I[NI4] · NH3, ein neues Derivat des Iodstickstoffs

I[NI₄] · NH₃, a New Derivate of Nitrogen Triiodide The former unknown compound I[NI₄] · NH₃ can be prepared in a closed vessel in the presence of a trace of water from nitrogen triiodide NI₃ · NH₃. It crystallizes hexagonal in the space group P6₃mc with a = 842.5 pm, c = 876.5 pm and Z = 2 formula units. Three corners of a nearly regular tetrahedron (d(N–I) = 219.0, 223.6 pm) are connected by trigonal-pyramidal coordinated iodine atoms with d(I–I) = 308.8 pm to puckered layers stacked in the direction of the c-axis. The molecule NH₃ fills the space between the iodine layers. It is coordinated to that iodine atom of the NI₄-tetrahedron which is not involved in the iodine net. Some chemical properties of the compound are reported.     

Untersuchungen an Stickstoff—Jod-Verbindungen. VII. Das IR-Spektrum des Stickstofftrijodid-1-Ammoniaks im Bereich der N–J-Grundschwingungen und Kraftkonstanten der N–J-Bindungen

Studies on nitrogen iodine compounds. VII. The IR spectrum of nitrogen triiodide-1 ammonia in the range of N—I fundamental vibrations and the valence force constants of the N—I bonds New infrared spectra in the region 33—600 cm^?1 of ¹⁴NI₃ · ¹⁴NH₃, ¹⁵NI₃ · ¹⁵NH₃ and ¹⁴NI₃ · pyridine, respectively, have been obtained. In addition, the infrared spectrum of ¹⁴NI₃ · ¹⁴ND₃, which has been prepared for the first time, was obtained. All absorption frequencies can be coordinated on the ground of the molecule model for the NI₃ scaffold with 5 atoms Z₂XY₂ of the symmetry C_2v which has been proved by X ray examination. A set of force constants has been calculated by approximation. The various nitrogeniodine valence force constants are discussed.     

Untersuchungen an Stickstoff-Jod-Verbindungen. X. Das Infrarotspektrum von Stickstofftrijodid-3-Ammoniak NJ3 · 3NH3 und Stickstofftrijodid-3-Deuteroammoniak NJ3 · 3ND3 im Bereich der N-J-Grundschwingungen

Studies on Nitrogen Iodine Compounds. X. The IR Spectra of NI₃ · 3NH₃ and NI₃ · 3ND₃ in the Region of N? I Fundamental Vibrations The IR spectra of NI₃ · 3 NH₃ and NI₃ · 3 ND₃ are similar to those of (NI₃ · NH₃)_n and (NI₃ · ND₃)_n, respectively. Especially the positions of the N? I vibrations are identical. From these results it is allowed to conclude that NI₃ · 3 NH₃ shows a N? I scaffold similar to the well known N? I scaffold of (NI₃ · NH₃)_n.     

UV-VIS- und Raman-spektroskopische Untersuchungen der grünen Lösungen von Stickstofftriiodid-1-Pyridin in Pyridin

UV-VIS-Spectroscopical Investigations of the Green Solutions of Nitrogen Triiodide-1-Pyridine in Pyridine Solid, crystalline nitrogen triiodide-1-pyridine has a polymeric structure similar to that of nitrogen triiodide-1-ammonia consisting of NI₄ tetrahedra linked to chains by common vertices. The solubility of both compounds in liquid ammonia is accomplished by a degradation of the chains involving protolysis equilibria with monoiodamine. UV-VIS-spectra of the green solutions of NI₃ pyridine in the aprotic solvent pyridine between ?30 and ?16°C and Raman-spectra of these solutions at ?30°C or quenched with liquid nitrogen at ?196°C show, that the chains are retained here at least to some extent. The solutions are instable even at low temperatures and decompose in a first order reaction yielding nitrogen and iodine. The halflife period at ?16°C is 5 hours, at ?30°C 20 hours.     

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.     

