Crystal Structure and Spectroscopic Studies of a New Organic Dihydrogenmonophosphate [2-NH2-6-CH3-C4H3N2O]2(H2PO4)2

Physicochemical properties of a new dihydrogenmonophosphate [2-NH ₂ -6-CH ₃ -C ₄ H ₃ N ₂ O] ₂ (H ₂ PO ₄ ) ₂ are described on the basis of X-ray crystal structure investigation. This compound crystallizes in the triclinic space group P-1. The unit cell parameters are: a = 7.667(3) Å, b = 8.204(5) Å, c = 14.761(6) Å, α = 98.85(4)°, β = 99.23(3)°, γ = 90.50(4)°, V = 905.0 ų, and Z = 2. The crystal structure was solved and refined to R = 0.037, using 4351 independent reflections. The atomic arrangement of this compound is built up by (H ₂ PO ₄ ) _n ^{n ?} chains. Each chain aggregates with organic molecules to form an open framework architecture through hydrogen bond interactions. The structure includes four types of hydrogen bonds. The first one, O─H─O, links the H ₂ PO ₄ groups to form (H ₂ PO ₄ ) _n ^{n ?} infinite inorganic chains parallel to the a axis. The three other types, O─H─O(carbonylic), N─H─O(carbonylic), and N─H─O, assemble the inorganic chains so as to build up a three-dimensional arrangement. This compound has also been investigated by IR, and solid-state ¹³ C and ³¹ P MAS NMR spectroscopies combined to ab initio calculations.     

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,Crystal Structure,and NMR Spectroscopy of a New P-Phenylenediamonium Diphosphate [p-NH3C6H4NH3]H2P2O7

Crystal growth and characterization by X-ray diffraction and NMR spectroscopy of a new p-phenylenediamonium diphosphate [p-NH₃ C ₆ H ₄ NH ₃]H ₂ P ₂ O ₇ are reported. This compound crystallizes in a triclinic unit cell P1 with the parameters a = 7.130(3), b = 9.047(3), c = 9.350(2) Å, α = 133.44(2)°, β = 95.02(2)°, γ = 107.11(4)°, Z = 2, V = 514.3(15) ų, and D _x = 1.848 g.cm^{? 3}. The crystal structure has been solved and refined to R = 0.0273, using 3678 independent reflections. The atomic arrangement is build up by infinite ribbons of [H₂ P ₂ O ₇] ^2? anions, extending along the a-direction at y = 1/2. Between these ribbons are located the p-phenylenediammonium entities, which form hydrogen bonds N─H…O with some external oxygen atoms of phosphoric groups. Crystallographic results are correlated with that of the solid state ¹³C and ³¹P MAS NMR spectroscopy.     

The Synthesis and Characterization of a New Cobalt Dimethylphenylpiperazinium Cyclotetraphosphate Hexahydrate,Co[C12 H19 N2]2 P4 O12.6 H2 O

Cobalt dimethylphenylpiperazinium cyclotetraphosphate hexahydrate, Co[C₁₂H₁₉N₂]₂P₄O₁₂.6H₂O, was synthesized by a reaction between cyclotetraphosphoric acid H₄P₄O₁₂, cobalt carbonate, and 1-(2,4-dimethylphenylpiperazine). It crystallizes in the triclinic system, space group P, with the following unit cell parameters: a = 7.336(1), b = 8.413(1), c = 14.926(2) Å, α = 87.46(1), β = 83.13(1), γ = 82.98(1)°, V = 907.3(2) ų, and Z = 1. The atomic arrangement can be described as layers containing P₄O₁₂ rings a and Co(H₂O)₆ octahedra spreading in the (001) planes between which are located the dimethylphenylpiperazinium groups via H-bonds. The synthesis and characterization by X-ray diffraction, IR absorption, and thermal analysis are described.     

Crystal Structure, (31P, 13C) MAS-NMR,IR Spectroscopy and Thermal Investigations of 2,6-Dimethylanilinium Dihydrogenmonophosphate Monohydrate

Chemical preparation, crystal structure, thermal analysis, IR absorption, and NMR studies are given for a new hybrid organic-inorganic compound, the (2,6-dimethyanilinium) dihydrogenophosphate monohydrate [C ₈ H ₁₂ N]H ₂ PO ₄ ·H ₂ O. This compound crystallizes in a triclinic P=1 unit-cell, with a = 7.392(5) Å, b = 8.323(3) Å, c = 10.306(5) Å, α = 95.769 (4)°, β = 102.642 (3)°, γ = 113.498(2)°, V = 554.88(5) Å ³ , and Z = 2. Its crystal structure is determined and refined to R = 0.040 with 1942 independent reflections. The atomic arrangement can be described by inorganic layers built by H ₂ PO ₄ ^? anions, and H ₂ O molecules with which the organic molecules perform different interactions to form a stable 3D network. Solid state ³¹ P and ¹³ C CP-MAS-NMR spectroscopies are in agreement with the X-ray structure.     

