Hydrothermal Synthesis,Crystal Structures and Characterization of Two Hydrogen Phosphates Templated by 4-Amino-2,2,6,6-tetramethylpiperidine

Abstract

Chemical preparations, crystal structures, thermal analyses, and IR spectroscopic studies are given for two new hydrogen phosphates templated by 4-amino-2,2,6,6-tetramethylpiperidine: (C₉H₂₂N₂)₂·(H₂PO₄)·(HPO₄)·(F)·H₂O (I) and (C₉H₂₂N₂)·(H₂PO₄)₂(II). The structures are determined by single crystal X-ray diffraction. Both compounds crystallize in the P2₁/c (N°14) monoclinic space group with the unit cell parameters: a = 14.856 (1) Å, b = 14.092 (2) Å, c = 14.7166 (9) Å, β = 118.434 (7)°, V = 2709.2 (4) Å ³, and Z = 4 for (I) and a = 9.803 (2) Å, c = 0.466 (2) Å, c = 15.640 (8) Å, β = 94.990 (4), V = 1598.68 (7) ų, and Z = 4 for (II).

The structure of I, refined to R = 0.042 and R_w = 0.067 for 6009 reflections (I ≥ 2σ (I)), exhibits infinite inorganic chains _∞((H₂PO₄)·(HPO₄)·(F)·H₂O)^4? linked together through weak hydrogen bonds to form layers onto which the diprotonated [C₉H₂₂N₂]^{2 +} amine molecules are anchored.

The structure of II, refined to R = 0.060 and R_w = 0.086 for 1435 reflections (I ≥ 2σ (I)), consists of _∞(H₂PO₄)^? (100) layers between which [C₉H₂₂N₂]²⁺ cations are inserted. A network of hydrogen bonds connects the different components. IR spectra of I and II show the characteristic bands of amine groups and phosphate anions.     

Synthesis,Crystal Structure,and Characterization of a New Adduct 3-Ammoniumphenyl Sulfone Dihydrogenphosphate Phosphoric Acid [C12H14N2SO2](H2PO4)2H3PO4

Abstract

A new adduct 3-ammoniumphenyl sulfone dihydrogenphosphate phosphoric acid, [C₁₂H₁₄N₂O₂S](H₂PO₄)₂H₃PO₄, has been synthesized by slow evaporation at room temperature using 3-aminophenyl sulfone as the structure-directing agent. The structure, determined by single-crystal X-ray diffraction at 293 K, can be described as inorganic layers built by H₂PO₄ ^? groups and H₃PO₄ molecules, parallel to the (a, c) planes at y = 0.5, between which molecules of the organic group [C₁₂H₁₄N₂O₂S]²⁺ are inserted. In this atomic arrangement, hydrogen bonds and van der Waals interactions between the different species play an important role in the tri-dimensional network cohesion. Solid-state ¹³C and ³¹P MAS NMR spectroscopies are in agreement with the X-ray structure.

[Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements for the following free supplemental resource: Tables S1 and S2. Figures S1 and S2.]

GRAPHICAL ABSTRACT      

Synthesis and Structure of a New Layered Zincophosphate Zn6(PO4)5(HPO4)·C8N5H28·5H2O, Intercalated with Quintuply Protonated Tetraethylenepentamine

A new two-dimensional zinc phosphate Zn₆(PO₄)₅(HPO₄)·C₈N₅H₂₈·5H₂O has been synthesized hydrothermally using tetraethylenepentamine (TEPA) as structure-directing agent and its structure was determined by means of single-crystal X-ray diffraction. The title compound crystallizes in the orthorhombic system, space group Pca2₁ (No.29) with lattice parameters a=18.6286(12) Å, b=8.0804(5) Å, c=22.5019(15) Å, V= 3387.1(4) ų, Z=4, R₁=0.0389 and wR₂=0.0862 [4042 observed reflections with I>2σ(I)]. The structure involves a network of ZnO₄, PO₄, and PO₃(OH) tetrahedra forming macroanionic inorganic layers with eight-membered apertures. The charge compensation is achieved by the quintuply protonated TEPA molecule in interlamellar space, which interact with the inorganic layers via hydrogen bonding.     

