F. Lefebvre

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 Å3, 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.

Bis(4-methyl­benzyl­ammonium) tetra­chloridozincate: a new noncentrosymmetric structure characterized by 13C CP–MAS NMR spectroscopy

A new noncentrosymmetric organic-inorganic hybrid material, (C(8)H(12)N)(2)[ZnCl(4)], has been synthesized as single crystals at room temperature and characterized by X-ray diffraction and solid-state NMR spectroscopy. Its novel structure consists of two 4-methylbenzylammonium cations and one [ZnCl(4)](2-) anion connected by N-H···Cl and C-H···Cl hydrogen bonds, two of which are three-centre interactions. The Zn(II) metal centre has a slightly distorted tetrahedral coordination geometry. Results from (13)C CP-MAS NMR spectroscopy are in good agreement with the X-ray structure. Density functional theory calculations allow the assignment of the carbon peaks to the independent crystallographic sites.

Synthesis, Structure, and Physicochemical Studies of Hexakis (5-Chloro-2,4-dimethoxyanilinium)cyclohexaphosphate Tetrahydrate

The physicochemical properties of a new organic cyclohexaphosphate, [5-Cl-2,4-(OCH3)2C6H2-NH3]6P6O18·4H2O, are discussed on the basis of an X-ray crystal structure investigation. This compound crystallizes in the monoclinic space group C2/c, with cell parameters a = 37.987(7) Å, b = 13.125(4) Å, c = 14.331(5) Å, β = 98.21(3)°, Z = 4, V = 7072(3) Å3. Its crystal structure is determined and refined to a final R = 0.058 for 5223 independent reflections. The atomic arrangement can be described as a layer organization built up by P6O18 ring anions and water molecules. Between these layers, the organic groups are located that form hydrogen bonds with oxygen atoms of P6O18 rings and water molecules. Intermolecular π–π stacking interactions between two neighboring organic cation rings help to establish the crystal packing. Solid 31P MAS-NMR spectroscopy is in agreement with X-ray structure. Ab initio calculations allow the attribution of the three phosphorus signals to the independent crystallographic sites. This compound is also characterized by thermal analysis and IR spectroscopy. Supplemental materials are available for this article. Go to the publishers online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.

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)Å3, 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.

Synthesis and Characterization of Bis(4-methylbenzylammonium) Tetrachloridocadmate(II)

The crystal structure of the new inorganic-organic hybrid compound [4-CH3C6H4CH2NH3]2[CdCl4] has been determined by single crystal X-ray diffraction. The compound crystallizes in the orthorhombic space group Pnma with lattice parameters , , u2009A, , u2009A3, and . The framework of the title compound is built upon layers parallel to (010) made up from corner-sharing CdCl6 octahedra. 4-Methylbenzylammonium cations are situated between the layers and connect them via an N–H⋯Cl hydrogen bonding network. The Cd atom is located on an inversion centre, and the coordination environment is described as distorted octahedral. Solid state 13C CP-MAS NMR spectroscopy is in agreement with the X-ray structure. DFT calculations allow the attribution of the carbon peaks to the independent crystallographic sites. Thermal analysis and infrared spectroscopy were also used to characterize the complex.

Synthesis and Characterization of a new Cyclohexaphosphate, (C9H14N)4(H3O)2(P6O18)

AbstractThe physicochemical properties of a new cyclohexaphosphate, (C9H14N)4(H3O)2(P6O18), prepared by an acid-base reaction between cyclohexaphosphoric acid H6P6O18 and 2,4,6-trimethylaniline, are discussed on the basis of X-ray crystal structure investigation. The crystal structure determination reveals that the complete cyclohexaphosphate anion, with chair conformation, is generated by crystallographic inversion symmetry. The asymmetric unit consists of two organic cations, one half-anion and one hydronium cation. The atomic arrangement can be described by thick layers built by P6O18 anions and H3O+ cations parallel to the (a, b) plane. Each cyclohexaphosphate group is connected to its adjacent neighbors by six hydronium ions through strong O-H...O hydrogen bonds. The protonated amines are located between these successive inorganic layers, in order to balance the negative charge of the inorganic framework by establishing N–H...O hydrogen bonds with the O atoms of the P6O18 anions. The three-dimensional cohesion is assured by different interactions (electrostatic, H-bonds, van der Waals) established between the various molecular components. This compound is also characterized by infrared spectroscopy and solid state MAS-NMR.n Graphical AbstractStructure and physicochemical properties of a new cyclohexaphosphate, (C9H14N)4(H3O)2(P6O18), are discussed on the basis IR spectrum, solid state MAS-NMR and X-ray crystal structure. The cyclohexaphosphate anion, with chair conformation, is generated by crystallographic inversion symmetry. The atomic arrangement can be described by thick layers built by P6O18 anions and H3O+ cations parallel to the (a, b) plane. Each cyclohexaphosphate group is connected to its adjacent neighbors by six hydronium ions through strong O-H…O hydrogen bonds.

Bis[4-(dimethyl­amino)­pyridinium] tetra­chloridozincate

In the title compound, (C7H11N2)2[ZnCl4], [ZnCl4]2− anions and 4-(dimethylamino)pyridinium cations are held together by various intermolecular interactions including Coulombic attraction, hydrogen bonding and π–π stacking interactions. Three Cl atoms of the [ZnCl4]2− tetrahedron act as acceptors in N—H⋯Cl hydrogen bonds. The hydrogen bonds, both of which are bifurcated, lead to the formation of a three-dimensional network. Within the network, intermolecular π–π stacking interactions with a centroid–centroid distance of 3.5911u2005(7)u2005Å arrange the 4-(dimethylamino)pyridinium cations into antiparallel dimers.

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) Å3, 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.

Physico-Chemical Studies of Tris (adamantan-1-aminium) Hexachlorostannate (IV) Chloride Monohydrate

The structural characteristics of organic ammonium salts of the hexahalogenostannates (IV) with a general formula (R-NH 3)3SnX 6 have not yet been studied extensively. In the course of investigating these types of materials, the title compound, a double salt of adamantan-1aminium chloride and hexahalogenostannate (IV), with the formula (C 10 H18 N) 3[SnCl 6]Cl·H 2O, was crystallized. Its asymmetric unit contains three independent cations of protonated adamantan-1-amine, one chloride anion, one Hexachlorostannate (IV) ion and a hydrate water molecule. The atomic arrangement can be described as inorganic SnCl 6 2- units isolated from each other by the organic cations, the chloride anions and the cocrystallized water molecules. The compound exhibits bifurcated and simple hydrogenbonding interactions between the ammonium groups, the water molecules and the chlorine atoms, with little variation in the hydrogen-bonding interactions. The 119 Sn, 13 C and 15 N CPMAS NMR spectra are in agreement with the X-ray structure.

4-Acetamido-anilinium nitrate monohydrate.

In the title hydrated salt, C8H11N2O+·NO3 −·H2O, the N—C bond distances [1.349u2005(2) and 1.413u2005(2)u2005Å] along with the sum of the angles (359.88°) around the acetamide N atom clearly indicate that the heteroatom has an sp 2 character. The ammonium group is involved in a total of three N—H⋯O hydrogen bonds, two of these are with a water molecule, which forms two O—H⋯O hydrogen bonds. All these hydrogen bonds link the ionic units and the water molecule into infinite planar layers parallel to (100). The remaining two N—H⋯O interactions in which the ammoniun group is involved link these layers into an infinite three-dimensional network.