Anilinium mono­hydrogen dl‐malate

Crystals of the title salt, [(C₆H₅NH₃)]⁺·[(HOOC(CH₂)CH(OH)COO)]⁻ or C₆H₈N⁺·C₄H₅O₅⁻, are built up from protonated anilinium residues and monodissociated dl ‐malate ions. The NH₃⁺ group of the anilinium cation is ordered at room temperature. Rotation of the NH₃⁺ group along the C(aromatic)—Nsp³ bond (often observed at room temperature in other anilinium salts) is prevented by N—H⋯O hydrogen bonds between the NH₃⁺ group and the malate anions. The anions are connected by four O—H⋯O hydrogen bonds into two‐dimensional sheets parallel to the (001) plane. The charged moieties, i.e. the anilinium cations and the sheets of hydrogen‐bonded malate anions, form two‐dimensional layers in which the phenyl rings of the anilinium residues lie perpendicular to the malate‐ion sheets. The conformation of the monodissociated malate ion in the crystal is compared with that obtained from ab initio molecular‐orbital calculations.     

The anilinium chloride adduct of 4‐bromo‐N‐phenylbenzene­sulfonamide

The title compound anilinium chloride–4‐bromo‐N‐phenyl­benzene­sulfonamide (1/1), C₆H₈N⁺·Cl⁻·C₁₂H₁₀BrNO₂S, displays a hydrogen‐bonded ladder motif with four independent N—H⋯Cl bonds in which both the NH group of the sulfonamide molecule and the NH₃ group of the anilinium ion [N⋯Cl = 3.135 (3)–3.196 (2) Å and N—H⋯Cl = 151–167°] are involved. This hydrogen‐bonded chain contains two independent R₄²(8) rings and each chloride ion acts as an acceptor of four hydrogen bonds.     

2‐Amino­anilinium phosphite

The solid‐state structure of the title compound, alternatively called 2‐amino­anilinium hydrogen phosphonate, C₆H₉N₂⁺·H₂PO₃^?, shows the monoprotonated di­amine mol­ecule to be multiply hydrogen bonded to HPO₃H^? anions. There is no inter‐phosphite hydrogen bonding, contrary to previous solid‐state observations of the species.     

Sulfonate salts of the therapeutic agent dapsone: 4‐[(4‐aminophenyl)sulfonyl]anilinium benzenesulfonate monohydrate and 4‐[(4‐aminophenyl)sulfonyl]anilinium methanesulfonate monohydrate

Dapsone, formerly used to treat leprosy, now has wider therapeutic applications. As is the case for many therapeutic agents, low aqueous solubility and high toxicity are the main problems associated with its use. Derivatization of its amino groups has been widely explored but shows no significant therapeutic improvements. Cocrystals have been prepared to understand not only its structural properties, but also its solubility and dissolution rate. Few salts of dapsone have been described. The title salts, C₁₂H₁₃N₂O₂S⁺·C₆H₅O₃S⁻·H₂O and C₁₂H₁₃N₂O₂S⁺·CH₃SO₃⁻·H₂O, crystallize as hydrates and both compounds exhibit the same space group (monoclinic, P2₁/n). The asymmetric unit of each salt consists of a 4‐[(4‐aminophenyl)sulfonyl]anilinium monocation, the corresponding sulfonate anion and a water molecule. The cation, anion and water molecule form hydrogen‐bonded networks through N—H…O=S, N—H…O_water and O_water—H…O=S hydrogen bonds. For both salts, the water molecules interact with one sulfonate anion and two anilinium cations. The benzenesulfonate salt forms a two‐dimensional network, while the hydrogen bonding within the methanesulfonate salt results in a three‐dimensional network.     

Crystal structure and luminescence of antimony(III) chloride complex with anilinium chloride

Crystal structure of (C₆H₅NH₃)₃[SbCl₅]Cl·H₂O is determined by X-ray analysis (a = 9.4155(13) Å, b = 11.4344(16) Å, c = 13.1584(18) Å, α = 113.483(2)°, β = 90.383(2)°, γ = 97.323(2)°, space group P \(\bar 1\), Z = 2, ρ_calc = 1.642 g/cm³). The crystal structure is based on [SbCl₅]^2? anions, anilinium cations (C₆H₅NH₃)⁺, isolated Cl^? anions, and water molecules. Structural features responsible for spectral and luminescent properties of the complex are discussed.     