A novel three-dimensional pillared-layer hybrid zinc phosphite featuring double-helical channels

A new zinc phosphite (C₂H₈N₂)_0.5(HPO₃)Zn has been hydrothermally synthesized from a mixture of ZnO, H₃PO₃, 4,4’-bipyridine, ethylenediamine, and H₂O. Single-crystal X-ray diffraction analysis reveals that the Zn ions are first interconnected by HPO₃ ²- ligands to produce a neutrally infinite two-dimensional inorganic layer with four- and eight-membered rings, which is further used as the second building units and helically pillared by bridging ethylenediamine molecules to form the scarcely reported three-dimensional pillared-layer hybrid zinc phosphite with double-helical channels due to the flexibility of the ethylenediamine ligands.     

Synthesis, structure and magnetic behavior of a new three-dimensional Manganese phosphite-oxalate: [C2N2H10][Mn2(OH2)2(HPO3)2(C2O4)]

A novel manganese phosphite-oxalate, [C₂N₂H₁₀][Mn₂^II(OH₂)₂(HPO₃)₂(C₂O₄)] has been hydothermally synthesized and its structure determined by single-crystal X-ray diffraction. The structure consists of neutral manganese phosphite layers, [Mn(HPO₃)]_∞, formed by MnO₆ octahedra and HPO₃ units, cross-linked by the oxalate moieties. The organic cations occupy the middle of the 8-membered one-dimensional channels. Magnetic studies indicate weak antiferromagnetic interactions between the Mn²⁺ ions.     

N‐(2‐Hydroxyethyl)ethylenediammonium hydrogenphosphate monohydrate

The title compound, C₄H₁₄N₂O²⁺·HPO₄^2?·H₂O, contains alternating interleaved layers of hydrogenphosphate and N‐(2‐hydroxyethyl)ethyl­enedi­ammonium moieties. The water mol­ecules are associated with channel‐like voids in the structure and a network of hydrogen bonds stabilizes the crystal packing.     

Oxyfluorinated compounds with an open structure XVI. Synthesis,structure determination and magnetic properties of Fe4F3(PO4)(HPO4)4(H2O)4(N2C3H12) [ULM-15]

Fe₄F₃(PO₄)(HPO₄)₄(H₂O)₄(N₂C₃H₁₂) (labelled ULM-15) was prepared hydrothermally (7 days, 453 K, autogenous pressure) in the presence of 1,3-diaminopropane as organic template. Its structure was determined by single crystal X-ray diffraction. ULM-15 is monoclinic (Space group C2/c (no 15)) with lattice parameters a = 24.176(1) , b = 14.558(1) , c = 7.186(1) , β = 102.3(1)°, V = 2470.8(3) ³, Z = 4. Its three-dimensional framework is constituted from corner-sharing FeX₆ (X = O, F, H₂O) octahedra and tetrahedral PO₄ and HPO₄ groups. The structure presents trans-chains of FeO₄F₂ octahedra related to ferric dimers [Fe₂O₈F₂(H₂O)₂] by tetrahedral units. They delimit 16-membered rings channels along [001] in which the diprotonated amines are inserted. ULM-15 shows 3D antiferromagnetic behaviour below T_N ≈ 22 K.     

Hydrothermal synthesis and characterization of a new layered gallophosphate JGP-L1 with a Ga/P ratio of non-unity

A new compound, Ga₆(OH)₄(HPO₄)₂(PO₄)₅·C₈H₂₈N₅·3H₂O (denoted JGP-L1), with a gallophosphate layer and a Ga/P ratio of 6/7 has been synthesized hydrothermally by using tetraethylenepentamine as template. It is characterized by powder X-ray diffraction (XRD), elemental analysis, inductively coupled plasma, and TGA analysis and structurally determined by single-crystal XRD analysis. JGP-L1 crystallizes in the orthorhombic, space group Pna2₁ (no. 33), with a=16.422(3), b=11.898(2), c=18.730(4) Å, V=3659.6(13) Å³ and Z=4. The structure of JGP-L1 is built up by alternating of Ga(OH)₂O₄ octahedra, Ga(OH)O₄ trigonal bipyramids and PO₄ (or HPO₄) tetrahedra to form inorganic sheets. It is noteworthy that JGP-L1 was synthesized with extremely low reactant concentration, where the reaction mixture exhibits a H₂O:Ga₂O₃ molar ratio of 2220:1.     

