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The Li1.746Nd4.494FeO9.493 (LNF) ternary phase, located in the Li2O-rich part of the Li2O–Nd2O3–Fe2O3 system, crystallizes with a cubic unit cell of dimension a = 11.9763 ( 3 ) A and the space group Im 3 m . Refinement on F resulted in R = 1.9 % . The structure is comprised of a network of corners, edges and faces sharing the coordination polyhedra of neodymium. In between this skeleton the regular octahedra of oxygen-coordinated iron and trigonal prisms of lithium are located. The Mossbauer spectra revealed the presence of Fe3+, Fe4+ and Fe5+ ions distributed on two symmetry-independent lattice positions.

Di- O -isopropylidene- and O -methanesulfonyl-protected 1- C -(6-chloro-1,2,4-triazolo[4,3- b ]pyridazin-3-yl)pentitols were prepared in three to four steps from d -galactose, d -glucose, d -mannose, and 2,3:5,6-di- O -isopropylidene-α- d -mannofuranose. Acid-catalysed treatment of (1 S )- and (1 R )-1- C -(6-chloro-1,2,4-triazolo[4,3- b ]-pyridazin-3-yl)-2,3:4,5-di- O -isopropylidene-1- O -methanesulfonyl- d -arabinitols in refluxing 1,2-dimethoxyethane furnished 3-(α- and β- d -arabinofuranosyl)-6-chloro-1,2,4-triazolo[4,3- b ]pyridazine, respectively. Several structures, including the structure of the 3-(β- d -arabinofuranosyl)-6-chloro-1,2,4-triazolo[4,3- b ]pyridazine, were also determined by single-crystal X-ray diffraction analysis.

Cycloadditions of various 1,3-dipoles to methyl (S)-1-tert-butoxycarbonyl-3-[(E)-cyanomethylidene]-2-pyrrolidinone-5-carboxylate (9) were studied. Reactions of 9 with diazomethane (10) and 2,4,6-trimethoxy-benzonitrile oxide (11), carried out under neutral conditions, gave the corresponding optically active spiro compounds 16-18 with low diastereoselectivity (20-30% diastereomeric excess). On the other hand, reactions of 9 with nitrile oxide 11 and nitrile imines 14, 15, carried out in the presence of a base, afforded racemic pyrazolo and isoxazolo fused 2-pyrrolidinones 21-23 in 82-86% diastereomeric excess. Optically active dipolarophile 9 was isomerized in the presence of basic alumina to give methyl (RS)-1-tert-butoxy-carbonyl-3-cyanomethyl-1,2-dihydro-2-oxo-5H-pyrrole-5-carboxylate (19). Treatment of the racemic dipolarophile 19 with dipoles 11 and 14, afforded fused 2-pyrrolidinones 23 and 21. These observations support compound 19 as the key-intermediate in the formation of racemic cycloadducts 21-23.

Dedicated to Professor Emeritus Miha Tisler on the occasion of his 75th birthday Treatment of methyl (S)-5-[(E)-(dimethylamino)methylidene]-2-oxotetrahydrofuran-5-carboxylate (2) with potassium cyanide in acetic acid gave (S)-5-[(E)-cyanomethylidene]-2-oxotetrahydrofuran-5-car-boxylate (3), which was used as chiral dipolarophile in 1,3-dipolar cycloadditions. Reactions of 3 with diazomethane (4) and nitrile oxides 5a-c afforded spirolactones 6–8 in 24-34% diastereomeric excess, while with diazomethane (4) in the presence of triethylamine, methyl 3-cyanomethyl-2-methoxyfuran-5-carboxylate (12) was obtained.

Some new aplysinopsin analogues were prepared by a simple coupling of N , N -(dimethylamino)methylidene substituted hydantoin, thiohydantoin, and thiazolone derivatives, with indole derivatives. Configuration around the exocyclic CC double bond was determined on the basis of long-range heteronuclear coupling constants using 2D HMBC correlation technique.

