The influence of the nature of the solvent on the crystal structure and the character of formation of hydrogen bonds inN′-(5-nitrofurfurylidene)isonicotinehydrazide

N(5-Nitrofurfurylidene)isonicotinehydrazide (1) was synthesized in the reaction of nicotinic acid hydrazide with 5-nitrofurfurol in anhydrous or aqueous ethanol. Crystals of different shape and color were obtained depending on the conditions of synthesis and the nature of the solvent. As was established by IR spectroscopy, compound1 in the crystalline state forms solvates of various types. An X-ray study of two different crystals, one obtained by recrystallization from methanol (1a), and the other obtained from aqueous acetic acid (1b), was performed. In the crystal structure of1a intermolecular hydrogen bonds (IMHB) of the NH...N(Py) type occur; the crystals1b are built of solvates with one molecule of acetic acid in which the components are bonded by the IMHB (Ac)O-H..N(Py). The solvates are linked in an infinite chain by the amidohydrate IMHB C=O...W...H-N.Translated fromlzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 2263–2268, September, 1996.     

Synthesis and crystal structure of 2′-(3,5-dioxo-1,2,4-triazinane-1-yl)acetic acid and the product of its reaction with copper(II) chloride

A new organic compound, 2-(3,5-dioxo-1,2,4-triazinane-1-yl)acetic acid, was prepared by transit template synthesis, and its crystal structure was determined. The ability of this compound to form stable metal complexes, where it acts as an N,O-chelating ligand, was demonstrated using its Cu(II) compound as an example.Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 3, 2005, pp. 187–194.Original Russian Text Copyright © 2005 by Filippova, Bologa, Simonov, Gdaniec, Gerbaleu.This revised version was published online in April 2005 with a corrected cover date.This revised version was published online in April 2005 with a corrected cover date.     

Synthesis and crystal structure of trans-dichloro(1,3-propylenediamine-n,n′-diacetato)platinum(IV) monohydrate

The trans-geometrical isomer of the first Pt(IV) complex with the tetradentate ligand 1,3-propylenediamine-N,N′-diacetate ion (pdda) was prepared by a direct synthesis from potassium hexachloroplatinate(IV) and pdda in the presence of lithium hydroxide. The crystal structure of trans-[Pt(pdda)Cl₂]·H₂O complex has been determined. The Pt(IV) ion has a distorted octahedral coordination due to intramolecular N–H···Cl interactions.     

Molecular and crystal structure of 4,5,4′,5′-tetrahydro-2,2′-(1,4-phenylene)bisoxazoline

4,5,4,5-Tetrahydro-2,2-(1,4-phenylene)bisoxazoline, which is one of the most promising stabilizers-consolidators of heterochain polymers, was studied by X-ray structural analysis.Deceased.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2506–2507, October, 1996.     

Molecular and crystal structure of 2,3-dimethyl-5-(2′-methylprop-1′-enyl)-6-(morpholyl-4′-carbonyl)-cyclohex-3-en-1-carboxylic acid

An X-ray structural examination is carried out for 2,3-dimethyl-5-(2′-methylprop-1′-enyl)-6-(morpholyl-4′-carbonyl)-cyclohex-3-en-1-carboxlic acid that is one of the products of the Diels-Alder reaction of an acyclic monoterpene alloocimene with maleic and citraconic anhydrides followed by the ring opening of adducts with morpholine to corresponding amides. The crystals are triclinic; a = 10.619(1) ?, b = 12.784(2) ?, c = 14.328(2) ?; α = 65.752(1)°, β = 87.932(1)°, γ = 78.120(1)°; V = 1733.0(3) ?³, P-1 space group, Z = 4 (two independent molecules). In both molecules, the anti-conformation of the carboxylic group is observed, the conformation being stabilized by an intramolecular hydrogen bond involving the carboxylic hydrogen atom and ketonic oxygen.     

Preparation ofN-chloroacetyl-N′-arylsulfonylureas and the crystal structure ofN-chloroacetyl-N′-(4-methylphenylsulfonyl)urea

Novel arylsulfonylureas were prepared by the reaction of chloroacetyl isocyanate with arylsulfamides. The structures of the compounds synthesized were determined by IR and¹H NMR spectra. An X-ray structural analysis ofN-chloroacetyl-N-(4-methylphenylsulfonyl)urea was carried out. It was found that the molecule has theanti-syn conformation stabilized by an intramolecular H-bond. In the crystal, the molecules are combined into centrosymmetrical dimers by intermolecular hydrogen bonds. The compounds considered exhibit moderate fungicide activity.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1786–1788, October, 1994.     