Hydrothermal Synthesis and Characterization Properties of C7H12N2[H2PO4]2.1/2H2O

An orthophosphoric hybrid material was successfully prepared by a hydrothermal reaction at 110 °C. A single crystal X-ray structure, thermal behavior, IR, and NMR spectroscopy investigations are given for a new organic cation bis dihydrogenomonophosphate C₇H₁₂N₂[H₂PO₄]₂.1/2H₂O. The latter has been synthesized hydrothermally using 2,4-diaminotoluene (DAT) and orthophosphoric acid. The atomic arrangement can be described as inorganic sheets alternating with inorganic-organic layers. The organic group C₇H₁₂N⁺ ₂ is located between inorganic groups to build multiple hydrogen bonds to ensure the three-dimensional cohesion network. The thermal behavior and IR, NMR and impedance spectroscopy studies are discussed for the powder samples of this compound.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

Na(H3NCH2CH2NH3)0.5[Co(C2O4)(HPO4)]: A novel phosphoxalate open-framework compound incorporating both an alkali cation and an organic template in the structural tunnels

The first open-framework metal phosphoxalate compound containing both an organic and an inorganic template in the same structure is reported. Na(H₃N⁺CH₂CH₂N⁺H₃)_0.5[Co(C₂O₄)(HPO₄)] (1) was synthesized hydrothermally via a direct metathesis reaction using the sodium salts of oxalate and phosphate in the presence of cobalt chloride and ethylenediamine dihydrochloride. The structure of 1 consists of a 3D framework built from the [Co(C₂O₄)]_n layers connected by HPO₄²⁻ group bridging two different cobalt centers between the adjacent layers. A major and a minor structural tunnels are created and occupied by the Na⁺ and H₃N⁺CH₂CH₂NH₃²⁺ ions, respectively, in the same structure. Single-crystal X-ray crystallographic data for 1 are: monoclinic, P2₁/c, a=5.8189(6), b=10.235(1), c=13.066(1) Å, β=96.671(2)°, Z=4, V=772.9(1) Å³, R=3.95% and R_w=6.37%.     

Hydrothermal Synthesis,Crystal Structure,and Thermal Stability of Two New Metal Phosphonates with a Pillared Layered Structure

Two new metal phosphonates with a 3D pillared layered framework based on N,N′‐piperazinebis(methylenephosphonic acid), H₂O₃PCH₂NC₄H₈NCH₂PO₃H₂ (H₄L), Sn[O₃PCH₂NHC₄H₈NHCH₂PO₃] ( 1 ) and Pb₃(OH)₂[O₃PCH₂NC₄H₈NCH₂PO₃] ( 2 ), have been synthesized under hydrothermal conditions and structurally characterized by single‐crystal X‐ray diffraction as well as with infrared spectroscopy, elemental analysis and thermogravimetric analysis. For compound 1 , each ψ‐square pyramidal SnO₄ unit is in turn corner‐shared by four CPO₃ tetrahedral from four different phosphonate ligands to form two‐dimensional inorganic puckered layers in ab planes. In compound 2 , the complicated inorganic layer (bc planes) is built up of ψ‐PbO₄N, PbO₆ and CPO₃ polyhedra. The overall structure for two compounds may be described in terms of alternating inorganic infinite layers and organic pillars {CH₂N(C₂H₄)₂NCH₂}, to form a 3D pillared layered structure.     

Synthesis and structure of [Zn8(HPO4)8(H2PO4)8]•[(C2H8N)8]•4H2O

A chain-like zincophosphate [Zn₈(HPO₄)₈(H₂PO₄)₈]•[(C₂H₈N)₈]•4H₂O was obtained at room temperature from a ZnO/P₂O₅/dimethylamine/H₂O mixture. The crystal structure was determined by single crystal X-ray diffraction. The symmetry is monoclinic a=1.26450(7)nm, b=1.08477(5)nm, c=1.46311(4)nm, β=98.793(5)°, space group Cc. The structure consists of chains of zinc-corner-sharing Zn₂P₂O₄ four rings. The negative charge of the chains is compensated by the protonated dimethylamine. The characterization by ³¹P solid state nmr spectroscopy is also reported.     