4‐Nitro­anilinium nitrate

The crystal structure of the title compound, C₆H₇N₂O₂⁺·NO₃⁻, is built up from 4‐nitro­anilinium cations and nitrate anions. The NO₂ group is coplanar with the aryl ring, which shows significant distortion from the ideal hexagonal form. The NO₃⁻ anion is planar but shows distortion from the C_3h symmetry that is predicted by molecular orbital calculations. Two of the three O atoms of the NO₃ group are involved in hydrogen bonds as acceptors.     

The 1:1 proton‐transfer compounds of 4‐(phenyldiazenyl)aniline (aniline yellow) with 3‐nitrophthalic, 4‐nitrophthalic and 5‐nitroisophthalic acids

The structures of the anhydrous 1:1 proton‐transfer compounds of the dye precursor aniline yellow [4‐(phenyldiazenyl)aniline], namely isomeric 4‐(phenyldiazenyl)anilinium 2‐carboxy‐6‐nitrobenzoate, C₁₂H₁₂N₃⁺·C₈H₄NO₆⁻, (I), and 4‐(phenyldiazenyl)anilinium 2‐carboxy‐4‐nitrobenzoate, C₁₂H₁₂N₃⁺·C₈H₄NO₆⁻, (II), and 4‐(phenyldiazenyl)anilinium 3‐carboxy‐5‐nitrobenzoate monohydrate, C₁₂H₁₂N₃⁺·C₈H₄NO₆⁻·H₂O, (III), have been determined at 130 K. In (I) the cation has longitudinal rotational disorder. All three compounds have substructures comprising backbones formed through strong head‐to‐tail carboxyl–carboxylate hydrogen‐bond interactions [graph set C(7) in (I) and (II), and C(8) in (III)]. Two‐dimensional sheet structures are formed in all three compounds by the incorporation of the 4‐(phenyldiazenyl)anilinium cations into the substructures, including, in the cases of (I) and (II), infinite H—N—H to carboxylate O—C—O group interactions [graph set C(6)], and in the case of (III), bridging through the water molecule of solvation. The peripheral alternating aromatic ring residues of both cations and anions give only weakly π‐interactive step features which lie between the sheets.     

Hydrogen bonding in 1:1 proton‐transfer compounds of 5‐sulfosalicylic acid with 4‐X‐substituted anilines (X = F,Cl or Br)

The crystal structures of three proton‐transfer compounds of 5‐sulfosalicylic acid (3‐carboxy‐4‐hydroxy­benzene­sulfonic acid) with 4‐X‐substituted anilines (X = F, Cl and Br), namely 4‐fluoro­anilinium 5‐sulfosalicylate (3‐carboxy‐4‐hydroxybenzenesulfonate) monohydrate, C₆H₇FN⁺·C₇H₅O₆S⁻·H₂O, (I), 4‐chloro­anilinium 5‐sulfosalicylate hemihydrate, C₆H₇ClN⁺·C₇H₅O₆S⁻·0.5H₂O, (II), and 4‐bromo­anilinium 5‐sulfosalicylate monohydrate, C₆H₇BrN⁺·C₇H₅O₆S⁻·H₂O, (III), have been determined. The asymmetric unit in (II) contains two formula units. All three compounds have three‐dimensional hydrogen‐bonded polymeric structures in which both the water molecule and the carboxylic acid group are involved in structure extension. With both (II) and (III), which are structurally similar, the common cyclic (8) dimeric carboxylic acid association is present, whereas in (I), an unusual cyclic (8) association involving all three hetero‐species is found.     