The 5,5-dimethylpyrazolidin-3-one (4), prepared from ethyl 3-methylbut-2-enoate (3) and hydrazine hydrate, was treated with various substituted benzaldehydes 5a – i to give the corresponding (1Z)-1-(arylmethylidene)-5,5-dimethyl-3-oxopyrazolidin-1-ium-2-ide azomethine imines 6a – i. The 1,3-dipolar cycloaddition reactions of azomethine imines 6a – h with dimethyl acetylenedicarboxylate (=dimethyl but-2-ynedioate; 7) afforded the corresponding dimethyl pyrazolo[1,2-a]pyrazoledicarboxylates 8a – h, while by cycloaddition of 6 with methyl propiolate (=methyl prop-2-ynoate; 9), regioisomeric methyl pyrazolo[1,2-a]pyrazolemonocarboxylates 10 and 11 were obtained. The regioselectivity of cycloadditions of azomethine imines 6a – i with methyl propiolate (9) was influenced by the substituents on the aryl residue. Thus, azomethine imines 6a – e derived from benzaldehydes 5a – e with a single substituent or without a substituent at the ortho-positions in the aryl residue, led to mixtures of regioisomers 10a – e and 11a – e. Azomethine imines 6f – i derived from 2,6-disubstituted benzaldehydes 5f – i gave single regioisomers 10f – i.

Ethyl (Z)-2-(2,3-dihydro-1,3-dioxo-1H-isoindol-2-yl)-3-(dimethylamino)propenoate was prepared in one step from ethyl (2,3-dihydro-1,3-dioxo-1H-isoindol-2-yl)acetate and bis(dimethylamino)-tert-butoxymethane and treated with various amines and hydrazines to afford the corresponding amino substituted products. Reactions of the titled compound with N,N'-, C,N-, and C,O'-ambident nucleophiles in refluxing acetic acid furnished the corresponding fused pyrimidinones, quinolizinones, and pyranones.

Simple and stereoselective syntheses of aplysinopsins and their analogs from either methyl 2-[(2,2-disubstituted ethenyl)amino]-3-(dimethylamino)prop-2-enoates 11 or 5-[(dimethylamino)methylidene]imidazolidine-2,4-diones 20 are described. The structures of products are established by 1H- and 13C-NMR, and NOESY spectroscopy, and X-ray crystal-structure analysis.

(PyH)2[MoOCl5] reacts with methanol and pyridine or 4-methylpyridine to give neutral oxomolybdenum(V) and oxomolybdenum(V,VI) clusters built of Mo2O4 2+ units, i.e. tetranuclear [Mo4O8(OCH3)2Cl2Py4]·2Py (Py=pyridine (C5H5N)) (i), [Mo4O8(OCH3)2Cl2(4-MePy)4]·2(4-MePy) (4-MePy=4-methylpyridine (C6H7N)) (ii), [Mo4O8(OCH3)4(4-MePy)4] (iii), hexanuclear [Mo6O12(OCH3)6Py4] (iv) and decanuclear [Mo10O26Py8]·7Py (v). It was shown by the X-ray structure analysis that i and iii contain the same [Mo4O4(μ2-O)2(μ3-O)2(μ2-OCH3)2]2+ core to which different peripheral ligands are attached. The structure of ii is analogous to that of i, based on the similarity of infrared and far infrared spectra. Molecules of iv were shown to contain a planar arrangement of six molybdenum atoms linked together by oxo and methoxo bridging groups. The X-ray structure analysis of v revealed the presence of molybdenum(V) and molybdenum(VI) atoms. Neutral, decanuclear molecules of v are built of four Mo2O4 2+ units which are connected with two molybdenum(VI) centres.

Reactions of (PyH)2[MoOCl5] with methanol and 3,5-lutidine or 3-methylpyridine carried out under conditions of solvothermal synthesis at 130°C have resulted in two Mo(V, VI) clusters containing the same molybdenum oxide framework, [Mo10O26(3,5-Lut)8]·2(3,5-Lut) (3,5-Lut=3,5-lutidine (C7H9N)) (i) and [Mo10O26(3-MePy)8]·(3-MePy) (3-MePy=3-methylpyridine (C6H7N)) (ii), and in a novel [Mo12O28(OCH3)2Cl2(3-MePy)8] (iv). [Mo10O26(3-MePy)8] (iii) was also obtained by oxidizing (NH4)2[MoCl5(H2O)] in a mixture of methanol, 3-methylpyridine and nitromethane. X-ray structural analyses revealed Mo2O4 2+ unit as a common structural motif in both cluster types. In i–iii ten molybdenum atoms are grouped into four Mo2 V pairs with MoMo bonds and two Mo(VI) sites. The oxomolybdenum core of iv is composed of six Mo2 V pairs connected through oxo and methoxo bridges.