Hydrogen‐bonded networks in crystals of 1‐(diaminomethylene)thiouron‐1‐ium perchlorate,hydrogen sulfate,dihydrogen phosphate and dihydrogen arsenate

Crystals of the title compounds, namely 1‐(diaminomethylene)thiouron‐1‐ium perchlorate, C₂H₇N₄S⁺·ClO₄⁻, 1‐(diaminomethylene)thiouron‐1‐ium hydrogen sulfate, C₂H₇N₄S⁺·HSO₄⁻, 1‐(diaminomethylene)thiouron‐1‐ium dihydrogen phosphate, C₂H₇N₄S⁺·H₂PO₄⁻, and its isomorphic relative 1‐(diaminomethylene)thiouron‐1‐ium dihydrogen arsenate, C₂H₇N₄S⁺·H₂AsO₄⁻, are built up from a nonplanar 1‐(diaminomethylene)thiouron‐1‐ium cation and the respective anion linked together via N—H...O hydrogen bonds. Both arms of the cation are planar, but they are twisted with respect to one another around the central N atom. Ionic and extensive hydrogen‐bonding interactions join oppositely charged units into layers in the perchlorate, double layers in the hydrogen sulfate, and a three‐dimensional network in the dihydrogen phosphate and dihydrogen arsenate salts. This work demonstrates the usefulness of 1‐(diaminomethylene)thiourea in crystal engineering for the formation of supramolecular networks with acids.     

Products of complex formation in CoCl<Subscript>2</Subscript>-1-amino-8-hydroxynaphthalene-2,4-disulfonic acid-α-hydroxy-α-phenylacetophenone (benzaldehyde and its hydroxy derivatives) systems

From the CoCl₂-1-amino-8-hydroxynaphthalene-2,4-disulfonic acid-benzoin (or benzaldehyde and its para- and ortho-hydroxy derivatives), complexes of the composition C₄₈H₃₈K₂N₂O₁₈S₄Co, C₁₇H₁₇ClKNO₁₁S₂Co, C₁₇H₁₆KNO₁₁S₂Co, and C₃₄H₂₄K₂N₂O₁₆S₄Co₂ were isolated. These compounds were identified and characterized by elemental and X-ray phase analysis, thermogravimetry, IR and diffuse reflectance spectroscopy, as well as magnetic susceptibility and electroconductivity measurements. The C₁₇H₁₆KNO₁₁S₂Co and C₃₄H₂₄K₂N₂O₁₆S₄Co₂ complexes were additionally studied by the extended X-ray absorption fine structure (EXAFS) method. Evidence for a monomeric structure of the former complex and for a hydroxyl-bridged dimeric structure of the latter was obtained.     

Synthesis and Characterization of a New Three‐dimensional Organically Templated Nickel‐Zinc Phosphate

A new organically templated nickel–zinc phosphate, [C₂N₂H₁₀]·[Ni_2.4Zn_3.6(PO₄)₄(HPO₄)]·H₂O, has been synthesized from an aqueous solution containing NiCl₂·6H₂O, Zn(OAc)₂·2H₂O, H₃PO₄ and ethylenediamine as the structure‐directing agent. The compound crystallizes in the monoclinic system, space group C2/c (No. 15), a = 19.1563(5), b = 5.0316(2), c = 21.1724(5) Å, α = 103.201(3)°, V = 1986.81(11) ų, Z = 4. It possesses a three‐dimensional framework constructed from MO₄ (M = Ni, Zn), PO₄, and HPO₄ tetrahedra through their vertices. One‐dimensional 8‐ring channels are found in the structure, with the diprotonated organic templates residing in the tunnels and interacting with the inorganic framework by extensive hydrogen bonds. The framework is characterized by infinite helical chains of corner‐sharing MO₄ (M = Ni, Zn) tetrahedra.     

Anilinium dihydrogen phosphate

The triclinic structure of the title compound, C₆H₈N⁺·H₂PO₄⁻, with three symmetry‐independent structural units (Z′ = 3), is formed of separate organic and inorganic layers alternating along the b axis. The building blocks of the inorganic layer are deformed H₂PO₄ tetrahedra assembled into infinite ladders by short and hence strong hydrogen bonds. The anilinium cations forming the organic layer are not hydrogen bonded to one another, but they are anchored by four N—H...O crosslinks between the dihydrogen phosphate chains of adjacent ladders. Two H atoms of each –NH₃ group then form one normal and one bifurcated N—H...O hydrogen bond to the P=O oxygens of two tetrahedra of one chain, while the third H atom is hydrogen bonded to the nearest O atom of an adjacent chain belonging to another dihydrogen phosphate ladder.     