Boron–π interactions in two 3-(dihydroxyboryl)anilinium salts analyzed by crystallographic studies and supported by the noncovalent interactions (NCI) index theoretical approach

In the title compounds, 3-(dihydroxyboryl)anilinium bisulfate monohydrate, C₆H₉BNO₂⁺·HSO₄⁻·H₂O ( I ), and 3-(dihydroxyboryl)anilinium methyl sulfate, C₆H₉BNO₂⁺·CH₃SO₄⁻ ( II ), the almost planar boronic acid molecules are linked by pairs of O—H…O hydrogen bonds, forming centrosymmetric motifs that can be described by the graph-set R₂²(8) motif. In both crystals, the B(OH)₂ group acquires a syn–anti conformation (with respect to the H atoms). The presence of the hydrogen-bonding functional groups B(OH)₂, NH₃⁺, HSO₄⁻, CH₃SO₄⁻ and H₂O generates three-dimensional hydrogen-bonded networks, in which the bisulfate (HSO₄⁻) and methyl sulfate (CH₃SO₄⁻) counter-ions act as the central building blocks within the crystal structures. Furthermore, in both structures, the packing is stabilized by weak boron–π interactions, as shown by noncovalent interactions (NCI) index calculations.     

Hexafluorosilicates of 2-substituted anilinium derivatives

The reaction of 45% fluorosilicic acid with methanol solutions of several 2-substituted anilines(L) gave hexafluorosilicates (LH)₂SiF₆. The products were studied by elemental analysis, IR spectroscopy, mass spectrometry, and thermogravimetry. The solubility and the hydrolytic stability of the salts were estimated. The structure of the complex [CH₃O(O)CC₆H₄NH₃]₂SiF₆ was determined by single-crystal X-ray diffraction. The ionic structure is composed of centrosymmetric SiF ₆ ^2? anions (the average Si-F bond length is 1.679(1) Å) and the [CH₃O(O)CC₆H₄NH₃]⁺ cations. The NH ₃ ⁺ group is the donor for the inner-cation H-bond with the carbonyl oxygen atom (NH···O), and for two ion-ion H-bonds (NH···F). The Si-F bond lengths correlate with the strengths of the H-bonds involving the corresponding fluorine atoms.     

X-ray diffraction study of acid anilinium dodecatungstenphosphate

Acid anilinium dodecatungstenphosphate of composition (C₆H₅NH₃)₂H[PW₁₂O₄₀] 2H₂O is synthesized and characterized by X-ray diffraction analysis, IR spectroscopy, and thermogravimetry. The crystals are monoclinic: space group P2₁/m, a = 9.940(2) , b = 15.412(3) , c = 16.201(3) , = 100.42(3)°, Z = 2, _calcd = 4.221 g/cm³. The structure contains heteropolyanions [PW₁₂O₄₀]^3–, cations [C₆H₅NH₃]⁺ and H⁺, and molecules of water of crystallization. The heteropolyanions and anilinium cations in crystal are linked by the electrostatic interaction and hydrogen bonds.__________Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 4, 2005, pp. 273–279.Original Russian Text Copyright © 2005 by Kaziev, Dutov, Quinones, Koroteev, Belskii, Stash, Kuznetsova.     

Differences and similarities among hypoxanthinium nitrate hydrate structures

Crystals of hypoxanthinium (6‐oxo‐1H,7H‐purin‐9‐ium) nitrate hydrates were investigated by means of X‐ray diffraction at different temperatures. The data for hypoxanthinium nitrate monohydrate (C₅H₅N₄O⁺·NO₃^?·H₂O, Hx1 ) were collected at 20, 105 and 285 K. The room‐temperature phase was reported previously [Schmalle et al. (1990). Acta Cryst. C 46 , 340–342] and the low‐temperature phase has not been investigated yet. The structure underwent a phase transition, which resulted in a change of space group from Pmnb to P2₁/n at lower temperature and subsequently in nonmerohedral twinning. The structure of hypoxanthinium dinitrate trihydrate (H₃O⁺·C₅H₅N₄O⁺·2NO₃^?·2H₂O, Hx2 ) was determined at 20 and 100 K, and also has not been reported previously. The Hx2 structure consists of two types of layers: the `hypoxanthinium nitrate monohydrate' layers (HX) observed in Hx1 and layers of Zundel complex H₃O⁺·H₂O interacting with nitrate anions (OX). The crystal can be considered as a solid solution of two salts, i.e. hypoxanthinium nitrate monohydrate, C₅H₅N₄O⁺·NO₃^?·H₂O, and oxonium nitrate monohydrate, H₃O⁺(H₂O)·NO₃^?.     