Synthesis,Crystal Structure,and Characterization of A New Hydrogen Phosphate Templated By 3-Aminophenyl Sulfone

Abstract

The synthesis and crystal structure of a new noncentosymmetric compound with the general formula: [C₄₈H₅₁N₈O₈S₄](HPO₄)H₂PO₄ are reported. The structure, determined by single-crystal X-ray diffraction at 150 K can be described as organic layers [C₄₈H₅₁N₈O₈S₄]³⁺ parallel to the (a and c) plane between which the inorganic groups consisting of H₂PO₄ ^? and HPO₄ ^2? entities are inserted as inorganic layers. In this atomic arrangement, H-bonds and Vander-Waals interactions between the different species play an important role in the tridimensional 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 to view the free supplemental file.     

Spezielle Alkylammoniumhexachlorometallate. I. Kristallisationsverhalten und Kristallstruktur von Diethylentriammoniumhexachlororhodat, [H3N(CH2)2NH2(CH2)2NH3][RhCl6]

Alkylammonium Hexachlorometallates. I. Crystallization Properties and Crystal Structure of Diethylenetriammonium Hexachlororhodate, [H₃N(CH₂)₂NH₂(CH₂)₂NH₃][RhCl₆] The reaction of RhCl₃ · 3H₂O with diethylenetriamine in 12 m hydrochloric acid yielded diethylenetriammonium hexachlororhodate [H₃N(CH₂)₂NH₂(CH₂)₂NH₃][RhCl₆] ( 1 ). Dark red single crystals of the compound were grown under hydrothermal conditions at a temperature interval of 180°C to 125°C in closed glass ampoules over several weeks (space group C2/c, a = 30.956(4) Å, b = 7.371(2) Å, c = 12.9736(15) Å, β = 113.787(11)°, Z = 8, 2385 reflections with I > 0, wR²(obs.) = 0.0279, R¹(I > 2σ(I)) = 0.0271). The crystal structure is determined by a complex framework of hydrogen bonds between the hexachlororhodate anions and the diethylenetriammonium cations.     

Synthesis,Crystal Structure,and Characterization of A New Adduct Bis-(2-Amino-3-Benzyloxypyridinium) Selenate Monohydrate [C12H13N2O]2SeO4.H2O

Abstract

A new adduct bis-(2-amino-3-benzyloxypyridinium) selenate monohydrate, [C₁₂H₁₃N₂O]₂SeO₄.H₂O, has been synthesized by slow evaporation at room temperature using 2-amino-3-benzyloxypyridine as the structure-directing agent. The structure, determined by single-crystal X-ray diffraction at 298 K, can be described as organic-inorganic tunnels with different forms built by infinite inorganic chains parallel to the c axis and connected to the organic cations. 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 ⁷⁷Se MAS NMR spectroscopy results are in agreement with the X-ray structure.

[Supplementary materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfer, and Silicon and the Related Elements for the following free supplemental files: Additional figures and tables.]     

Synthesis and Structure of a One‐Dimensional Aluminum Phosphate, [NH3(CH2)2NH2(CH2)3NH3]3+ [Al(PO4)2]3—

A one‐dimensional aluminum phosphate, [NH₃(CH₂)₂NH₂(CH₂)₃NH₃]³⁺ [Al(PO₄)₂]^3—, has been synthesized hydrothermally in the presence of N‐(2‐Aminoethyl‐)1, 3‐diaminopropane (AEDAP) and its structure determined by single crystal X‐ray diffraction. Crystal data: space group = Pbca (no. 61), a = 16.850(2), b = 8.832(1), c = 17.688(4)Å, V = 2632.4(2)ų, Z = 8, R₁ = 0.0389 [5663 observed reflections with I > 2σ(I)]. The structure consists of anionic [Al(PO₄)₂]^3— chains built up from AlO₄ and PO₄ tetrahedra, in which all the AlO₄ vertices are shared and each PO₄ tetrahedron possesses two terminal P=O linkages. The cations, which balances the negative charge of the chains, are located in between the chains and interact with the oxygen atoms through strong N—H···O hydrogen bonds. Additional characterization of the compound by powder XRD and MAS‐NMR has also been performed and described.     