Syntheses,characterization, and crystal structures of two fluorinated gallium phosphates templated by organic amines

Two fluorinated gallium phosphates templated by organic amines, (C₄H₁₅N₃)[Ga₃F₂(PO₄)₃] (1) and [(C₂H₁₀N₂)(C₂H₉N₂)][Ga₃F₄(HPO₄)₄] (2), have been synthesized under hydrothermal and solvothermal conditions, respectively. The compounds were characterized by elemental analyses, FT-IR spectroscopy, and powder X-ray diffraction. Their crystal structures were determined from single-crystal X-ray diffraction. The crystal structure of 1 has a 3-D framework with 10-membered ring channels along the b-axis. The crystal structure of 2 is an infinite 1-D chain structure, further forming a 3-D supramolecular structure with pseudo 10-membered ring channels along the a-axis through O–H?···?O hydrogen bonds. The protonated organic amine cations are located in the inorganic channel and interact with the polyanion framework both electrostatically and via N–H?···?O and N–H?···?F hydrogen bonds.     

Complexes of apatitic layered compound Ca8(HPO4)2(PO4)4·5H2O with dicarboxylates

Octacalcium phosphate(OCP), Ca₈(HPO₄)₂(PO₄)₄·5H₂O, consists of alternative stackings of layers with an apatitic structure and a brushite-like composition. Here we consider whether or not OCP is able to complex with organic substances. The interplanar spacing (d₁₀₀) of OCP prepared in the presence of dicarboxylates (RC₂O₄ ^2–; R=organic group) expanded from the original value of 18.7 Å to 19.2–26.1 Å depending on the length of R. Examples of R were C_nH_2n(n=1–6), CH(CH₃)CH₂, C(CH₃)=CH, CH=CH, CH₂CH=CHCH₂ and C₆H₄. Structural considerations and experimental data suggested that dicarboxylates were incorporated into the OCP structure through the replacement of HPO₄ ^2– by RC₂O₄ ^2–.     

A new hybrid organic–inorganic chain: [(phen)Cu–μ‐(κ2O:O′‐VP2O10H3)2–Cu(phen)]n

The structure of the title compound, poly[(dihydrogenphosphato‐κO)(μ₃‐hydrogenphosphato)di‐μ‐oxido‐(1,10‐phenanthroline)copper(II)vanadium(V)], [CuV(HPO₄)(H₂PO₄)O₂(C₁₂H₈N₂)]_n, is defined by [(phen)Cu–μ‐(κ²O:O′‐VP₂O₁₀H₃)₂–Cu(phen)] units (phen is 1,10‐phenanthroline), which are connected to neighbouring units through vanadyl bridges. Neighbouring chains have no covalent bonds between them, although they interdigitate through the phen groups viaπ–π interactions.     

New organically templated gallium oxalate-phosphate structures based on Ga4(PO4)4(C2O4) building unit

Five organic-inorganic hybrid gallium oxalate-phosphates, [Ga₂(PO₄)₂(H₂O)(C₂O₄)_0.5](C₃N₂H₁₂)_0.5(H₂O) (1), [Ga₂(PO₄)₂(C₂O₄)_0.5](C₂N₂H₁₀)_0.5(H₂O) (2), [Ga₂(PO₄)₂(C₂O₄)_0.5](C₃N₂H₁₂)_0.5 (3), [Ga₂(PO₄)₂(H₂PO₄)_0.5(C₂O₄)_0.5](C₄N₃H₁₆)_0.5 (H₂O)_1.5 (4) and [Ga_2.5(PO₄)_2.5(H₂O)_1.5(C₂O₄)_0.5](C₄N₃H₁₅)_0.5 (5), have been synthesized by using 1,3-diaminopropane, ethylenediamine and diethylene triamine as structure-directing agents under hydrothermal condition. The structures of 1-5 are based on Ga₄(PO₄)₄(C₂O₄) building unit made up from Ga₂O₈(C₂O₄) oxalate-bridging dimer and alternating PO₄ and GaO₄ tetrahedral units. Compound 1 is layered structure where the building units link together in the same orientation. Corner sharing of these similar layers result in three-dimensional (3-D) structure 2. However, in compound 3, the building units arrange in a wave-like way to generate two types of eight member ring (8MR) channels. Both 4 and 5 contain the layers where the building units have an opposite orientation. Those layers are linked by H₂PO₄ group and Ga(PO₄)(H₂O)₃ cluster, respectively, to form 3-D frameworks with 12MR large pore channels. Compounds 2-5 exhibit intersecting 3-D channels where the protoned amines are located.