Synthesis and Structure of Dicyclohexylammonium Tri‐tert‐pentoxysilanethiolate and 5‐Aminopentylammonium Tri‐tert‐pentoxysilanethiolate

Tri–tert–pentoxysilanethiol, (EtMe₂CO)₃SiSH, reacts with dicyclohexylamine and 1,5–diaminopentane yielding ion‐quadruples connected by hydrogen bonds: [{(C₆H₁₁)₂NH₂}⁺{(EtMe₂CO)₃SiS}^?]₂ ( 1 ) and [{H₂N–C₅H₁₀–NH₃}⁺{(EtMe₂CO)₃SiS}^?]₂ ( 2 ). The compounds were characterized by X–ray diffraction, elemental analysis, IR and NMR. Both compounds form dimers, composed of two thiolate anions and two ammonium cations. The dimers have a central core of eight–membered rings built due to the formation of four charge–assisted N⁺–H···^?S–hydrogen bonds. Additional N⁺–H···N hydrogen bonds are found in the case of 2 , linking the dimers into infinite two–dimensional sheets.     

Synthesis,characterization and crystal structure of the anilinium β-octamolybdate dihydrate

The anilinium β-octamolybdate dihydrate has been prepared in acidic aqueous solution. TG, DTG, IR and ¹H NMR techniques have been used to identify the compound. It belongs to a series of molybdates of alkyl-N- and -N,N-substituted anilinium cations. Single crystals have been analyzed by X-ray diffraction. Crystal data are: (C₆H₈N)₄[Mo₈O₂₆] · 2H₂O, space group P$\text{1}$, Z = 1, a = 10.007(1), b = 8.014(2), c = 14.645(8)Å, α = 109.81(3), β = 108.59(2), γ = 85.44(2)°, V = 1052.9(6) ų, D_o = 2.49(1), D_x = 2.52 mg m^?3, R = 0.026 and R_w = 0.031 for 5297 observed reflexions. The crystal structure consists of discrete [β-Mo₈O₂₆]^4? polyanions, two crystallographically independent (C₆H₈N)⁺ cations and one independent water molecule. Polyanions are linked to the cations and to the water molecules by hydrogen bonds of types NH…O and OH…O.     

Luminescence of antimony(III) halide complexes with aniline

The antimony(III) chloride and bromide complexes with aniline, (C₆H₅NH₃)₂SbCl₅·(C₆H₅NH₃)Cl·H₂O (I) and (C₆H₅NH₃)₂SbBr₅ (II), were synthesized, and their spectral luminescence properties were studied. An interesting peculiarity of I and II is the possibility of selective excitation of luminescence in the π system of the (C₆H₅NH₃)⁺ outer sphere anilinium cation and intrinsic luminescence of the s ² ion. The population scheme for the luminescent antimony ³ P ₁ level in I and II is discussed using the luminescence, UV, and photoelectron spectroscopy data. Original Russian Text ? T.V. Sedakova, A.G. Mirochnik, V.E. Karasev, 2009, published in Zhurnal Fizicheskoi Khimii, 2009, Vol. 83, No. 2, pp. 380–382.     

The formation of the anilinium ion from the ammonium ion in the ammonia chemical ionization of substituted benzenes

Compounds C₆H₅X(X ? F, Cl, Br, NO₂, CN, OCH₃) have been studied under chemical ionization conditions with ammonia as reagent gas. A pulsed electron beam and time resolved ion collection has allowed the determination of the reaction leading to the formation of [C₆H₅NH₃]⁺ (m/z 94). [NH₄]⁺ reacts with C₆H₅X(X ? F, Cl, Br) to yield m/z 94 but C₆H₅X (X ? CN, NO₂) forms this ion only by reactions involving either [NH₃]⁺ or [C₆H₅X]⁺. C₆H₅OCH₃ does not form m/z 94.     