Two inclusion compounds of guanylthiourea and 1,3,5-thiadiazole-5-amido-2-carbamate

In the crystal structure of [(n-C₄H₉)₄N]⁺·[NH₂(C₂N₂S)NHCOO^?]·NH₂CSNC(NH₂)₂ (1), guanylthiourea molecules and 1,3,5-thiadiazole-5-amido-2-carbamate ions are joined together by intermolecular N–H…O, N–H…N, and weak N–H…S hydrogen bonds to generate stacked host layers corresponding to the (110) family of planes, between which the tetra-n-butylammonium guest cations are orderly arranged in a sandwich-like manner. In the crystal structure of [(n-C₃H₇)₄N]⁺·[NH₂(C₂N₂S)NHCOO^?]·NH₂CSNC(NH₂)₂·H₂O (2), the tetrapropyl ammonium cations are stacked within channels each composed of hydrogen bonded ribbons of guanylthiourea molecules, 1,3,5-thiadiazole-5-amido-2-carbamate ions and water molecules.     

A New Solvated Phosphoric Triamide, [(C6H4(3-CH3)NH)3P(O)] · (C2H5OH): A Database Analysis of N Atom Geometry in Compounds with an [N]3P(O) Fragment

Abstract

In the crystal structure of the title compound C₂₁H₂₄N₃OP · C₂H₅OH, there are three crystallographically independent phosphoric triamide molecules and three ethanol molecules. The environments of the nitrogen atoms are practically planar. The phosphorus atoms display a distorted tetrahedral environment; the maximum and minimum values of angles are observed for one O?P?N and one N?P?N angles, respectively. In this structure, the phosphoramide and ethanol molecules are linked by some different intermolecular O?H···O and N?H···O hydrogen bonds to form chains. The title solvated compound has been further characterized by IR and ³¹P{¹H}, ¹H and ¹³C NMR spectroscopy. The geometry of the nitrogen atoms in this compound is analyzed and compared with those of analogous structures deposited in the Cambridge Structural Database (CSD; Allen, Acta Cryst. 2002, B58, 380-388).     

The coordination properties of aminobenzoate ligands in complexes with alkali metals

The crystal structures of sodium 4-amino-2-hydroxybenzoate dihydrate [NaL·2H₂O, L?= C₆H₃(NH₂)(OH)COO] and potassium 2-aminobenzoate monohydrate [KL*·H₂O, L*?=?C₆H₄(NH₂)COO] were determined by X-ray diffraction methods. The compound NaL·2H₂O crystallizes in the monoclinic system, space group P2₁/c with a?=?8.820(2), b?=?14.632(3), c?=?6.948(2)?Å, β?=?97.88(3)°. The structure consists of sodium ion pairs joined together by tridentate 4-amino-2-hydroxybenzoate moieties creating a polymeric chain. In the metal centres, two water molecules bridge the sodium atoms. Five oxygen atoms and one nitrogen atom form a distorted octahedral environment. The compound KL*·H₂O crystallizes in the monoclinic system, space group P2₁/c with a?=?14.684(3), b?=?7.618(2), c?=?7.512(2)?Å, β?=?96.95(3)°. The structure consists of octacoordinated potassium atoms bonded with three water molecules and five carboxylate oxygen atoms. Water molecules appear as bridging ligands. The 2-aminobenzoate ligand acts as a pentadentate ligand with the molecular network stabilized by hydrogen bonds. Among the polymeric chains in both structures appear noncovalent interactions of type N?H···X.     

Solvothermal Synthesis,Crystal Structure,and Properties of a New Organic‐Templated Holmium Sulfate with 1D Single Ladder Chains

A new organic amine templated 1D holmium sulfate (C₂H₈N)[Ho(SO₄)₂ · H₂O] ( 1 ) has been synthesized and solvothermally and structurally characterized by single‐crystal X‐ray diffraction, IR spectroscopy, thermogravimetric and X‐ray diffraction analyses as well as scanning electron microscopy (SEM). The structure of framework 1 is constructed from HoO₈ polyhedra and SO₄ tetrahedra. S(1) and S(2) connects Ho(1) and its crystallographic partners by using three S–O–Ho linkages to generate double chains, whereas the adjacent double chain are connected by μ₃‐O (O₅) atoms to form a novel single ladder chains.     

Crystallographic report: Diiodo[tris(2‐pyridyl)amine]mercury(II), [(C5H4N)3N]HgI2

In mononuclear HgI₂[(C₅H₄N)₃N], mercury is tetrahedrally coordinated by two nitrogen atoms of a tris(2‐pyridyl)amine ligand and two iodides. The coordination moieties are connected by weak intermolecular Hg(II)···I interactions to give a one‐dimensional structure. Copyright © 2003 John Wiley & Sons, Ltd.     