The crystal structure of the inclusion complex of cyclomaltoheptaose (β-cyclodextrin) with 3,5-dimethylbenzoic acid

The crystal of theCD-3,5-dimethylbenzoic acid inclusion complex is triclinicP1 witha=15.707(3),b=15.694(3),c=15.999(3) Å, =101.502(5),=101.557(5), =103.805(4)°,V=3624 ų, andZ=1. Two crystallographically independentCD molecules form a dimer by means of hydrogen bonds between secondary hydroxyl groups in which disordered guest molecules in six orientations are accommodated. In two of them the guest molecules are situated at the dimer interface, their carboxyl groups interacting with the carboxyl groups of two other guest orientations that are found on either side of the monomer cavity. In the two last orientations the guest molecules enter the monomer cavities in an opposite sense with the carboxyl groups protruding from the primary side and are stabilized by cyclodextrin hydroxyl groups. A dense water network is formed in the interdimer space consisted of 18.2 water molecules distributed over 24 sites. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82175 (61 pages).Dedicated to Professor József Szejtli.     

Synthesis and crystal structure of cyclotris-(4,4′-thiodiphenylene ketone)

The side reaction of macrocyclization that occurs during the synthesis of poly-(1,4-phenylenesulfide ketone) by polycondensation of a 4,4-dihalobenzophenone with sodium sulfide was studied. It was found that the major product of this reaction is a cyclic trimer, cyclotris-(4,4"-thiodiphenylene ketone) (1). Despite the fact that ketone bridges are more rigid than sulfide bridges, the yield of the macrocycle is rather high, as it is in the synthesis of poly-(1,4-phenylenesulfide), and reaches 20% under high dilution conditions. The structure of 1 was investigated by X-ray diffraction analysis (R = 0.069 on 3138 reflections). Macrocycle 1 is strongly flattened in the crystal; the conformation observed is determined by the packing, since stereochemical analysis indicates high flexibility of the macrocycle. The solvate acetone molecules incorporated in the crystal are disordered, nevertheless, they are strongly fixed in the cavities and channels of the crystal structure.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1460–1466, August, 1994.     

Synthesis and functionalization oftrans-2-(2′-aminocyclohexyloxy)-andtrans-2-(2′-azidocyclohexyloxy)acetic acid

Summary Synthesis of the hydrochloride oftrans-2-(2-aminocyclohexyloxy)acetic acid (4) fromtrans-2-(2-azidocyclohexyloxy)acetic acid (1) is described.4 was acylated at the amino group to give compounds5–8.1 was converted into acid chloride (9) and amides10–13.

---

Synthese und Funktionalisierung dertrans-2-(2-Aminocyclohexyloxy)- undtrans-2-(2-Azidocyclohexyloxy)essigsäure

Zusammenfassung Die Synthese destrans-2-(2-Aminocyclohexyloxy)essigsäurehydrochlorids (4), ausgehend vontrans-2-(2-Azidocyclohexyloxy)essigsäure (1), wird beschrieben.4 wurde durch Acylierung der Aminogruppe in die Verbindungen5–8 übergeführt.1 wurde in das Säurechlorid9 und die Carbonsäureamide10–13 umgewandelt.

     

Synthesis and crystal structure determination of the triflate salt of diacetonitrile(2,2′-bipyridine)platinum(II)

Reaction of [Pt(bipy)Cl₂] (bipy = 2,2′-bipyridine) with an excess of silver triflate in refluxing acetonitrile readily affords [Pt(bipy)(MeCN)₂](CF₃SO₃)₂ as a yellow, crystalline solid. A single crystal X-ray diffraction study shows that the cations are arranged in a zig-zag manner in rows parallel to the b axis of the monoclinic unit cell. Consideration of the crystal structures of related bipyridyl ligand complexes of platinum(II), leads to the conclusion that a stacked structure with intermolecular Pt…Pt interactions for the title compound is prevented by the electrostatic repulsion between adjacent cations that are doubly charged.     

Synthesis and crystal structure of the lithium perrhenate monohydrate LiReO4·H2O

A new monohydrate of lithium perrhenate LiReO₄·H₂O was prepared by dehydration of LiReO₄·1.5H₂O at room temperature. The single crystals of LiReO₄·H₂O were obtained by crystallisation from the isoamyl acetate solution of LiReO₄·1.5H₂O. The structure of monohydrate (a=5.6674(4), b=10.771(1), c=7.4738(7) Å, β=102.422(7)°, R₁=0.0414, space group P2₁/a, Z=4) is built up from LiO₃(H₂O)₂ trigonal bipyramids and ReO₄ tetrahedra sharing common edges and corners inside the layers. The layers are connected together by hydrogen bonds. The relationships between the structures of sesquihydrate, monohydrate and anhydrous LiReO₄ are discussed.     