(M)‐ and (P)‐8‐[(1S,2R)‐2‐hydroxy‐1‐methyl‐2‐phenylethyl]‐8‐methyl‐8,9‐dihydro‐7H‐dinaphth[2,1‐c:1′,2′‐e]azepinium bromide solvates

The title compounds are diastereoisomers with antipodean axial chirality. The M isomer crystallizes as a (1/3) acetone solvate, C₃₂H₃₀NO⁺·Br^?·3C₃H₆O, while the P isomer crystallizes as a (1/1) di­chloro­methane solvate, C₃₂H₃₀NO⁺·Br^?·CH₂Cl₂. In each structure, O—H?Br hydrogen bonds link the cations and anions to give ion pairs. The seven‐membered azepinium ring adopts the usual twisted‐boat conformation and its ring strain causes a slight curvature of the plane of each naphthyl ring.     

Potassium hydrogen trans‐glutaconate monohydrate at 295, 245 and 40 K,and its rubidium analogue at 298 K

A centrosymmetric and short O—H?O hydrogen bond was found in isomorphic crystals of potassium hydrogen trans‐glutaconate monohydrate (potassium hydrogen trans‐pent‐2‐ene‐1,5‐dioate, K⁺·C₅H₅O₄^?·H₂O), (I), and rubidium hydrogen trans‐glutaconate monohydrate (rubidium hydrogen trans‐pent‐2‐ene‐1,5‐dioate, Rb⁺·C₅H₅O₄^?·H₂O), (II). The O?O distance at room temperature is 2.444 (3) Å in (I), and 2.417 (4) Å in (II). The O?O distance for (I) showed no significant decrease at low temperatures.     

Synthesis and crystal structures of 2,4,6-pyridine-tricarboxylic anions/guanidinium and tetraalkylammonium inclusion compounds

Two different hydrogen-bonded inclusion compounds, [2,4,6-C₅H₂N(COO^?)₃]_0.5·[C(NH₂) ₃ ⁺ ]_0.5·[(C₂H₅)₄N⁺]·2H₂O (1) and [2,4,6-C₅H₂N(COO^?)₃]·[C(NH₂) ₃ ⁺ ]·[(C₂H₅)₄N⁺]·[(C₃H₇)₄N⁺]·6H₂O (2) are reported in this paper, in which 2,4,6-pyridine-tricarboxylic anions, guanidiniums and water molecules jointly construct host lattices while tetraalkylammonium cations are accommodated as guest species. Both two compounds formed sandwich-like hydrogen-bond inclusion compounds. In compound 1, the dimers composed of 2,4,6-pyridine-tricarboxylic anions and guanidiniums form 2D hydrogen-bonded layers by connecting with water molecules. In compound 2, 2,4,6-pyridine-tricarboxylic anions, guanidiniums and water molecules contribute to generate an undulate rosette hydrogen-bonded architecture. Interestingly, in compound 2, there are two species of guest molecules, tetraethylammonium and tetrapropylammonium, which are alternately arranged between the neighboring layers. Mixed guest cations accommodated in hydrogen-bonded inclusion compounds are seldom seen.     

Reaction of ammonia with accelerated benzoyl ions under multiple-collison conditions in a triple quadrupole instrument

The reaction of benzoyl ion with ammonia in multiple-collision conditions in the second quadrupole assembly of a triple quadrupole mass spectrometer at (laboratory) ion kinetic energies from 0 to 20 eV produced the even-electron ions [C₆H₅]⁺, [C₆H₅NH₃·(NH₃)_m]⁺ (m = 0, 1) and [C₆H₅CONH₃·(NH₃)_n]⁺ (n = 0, 1, 2, 3) and the odd-electron ions [C₆H₄NH₃·(NH₃)_p]⁺· (p = 0, 1). Thermochemical information could not be obtained under multiple-collision conditions: both exothermic and endothermic reactions were observed, with no translational-energy onset measurable for the endothermic processes, nor decrease in the yield of the exothermic processes at high energies. The behaviour of cluster-ion intensities as pressure varied was qualitatively as expected. There are pressure and energy regions where spectra change little; if this feature were to be general, it would point to some utility for these conditions in qualitative analysis.