Simple synthetic routes for the preparation of octanuclear oxomolybdenum(V) clusters with stoichiometry [Mo8O16(OCH3)8L4] (L=4-methylpyridine (4-MePy) (a), 4-ethylpyridine (4-EtPy) (b), 4-tert-butylpyridine (4-ButPy) (c), pyridine (Py) (d), 3-methylpyridine (3-MePy) (e), 3,5-lutidine (3,5-Lut) (f)) are described. Crystal structures of e and f were investigated by X-ray diffraction. The puckered ring structure made up of eight molybdenum atoms linked together by pairs of methoxy groups and pairs of oxo groups was recognized in both. The solubility of the compounds in pyridines was employed for the substitution of coordinated pyridine for a different pyridine. The octanuclear clusters have been found to react in pyridines at elevated temperatures to oxomolybdenum(V,VI) clusters with the formula [Mo10O26L8].

Complexes of [LnCl3L] (Ln=La, Nd, Sm, Eu, and L=diethylene glycol dimethyl ether, diglyme; Ln=La, Pr, and L=dimethoxyethane, DME) were prepared from the lanthanide oxides and hydrogen chloride, which was formed in situ from chlorotrimethylsilane and water. When hexamethylphosphoramide (HMPA) was added to the suspension of the prepared DME and diglyme complexes in toluene, fac-[LnCl3(HMPA)3] (Ln=La, Pr, Nd, Sm, Eu, Gd) complexes, isomorphous according to the unit cell determination, were formed. The crystal structure of [SmCl3(HMPA)3] was determined. Each samarium atom is octahedrally coordinated by three chlorine atoms and three HMPA molecules, which are distributed in a facial mode. The exchange of coordinated and free HMPA, as well as the reversible fac–mer isomerization of [LaCl3(HMPA)3], was observed by variable temperature 1H NMR spectroscopy. The associative mechanism of the exchange and isomerization was proposed.

Crystals of (NH3OH)2TiF6ċ2H2O have been isolated. The compound crystallizes in the monoclinic system (P21/c, No. 15) with cell parameters of a=6.203(1) A, b=10.057(1) A, c=7.464(1) A, and β=110.653(6)°. Reactions in the system In (OH)3– NH3OHF – HF have been investigated. Crystals of (NH3OH)3InF6 were isolated from aqueous solution. The compound crystallizes in the trigonal system (R3c) with a=b=c=7.764(2) A, α=β=γ=97.21(4)°. The thermal decomposition of both compounds was studied by TG and DSC analysis; the decomposition products were characterized by X-ray powder diffraction.

Complexes of [LnCl3(dme)2] (Ln=Sm, Gd; dme=dimethoxyethane)were prepared in dimethoxyethane solution from the lanthanide oxides and hydrogen chloride, which was formed in situ from chlorotrimethylsilane and water. The recrystallization of[LnCl3(dme)2] from tetrahydrofuran in the presence of tetramethylethylenediamine (tmeda) resulted in [LnCl3(thf)2(tmeda)] (Ln=Sm,Gd). The samarium and gadolinium complexes were found to be isomorphous by unit cell determination. Each seven-coordinated gadolinium atom adopts a distorted pentagonal bipyramidal geometry with chlorine atoms in axial positions. The thermal decomposition of the compounds in argon resulted in LnOCl.

4(R)-(6-Chloro-s-triazolo[4,3-b]pyridazinyl-3)-1,4-furanoses 10 and 11, 5(R)-(6-chloro-s-triazolo[4,3-b]pyridazinyl-3)-1,5-pyranose 13, and 2(S),3(R)-dihydro-5-(6-chloro-s-triazolo[4,3-b]pyridazinyl-3)-2,3-O-isopropylidenefuran (12) were prepared by cyclization of hydrazones 6–9 obtained from 6-chloro-3-hydrazinopyridazine (1) and aldofuranoses 2, 3 and 4, and aldopyranose 5.