(NH3CH2CHNH2CH3)2[WVIO2(OC6H4O)2]的合成、晶体结构及其与ATP相互作用的NMR性质研究

在室温下, 选用具有手性特征的1,2-丙二胺(1,2-propanediamine)为对阳离子, 由正四丁基铵十钨酸盐和邻苯二酚反应, 得到了钨酶活性结构因子仿生配合物(NH3CH2CHNH2CH3)2[WVIO2(OC6H4O)2], 用单晶X射线衍射测定了其晶体结构, 晶体属单斜晶系, 空间群为P21/n, a＝1.1099(3) nm, b＝1.0416(3) nm, c＝1.8874(6) nm, β＝96.492(6)°, V＝2.1679(11) nm3, z＝4, R1＝0.0445, wR2＝0.0682; 并对它进行了IR, 1H NMR和UV-Vis谱学表征. 利用NMR研究了其与三磷酸腺苷(ATP)的相互作用, 结果发现手性特征的1,2-丙二胺及邻苯二酚苯环的1H化学位移在与ATP混合前后均呈现出较大的差异, 分析得出: 配合物中的金属离子在D2O中大多数均以W(V)价态存在, 但在与ATP共存时转化为W(VI), 并与配体发生了解离.     

(NH2CH2CH2NH3)4[WⅤO2(OC6H4O)2]2(NH3CH2CH2NH3)·H2O的合成、晶体结构、EPR以及与同构物的比较

Cis-dioxo-catecholatotungsten(Ⅴ) complex (NH₂CH₂CH₂NH₃)₄[W^ⅤO₂(OC₆H₄O)₂]₂(NH₃CH₂CH₂NH₃)·H₂O (1) was synthesized at room temperature by the reaction of tetrabutyl ammonium decatungstate with catechol in the mixed solvent of CH₃OH, CH₃CN and NH₂CH₂CH₂NH₂. The crystal structure of complex was determined by X-ray diffraction structural analysis. The results show that complex belongs to monoclinic system with space group P2₁/c,a=0.712 8(3) nm, b=3.082 3(11) nm, c=0.982 8(4) nm, β=102.639(6)°, V=2.106 8(14) nm³, Z=2, R₁=0.062 8, wR₂=0.183 7. Compared the complex with its analogous complexes (NH₂CH₂CH₂NH₃)₃[Mo^ⅤO₂(OC₆H₄O)₂], it is found that the coordination structure of W have no changes in the processing of electron transfer of tungsten-containing enzymes from the result of the similarity of the EPR spectra of the complexes and flavoenzyme from milk. CCDC: 272937.     

The Synthesis and Characterization of 2-Amino-3-methylpyridinium Dihydrogenmonophosphate: (C6H9N2)H2PO4

A new crystal of 2-amino-3-methylpyridinium dihydrogenmonophosphate has been prepared and characterized by X-ray crystallography, thermal analysis, and impedance and NMR spectroscopies. This compound crystallizes in the triclinic space group P with a = 7.343(2) Å, b = 7.987(2) Å, c = 8.116(4) Å, α = 77,62(3)°, β = 77,74(3)°, γ = 87,03(2)°, V = 454.3 (3)ų, and Z = 2. The crystal structure was solved and refined to R = 0.030 with 1602 independent reflections. The atomic arrangement can be described as (H₂PO₄ ^?)_n polymeric chains anchoring the 2-amino-3-methylpyridinium cations through short hydrogen bonds. All ring atoms of the organic entity are coplanar. The exocyclic N atom is an electron receiving center, which is consistent with features of imino resonance evidenced by bond lengths and angles. Solid state ³¹P, ¹³C, and ¹⁵N CP-MAS-NMR spectroscopies are in agreement with the X-ray structure. Ab initio calculations allow the attribution of carbons and nitrogen to the independent crystallographic sites.     

The Synthesis and Characterization of a New Layered Chlorozincophosphate Zn(HPO4)Cl[C4H10N]

Along a systematic study of open-framework materials aiming at producing new molecular sieves, we characterized a new zincophosphate Zn(HPO₄)Cl[C₄H₁₀N]. It was synthesized under mild conditions (r.t.) in the presence of pyrrolidinium as an organic-structure directing agent. The structure of this compound, determinated by single crystal X-ray diffraction, consists of anionic parallel [Zn(HPO₄)Cl]^? sheets alternating with thick slabs of organic molecules (C₄H₁₀N)⁺. These latters are linked to the anionic sheets through hydrogen bonds. Zn(HPO₄)Cl[C₄H₁₀N] crystallizes in the monoclinic system and the space group C2/c (No. 9) with cell parameters a = 24,83(9), b = 9,258(5), c = 8.778(3), β = 110,45(4), Z = 8, V = 1891.0(14) Åt³, R = 0.045, and R_w = 0.07. Solid state ³¹P and ¹³C MAS NMR spectroscopies are in agreement with the X-ray structure.     