Synthesis and crystal structure of (2.2.2-cryptand)(nitrato-O,O’)lead(II) nitrate monohydrate

A new complex, (2.2.2-cryptand)(nitrato-O,O’)lead(II) nitrate monohydrate [Pb(NO₃)(Crypt-222)]⁺ · NO ₃ ^? · H₂O, is synthesized and characterized by X-ray crystallography. The structure of the complex (space group Pbca, a = 14.196 Å, b = 14.001 Å, c = 26.745 Å, Z = 8) is solved by direct methods and refined by the full-matrix least-squares method in the anisotropic approximation to R = 0.073 for 3474 unique reflections (CAD4 automated diffractometer, λMOK _α). The structure contains the host-guest complex cation [Pb(NO₃)(Crypt-222)]⁺. The Pb²⁺ cation is located in the cavity of the 2.2.2-cryptand ligand and is coordinated by all eight heteroatoms (6O + 2N) of the cryptand ligand and two O atoms of the NO ₃ ^? ligand. The coordination polyhedron of the Pb²⁺ cation (ten-coordinate) is a strongly distorted hexagonal bipyramid with a base of four O atoms and two N atoms of the cryptand ligand and with two bifurcated axial vertices at two O atoms of the nitrate ligand and two O atoms of the cryptand ligand. The disordered NO ₃ ^? anion and the water molecule are linked by hydrogen bonds.     

Solvent-dependent conformational polymorphism in the crystal structure of mercuric bromide adduct of 1,1′-bis(diphenylphosphino)ferrocene

Two polymorphs of dinuclear mercury–iron complexes, [HgBr₂(dppf)] (1) where dppf is 1,1′-bis(diphenylphosphino)ferrocene, are prepared and crystal structures are determined by X-ray crystallography. The reaction of mercury(II) bromide with dppf in methanol–dichloromethane led to orange block polymorph. After crystallization of this complex in DMSO, a red needle polymorph was obtained.     

Molecular structure of 2,3-(4′-phenylacetyl)- and 2,3-(4′-diphenylacetyl)-benzo-15-crown-5

The conformational state of two benzo-crown ethers with substantially different physiological activity, 2,3-(4-phenylacetyl)- and 2,3-(4-diphenylacetyl)benzo-15-crown-5, was studied in crystals and solutions in CH₃CN and CCl₄ by x-ray crystallographic analysis, IR spectroscopy, and conformational calculations by the method of molecular mechanics. Transition from the crystalline state to solutions was found to be accompanied by a substantial change in the conformation of the macrocyclic ring of all the compounds studied. The nature of the substituent in the benzene ring and the polarity of the solvent have an influence on the conformational state of the macrocyclic ring of the free ligand, which, however, is not the determining factor in the change in the activity of the compounds. The COCCOC fragments of the macrocyclic framework are conformationally labile, readily passing from gauche to trans conformations and the reverse, which is promoted by the negligible energy barriers between the different conformations, determined in the work by a molecular mechanics method.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1819–1825, August, 1991.     

The crystal structure of the “A(NbAlIr)” phase

The identity of the “A(NbAlIr)”-phase [1] crystal structure with that of the MgZn₂-Laves C-14 type has been confirmed (space group P6₃/mmc).The atomic positions, Isotropic temperature factors and corresponding standard deviations have been determined.The discrepancy factor, R, obtained for the 0kl, 1kl, 2kl, 3kland 4kl layers has an average value of 0.1324.     

Synthesis,crystal structure,thermal decomposition,and explosive properties of [Bi(tza)3] n (tza = tetrazole acetic acid)

A coordination compound based on tetrazole acetic acid (Htza) and bismuth(III), [Bi(tza)₃] _n , was synthesized and characterized by single crystal X-ray diffraction analysis, elemental analysis, FT-IR, and ¹H NMR spectroscopy. The crystallographic data show that the crystal belongs to monoclinic, P2₁/n space group, a?=?0.91968(19)?nm, b?=?0.94869(19)?nm, c?=?1.7824(4)?nm, β?=?101.488(3)°, and Z?=?4. The central bismuth(III) is nine-coordinate by three nitrogens from three tetrazole rings and six oxygens of the carboxylate of another three tza^? ions, with each tza^? tridentate, chelating, bridging coordination. The coordination bonds and the intramolecular hydrogen bonds make the complex pack into a layered structure in polymer form. The thermal decomposition mechanism of the title complex was investigated by DSC and TG-DTG techniques. Under nitrogen at a heating rate of 10°C?min^?1, thermal decomposition of the complex contains two intense exothermic processes between 217.4°C and 530.3°C in the DSC curve; the final decomposed residue at 570°C was Bi₂O₃. Sensitivity tests showed that [Bi(tza)₃] _n was sensitive to impact and flame stimulus.