The recrystallization of [{Ti(C5Me5)F3}4CaF2] 1 and [{Ti(C5Me4Et)F3}4CaF2] 2 in the presence of an excess of hmpa (hexamethylphosphoramide) resulted in the formation of [{Ti(C5Me5)F3}4(CaF2)(hmpa)] 3 and [{Ti(C5Me4Et)F3}4(CaF2)(hmpa)] 4, respectively. The adducts 3 and 4 were spectroscopically characterized and the molecular structure of 4 was determined, showing a co-ordination of calcium by eight fluorine atoms from two [Ti2(C5Me4Et)2F7]– moieties and by an oxygen atom of an hmpa ligand. Adduct formation and solution behavior of 2 in different solvents was studied by 1H and 19F NMR and variable-temperature NMR. A temperature dependent equilibrium between 2 and a solvated form 2·solv (solv = solvent molecule) is proposed. With increase of the temperature the equilibrium between 2 and 2·solv was observed to be entropy-shifted to the non-solvated form.

The synthesis of ethyl 2-(2-acetyl-2-benzoyl-1-ethenyl)amino-3-dimethylarninopropenoate (4) from benzoylacetone (1) via 3-dimethylarninomethylenebenzoylacetone (2) and ethyl N-(2-acetyl-2-benzoyl-1-ethenyl)glycinate (3) and its transformation into 4-benzoyl-2-ethoxycarbonyl-3-methylpyrrole (9) is described. Cyclization of 4 into 9 represents a new synthesis of polysubstituted pyrroles.

Alkyl (E,Z)-2-(2-benzoyl-2-ethoxycarbonyl-1-ethenyl)amino-3-dimethylaminopropenoates 1a,b react with het-eroarylamines 2 to give alkyl 2-(2-benzoyl-2-ethoxycarbonyl-1-ethenyl)amino-3-heteroarylaminopropenoates 3-13. These were cyclized into fused 3-(2-benzoyl-2-ethoxycarbonyl-1-ethenyl)amino-4H-azolo- (or azino)-pyrim-idin-4-ones 14-18. 2-Benzoyl-2-ethoxycarbonyl-1-ethenyl group can be easily removed from 3-(2-benzoyl-2-ethoxycarbonyl-1-emenyl)amino-8-memyl-4H-pyrido[1,2-a]pyrimidin-4-one (14) to give 3-amino-8-methyl-4H-pyrido[1,2-a]pyrimidin-4-one (19). The structure of 1a was confirmed by X-ray analysis.

Open-chain C-nucleosides, 1-(s-triazolo[4,3-x]azinyl-3)polyols 13–18 were prepared by one-pot synthesis from hydrazinoazines 20a,c and various D-aldoses 1–6. No protective groups were required for these transformations. 1-(s-Triazolo[4,3-b]pyridazinyl-3)-D-xylo-tetritol (15a) was isolated and characterised in the form of its 4-O-triphenylmethyl derivative 19. Reaction of hydrazinopyridazines 20a,b with methyl 2,3-di-O-acetyl-L-threuronate (22), followed by treatment with bromine, gave the corresponding (2R,3S)-2,3-diacetoxy-3-(s-triazolo[4,3-b]pyridazinyl-3)propanoic acid methyl esters 24a,b. Acetonisation of 1-(6-chloro-s-triazolo[4,3-b]pyridazinyl-3)-D-gluco-pentitol (17a) gave a mixture of isomeric bis-acetonides 25 and 26, while acetonisation of 1-(6-chloro-s-triazolo[4,3-b]pyridazinyl-3)-D-manno-pentitol (18a) gave acetonide 27 as a single isomer.

Reaction of rel-(4R,5R)-4-benzoylamino-5-phenyl-3-pyrazolidinone (4) with aromatic aldehydes 5a-f gave the corresponding (1Z)-rel-(4R,5R)-1-arylmethylene-4-benzoylamino-5-phenyl-3-pyrazolidinon-1-azomethinimines 6a-f. 1,3-Dipolar cycloadditions of azomethinimines 6a-f to various dipolarophiles, which were found to proceed regio- and stereo-selectively, afforded the corresponding pyrazolo[1,2-a]-pyrazoles 8a-f, 10, and 13–16. Reaction of azomethinimine 6a with hydrogen cyanide gave rel-(5R,6R)-6-benzoylamino-5,6-dihydro-3,5-diphenyl-1-oxo-1H,7H-pyrazolo[1,2-a][1,2,3]triazole (18) as a representative of a new ring system.