Synthesis and characterization of a new monophosphate (C<Subscript>6</Subscript>H<Subscript>16</Subscript>N<Subscript>2</Subscript>)(H<Subscript>2</Subscript>PO<Subscript>4</Subscript>)<Subscript>2</Subscript>

Chemical preparation, crystal structure, and NMR spectroscopy of a new trans-2,5-dimethylpiperazinium monophosphate are given. This new compound crystallizes in the triclinic system, with the space group P-1 and the following parameters: a = 6.5033(3), b = 7.6942(4), c = 8.1473(5) Å, α = 114.997(3), β = 92.341(3), γ = 113.136(3), V = 329.14(3) ų, Z = 1, and D_x = 1.565 g cm^?3. The crystal structure has been determined and refined to R = 0.030 and R _w(F ²) = 0.032 using 1558 independent reflections. The structure can be described as infinite [H₂PO₄] _n ^n? chains with (C₆H₁₆N₂)²⁺ organic cations anchored between adjacent polyanions to form columns of anions and cations running along the b axis. This compound has also been investigated by IR, thermal, and solid-state, ¹³C and ³¹P MAS NMR spectroscopies and Ab initio calculations.     

Synthesis,Single Crystal Structure Determination and Rietveld Refinement of Cadmium Tetrametaphosphimate Octahydrate Cd2(PO2NH)4·8H2O

Cd₂(PO₂NH)₄ · 8H₂O crystallizes in space group P2₁/c (no. 14), Z = 2, with a = 648.5(2), b = 1070.5(2), c = 1328.7(3) pm and β = 103.11(3) °. The structure, isotypic with M₂(PO₂NH)₄ · 8H₂O (M = Mg, Mn, Co, Ni, Zn), is composed of Cd²⁺ and (PO₂NH)₄^4? ions as well as crystal water molecules. The P₄N₄ rings of the (PO₂NH)₄^4? ions exhibit a slightly distorted chair‐2 conformation, which has been described by torsion angles, displacement asymmetry parameters and puckering parameters. The tetrametaphosphimate anions are connected forming layers. These layers are linked solely by hydrogen bonds, forming a three‐dimensional network.     

Preparation and Crystal Structure of an Acidic Long-chain Polyphosphate: CaH2(PO3)4

Preparation and crystal structure of an acidic polyphosphate of calcium is described. CaH₂(PO₃)₄: monoclinic, P2₁/c, with Z = 2, and a = 5.686(1), b = 9.676(4), c = 8,844(3) Å, β = 92.35(2)°. The crystal structure was solved using 2 321 unique reflections with a final R value of 0.017. The compound is characterized by infinite (PO₃)_n chains running along c and linked together in a three-dimensional way by Ca? O and hydrogen bonds. The two-dimensional linkage of the phosphoric chains by hydrogen bonds is compared to those already observed in ErH(PO₃)₄ and BiH(PO₃)₄.     

Influence of coordination on N-H X hydrogen bonds. Part II. Zn(NH3)2Br2 and Ni(NH3)2X2 (X is Cl and Br)

Microcrystalline samples of Zn(NH₃)₂Br₂ and Ni(NH₃)₂X₂ (X is Cl⁻ and Br⁻) have been investigated from 100 to 293 K using X-ray diffraction and IR spectroscopy measurements (range 400–4000 cm⁻) performed with isotopically dilute (5% deuterated) samples. Values of Δν(ND)/ΔT for all compounds hint at the existence of hydrogen bonds. Zn(NH₃)₂Br₂ shows The dynamics of ammonia molecules even at 100 K, and no indications are apparent that dynamic disorder of ammonia molecules takes place in Ni(NH₃)₂X₂ (X is Cl⁻ and Br⁻). A comparison between octahedrally coordinated ammoniates [Ni(NH₃)₆]Br₂, Ni(NH₃)₂Br₂ and [Zn(NH₃)₆]Br₂ with tetrahedrally coordinated ones [Zn(NH₃)₂Br₂] leads to the conclusion that the lower coordination number increases the strength of the hydrogen bonds. Because this effect is small, it is not possible to separate the influence of the type of coordinating ions for one coordination number from the influence of the coordination number itself.     

Synthesis and Characterization of a Novel Binuclear Cobalt(II) Complex with Discrete Water Clusters (H2O)8

A new octameric water cluster was observed in the complex Co₂(dptc)(bipy)₂(H₂O)₆ · 4H₂O ( 1 ) (H₄dptc = diphenyl‐3,3′,4,4′‐tetracarboxylic acid; bipy = 2,2′‐bipyridine), which was characterized by single‐crystal X‐ray diffraction, elemental analysis and IR spectroscopy. The centrosymmetric octamer consists of a water hexamer in the chair form and two water molecules and brings to light a novel mode of the cooperative association of water molecules. Those complex units are connected into a 2D infinite layer framework through hydrogen bonding. Consequently, the 2D layers are further aggregated by hydrogen bonding with octameric subunits and π ··· π stacking interactions to form a 3D supramolecular architecture.