Crystal Structures of Benzenselenonylamides C6H5SeO2NXY,X, Y = H,CH3, at 120 K. Twinned structure of C6H5SeO2NH2

The X-ray structures at 120 K of C₆H₅SeO₂N(CH₃)₂ ( 1 ) and C₆H₅SeO₂NHCH₃ ( 2 ) were determined from single crystal data, the structure of C₆H₅SeO₂NH₂ ( 3 ) was determined from a twin. The structure of ( 1 ) is composed of isolated molecules, that of ( 2 ) of dimers via H-bonds and the structure of ( 3 ) forms infinite chains. The Se? N lengths are 1.815(2) Å for ( 1 ), 1.791(2) Å for ( 2 ), and 1.781(6) Å for ( 3 ).     

一维双链镉(Ⅱ)配合物[Cd(C5H5N)CH2C(OH)(PO3)(PO3H)·3H2O]n的合成与晶体结构

A new cadmium complex [Cd(C₅H₅N)CH₂C(OH)(PO₃)(PO₃H)·3H₂O]_n((C₅H₄N)CH₂C(OH)(PO₃H₂)₂=1-hydroxy-2-(2-pyridyl)ethylidene-1,1-diphosphonate acid) has been synthesized under hydrothermal conditions. Single crystal structure determination reveals that the compound has a ladder-like chain structure in which the edge-shared {CdO₆} octahedra are linked by {CPO₃} tetrahedra through corner-sharing. The chains of {Cd(C₅H₅N)CH₂C(OH)(PO₃)(PO₃H)}_n are linked by inter-chain hydrogen bonds, forming a supramolecular layer. CCDC: 722396.     

Die Kristallstruktur des 1 : 1-Adduktes zwischen Antimontrichlorid und Diphenylammoniumchlorid,SbCl3 · (C6H5)2NH2+Cl−

The Crystal Structure of the 1:1 Addition Compound between Antimony Trichloride and Diphenylammonium Chloride, SbCl₃ · (C₆H₅)₂NH₂⁺Cl^? The 1:1 addition compound between antimony trichloride and diphenylammoniumchloride SbCl₃ · (C₆H₅)₂NH₂⁺Cl^? crystallizes in the monoclinic space group P2₁/n with a = 5.668(8), b = 20.480(12), c = 14.448(17) Å, β = 110.4(1)° and Z = 4 formula units. Chains of SbCl₃ molecules and anion cation chains are bridged by Cl ions and form square tubes. The coordination of the Sb atoms by Cl atoms by Cl atoms and Cl ions is distorted octahedral. Mean distances are Sb? Cl = 2.37 Å for Sb? Cl (3×), 3.09 Å for Sb…Cl^? (2×) and 3.42 Å for Sb…Cl (1×). The Sb…Cl^? contacts and hydrogen bonds NH…Cl^? at 3.15 Å generate tetrahedral coordination of the Cl ions.     

Untersuchungen an Stickstoff-Jod-Verbindungen. IX. Präparative und infrarotspektroskopische Untersuchungen an Jod-Komplexen von N-Jodmethylaminen

Studies of Nitrogen Iodine Compounds. IX. Preparation and I. R. Investigations of Iodine Complexes of N-Iodine Methylamines [CH₃NI₂]₂ · I₂, [(CH₃)₂NI]₂ · I₂ and (CH₃)₂NI · I₂, have been prepared. The IR-spectra have been obtained in the region 33–4000 cm^?1. The spectra can be coordinated on the ground of a molecule model with 5 atoms Z₂XYW of the symmetry C_s and are compared to that of CH₃NI₂. The structures of the compounds are proposed to be monomolecular.     

