H2O)2]·(H2O)2: a New 2D Hybrid Zinc Phosphite with Neutral Framework

AbstractA new layered inorganic‐organic hybrid zinc phosphite, [(HEA)2Zn5(HPO3)6(H2O)2]·(H2O)2 (EA = ethanolamine), has been hydrothermally synthesized and structurally characterized by single crystal X‐ray diffraction, FTIR, elemental analysis, powder X‐ray diffraction and thermogravimetric analysis. The compound crystallizes in the triclinic system, space group $P{\bar 1}$ (No. 2), a = 8.6068(2) Å, b = 10.1061(2) Å, c = 10.2804(4) Å, α = 117.680(3)°, β = 95.917(2)°, γ = 101.716(2)°, V = 755.00(2) Å3, and Z = 1. The structure consists of ZnO4 tetrahedra, ZnO4(OH)2 octahedra and HPO3 pseudopyramids which are linked together through their vertexes forming neutral sheet‐like architecture. The adjacent layers are stably packed together and exhibit interesting 3‐D supramolecular framework through multipoint hydrogen bonds between the neutral framework and the extra‐framework water molecules.

Synthesis and Characterization of a Purely Inorganic Open‐framework Bimetallic Phosphite with Intersecting 12‐ and 16‐membered Ring Channels

AbstractA new three‐dimensional open‐framework cobalt‐zinc phosphite [Co(H2O)4Zn(HPO3)2]·H2O (1), has been prepared under hydrothermal conditions and characterized by single‐crystal X‐ray diffraction, XRD, IR and SQUID magnetometer. The compound crystallizes in the triclinic space group $P{\bar 1}$ with a = 7.552(5), b = 7.671(5), c = 9.443(5) Å, α = 88.538(5)°, β = 89.109(5)°, γ = 87.056(5)°, V = 546.1(6) Å3, Z = 2. The structure of 1 consists of corner‐shared (cs) four‐membered‐ring chains formed by alternating ZnO4 tetrahedra and HPO3 pseudopyramids, which are further linked through CoO2(H2O)4 octahedra giving rise to a three‐dimensional (3‐D) neutral open‐framework with intersecting 12‐ and 16‐MR channels. The synthesis of system required the presence of L‐histidine which is not incorporated into the structure of the product. It is noteworthy that compound 1 represents the only known example of purely inorganic open‐framework cobalt‐zinc phosphite.

2H3O·[Co8(HPO3)9(CH3OH)3]·2H2O: An Open-Framework Cobalt Phosphite Containing Extra-Large 18-Ring Channels

A new open-framework cobalt phosphite 2H3O·[Co8(HPO3)9(CH3OH)3]·2H2O with extra-large 18-ring channels has been synthesized solvothermally. Its structure features novel 2D cobalt–oxygen 18-net sheets which are linked by HPO3 pseudo-pyramids to form a 3D open framework with pendent –CH3 groups protruding into the 18-ring channels.

2-Hydroxypropane-1,3-diammonium bis(phosphonato)zincate(II) hemihydrate

In the title compound, (C3H12N2O)[Zn(HPO3)2]·0.5H2O, the inorganic macroanionic chain is built up from ZnO4 tetrahedra and HPO3 pseudo-pyramids sharing vertices. The organic dication shows positional disorder of its central –OH group in a 0.614 (7):0.386 (7) ratio. The components interact by way of O—H...O and N—H...O hydrogen bonds. The Zn atom lies on a crystallographic twofold axis and one C atom, the disordered O atoms of the –OH groups and the water O atom lie on a crystallographic mirror plane.

A Novel Layered Bimetallic Phosphite Intercalating with Organic Amines: Synthesis and Characterization of Co(H2O)4Zn4 (HPO3) 6×C2N2H10.

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