Bis[N-(isonitrosoacetophenone)-N′-benzoylhydrazonato-k<Superscript>3</Superscript>O,N,N′]nickel(II) dimethylformamide disolvate hemihydrate: Synthesis,crystal structure,and spectroscopic and electronic properties

In the title complex, [Ni(C₃₀H₂₄N₆O₄)]₂ · 4C₃H₇NO · H₂O (I), the Ni(II) atoms are six-coordinated by two N atoms and one O atom of each of the two tridendate benzoylhydrazone ligands, leading to a distorted octahedral geometry. In the environment of Ni(II) atoms, the equatorial planes are approximately perpendicular. The structure is stabilized by O-H...O, O-H...N, and C-H...O intra- and intermolecular hydrogen bonding, resulting in the formation of infinite chains running along the x axis of the triclinic cell. The structure of the compound was characterized by IR and UV spectra, elemental analyses, and X-ray diffraction techniques.     

First Characterization of an Extended Ammonium‐Ammonia Complex [{NH4(NH3)4}+(μ‐NH3)2] in the Crystal Structure of [NH4(NH3)4][Co(C2B9H11)2] · 2 NH3

The compound [NH₄(NH₃)₄][Co(C₂B₉H₁₁)₂] · 2 NH₃ ( 1 ) was prepared by the reaction of Na[Co(C₂B₉H₁₁)₂] with a proton‐charged ion‐exchange resin in liquid ammonia. The ammoniate 1 was characterized by low temperature single‐crystal X‐ray structure analysis. The anionic part of the structure consists of [Co(C₂B₉H₁₁)₂]^‐ complexes, which are connected via C‐H···H‐B dihydrogen bonds. Furthermore, 1 contains an infinite equation/tex2gif-stack-2.gif[{NH₄(NH₃)₄}⁺(μ‐NH₃)₂] cationic chain, which is formed by [NH₄(NH₃)₄]⁺ ions linked by two ammonia molecules. The N‐H···N hydrogen bonds range from 1.92 to 2.71Å (DHA = Donor···Acceptor angles: 136‐176°). Additional N‐H···H‐B dihydrogen bonds are observed (H···H: 2.3‐2.4Å).     

Complexation of N-Allyl Derivatives of Morpholinium with Copper(I) Halides: Synthesis and Crystal Structure of [C4H8ON(C3H5)2]+[Cu4Cl5]–, [C4H8ONH(C3H5)]+[CuBr2]–, and [C4H8ONH(C3H5)]+[CuBr1.41Cl0.59]–

The compounds [C₄H₈ON(C₃H₅)₂]⁺[Cu₄Cl₅]^– (I), [C₄H₈ONH(C₃H₅)]⁺[CuBr₂]^– (II), and [C₄H₈ONH(C₃H₅)]⁺[CuBr_1.41Cl_0.59]^– (III) were prepared for the first time by ac electrochemical synthesis from mono- and di-N-allyl derivatives of morpholinium and copper(I) halides in ethanol solution and structurally characterized. In the structure of I π-complex, the centrosymmetric Cu₈Cl₁₀ fragments are associated into layers perpendicular to the b axis. The N,N"-diallylmorpholinium cation functions as a bridge, which coordinates two copper atom of the adjacent inorganic fragments by both allyl groups. The trigonal-pyramidal surrounding of the Cu(I) atom, as well as the distorted tetrahedral coordination sphere of Cu(2), involves three chlorine atoms and the C=C bond, whereas the planar trigonal surrounding of the Cu(3) atom and trigonal-pyramidal surrounding of the Cu(4) atom involve only chlorine atoms. In the isostructural II and III σ-complexes, the edge-shared CuX₄ tetrahedra form the infinite copper-halide chains running along the a axis. The inorganic fragments and organic N-allylmorpholinium cations are united into the three-dimensional crystal structures by N–H···X and C–H···X (X = Cl, Br) hydrogen bonds.     

Nieuwland's cuprocatalytic reaction in terms of crystal chemical analysis

Crystallochemical treatment of the Nieuwland reaction is carried out on the basis of structural data obtained for crystalline acetylene complexes of the formulas NH₄Cu₈Cl₉·4C₂H₂·1/2HCu₂Cl₃·H₂O (I), NH₄Cu₃Cl₄·C₂H₂ (II), KCu₈Cl₉·4C₂H₂·1/2HCu₂Cl₃·H₂O (III), KCu₃Cl₄·C₂H₂ (IV), (NH₄)₂Cu₃Cl₅·4/9H₂O·(xC₂H₂) with x=0 (Va), 1/9 (Vb), and 4/9 (Vc) and divinylacetylene (DVA) copper chloride compounds 2CuCl·DVA (VI) and 3CuCl·DVA (VII). Because of the π-coordination of a copper atom, the C≡C bond of the acetylene molecule is activated, as indicated by its significant (up to 1.32 Å) stretch (complexes I and II). The zeolite-like structure of complexes Va-Vc, which form in a catalytic solution, is realized as an infinite {[Cu₁₀₈Cl₁₆₈(H₂O)₁₆]^60?}_n anion with discrete [Cl(NH₄)₆]⁵⁺ cations inside. In this structure, only 16 Cu(1) atoms have a trigonal-pyramidal environment with the oxygen atom of the crystallization water located in the vertex (d_Cu?O=2.79 Å). Under the liquid-phase conditions of the Nieuwland reaction, these copper atoms are active centers stimulating the reaction to the subsequent acetylene oligomerization due to the π-interaction with the C₂H₂ molecule. The mutual arrangement of the catalytically active Cu(1) atoms in structure Va serves as a matrix for the synthesis of DVA, as shown by the structure of the 2CuCl·DVA adduct.     

Supramolecular Assemblies of Mononuclear and Polymeric Nickel(II) Glutarato Complexes via π‐π Stacking Interactions and Hydrogen Bonds: [Ni(H2O)3(phen)(C5H6O4)] · H2O and [Ni(H2O)2(phen)(C5H6O4)]

Syntheses of the sky blue complex compounds [Ni(H₂O)₃(phen)(C₅H₆O₄)] · H₂O ( 1 ) and [Ni(H₂O)₂(phen)(C₅H₆O₄)] ( 2 ) were carried out by the reactions of 1,10‐phenanthroline monohydrate, glutaric acid, NiSO₄ · 6 H₂O and Na₂CO₃ in CH₃OH/H₂O at pH = 6.9 and 7.5, respectively. The crystal structure of 1 (P 1 (no. 2), a = 14.289 Å, b = 15.182 Å, c = 15.913 Å, α = 67.108°, β = 87.27°, γ = 68.216°, V = 2934.2 ų, Z = 2) consists of hydrogen bonded [Ni(H₂O)₃‐ (phen)(C₅H₆O₄)]₂ dimers and H₂O molecules. The Ni atoms are octahedrally coordinated by two N atoms of one phen ligand, three water O atoms and one carboxyl O atom from one monodentate glutarato ligand (d(Ni–N) = 2.086, 2.090 Å; d(Ni–O) = 2.064–2.079 Å). Through the π‐π stacking interactions and intermolecular hydrogen bonds, the dimers are assembled to form 2 D layers parallel to (0 1 1). The crystal structure of 2 (P2₁/n (no. 14), a = 7.574 Å, b = 11.938 Å, c = 18.817 Å, β = 98.48°, V = 1682.8 ų, Z = 4) contains [Ni(H₂O)₂(phen)(C₅H₆O₄)_2/2] supramolecular chains extending along [010]. The Ni atoms are octahedrally coordinated by two N atoms of one phen ligand, two water O atoms and two carboxyl O atoms from different bis‐monodentate glutarato ligands with d(Ni–N) = 2.082, 2.105 Å and d(Ni–O) = 2.059–2.087 Å. The supramolecular chains are assembled into a 3 D network by π‐π stacking interactions and interchain hydrogen bonds. A TG/DTA of 2 shows two endothermic effects at 132 °C and 390 °C corresponding to the complete dehydration and the lost of phen.     

Synthese und Kristallstruktur von Ammin(μ3‐L‐glutamato)kupfer(II)

Synthesis and Crystal Structure of Ammine(μ₃‐L‐glutamato)copper(II) [Cu(L‐Glu)H₂O]·H₂O reacts with aqueous ammonia to give the ammine complex [Cu(L‐Glu)NH₃] ( 1 ). 1 forms orthorhombic crystals, space group P 2₁2₁2 with a = 1585,1(1) pm; b = 979,46(7) pm and c = 504,70(5) pm. In the crystal structure of 1 the copper atoms are linked by μ₃‐glutamate units to give a 2D layer structure. The copper atoms exhibit a square‐pyramidal coordination with two N atoms and two O atoms in the base plane and one O atom at the apex of the pyramid. The crystal structure is stabilized by a 3D network of N–H···O hydrogen bridges.