Cobalt-containing aluminophosphate AlPO 4 -CJ2 was hydrothermally synthesized and characterized using single crystal X-ray diffraction. It was shown to possess 7.2(3) % of isomorphously substituted cobalt in a 5-coordinate Al framework site and a 4-coordinated extra-framework Co (II) ion in a distorted square-planar arrangement with one terminal fluoride atom and three framework oxygen atoms (7.2(3)% occupancy). The Co incorporation does not change the cell parameters significantly ( a = 9.444(1), b = 9.588(1), c = 9.928(1)A). The orthorhombic P2 1 2 1 2 1 symmetry found for the Co-free analogue is also retained.

In connection with our studies on potential bioactive compounds some new polysubstituted 3-thiocarbamoylthiazolidines 5, 6, 7, 9 and 10 were prepared in the reaction between 2-(2-methoxy-phenyl)iminothiazolidine (2) and sulfamoylphenyl isothiocyanates 3 and 4a-c. The structures for compounds 2 and 5 were established by X-ray analyses, showing that the reaction is taking place at the endo-cyclic nitrogen atom of thiazolidine ring.

Die Losungen thiooxalatverbruckter Zweikernkomplexe mit terminalen Triphenylphosphanliganden sind lichtempfindlich und zersetzen sich uberwiegend unter Zerfall des Thiooxalato-Bruckenliganden. μ-1,1-Dithiooxala-to-bis[bis(triphenylphosphan)-kupfer(I)], [{(Ph3P)2Cu}2(i-dto)], bildet in Dichlormethan unter Verlust des Thiooxalato-Bruckenliganden den chloroverbruckten Kupfer(I)-Zweikernkomplex μ-Dichlorotris(triphenylphosphan)dikupfer(I), [(Ph3P)2CuCl2Cu(Ph3P)]. μ-Trithiooxalato-bis[bis(triphenyl-phosphan)kupfer(I)], [{(Ph3P)2Cu}2(trto)], zersetzt sich in Pyridin unter Bildung von Hydrogensulfidopyridin-bis(triphenylphosphan)kupfer(I), [(Ph3P)2 (py)CuSH]. Der gebildete Komplex kristallisiert in der triklinen Raumgrupe P1, mit dem Elementarzellenparametern a = 9,488(2) A, b = 10,472(3) A, c = 19,351 (3) A, α = 85,03(2)°, β = 86,99(2)° und γ = 68,36(2)°. Im Unterschied dazu bleibt beim entsprechenden Tetrathiooxalat-Zweikernkomplex, [{(Ph3P)2Cu}2(tto)], der Thiooxalato-Bruckenligand offensichtlich erhalten. Die angenommenen Reaktionswege konnten durch quantenchemische Berechnungen (EHT) gestutzt werden. Photolytic Reactions of Binuclear Thiooxalate Complexes – Crystal and Moleculer Structure of Hydrogensulfidopyridinebis(triphenylphosphane)copper(I) Solutions of the binuclear, thiooxalato bridged complexes with capping triphenylphosphane ligands are lightsensitive and decompose mainly with decomposition of the bridging thiooxalate. From μ-1,1-Dithiooxalatobis[bis(triphenylphosphane)copper(I)], [{(Ph3P)2Cu}2(i-dto)], in dichloromethane the binuclear copper(I) complex μ-dichlorotris(triphenylphosphane)dicopper(I), [(Ph3P)2CuCl2Cu(Ph3P)], with the total lost of the bridging thiooxalato ligand is formed. μ-Trithiooxalato-bis-[bis(triphenylphosphane)copper(I)], [{(Ph3P)2Cu}2(trto)], decomposes in pyridine with the formation of hydrogensulfidopyridinebis(triphenylphosphane)copper(I), [(Ph3P)2(py)CuSH]. This complex crystallizes in the triclinic space group P1, with the unit cell parameters a = 9,488(2) A, b = 10,472(3) A, c = 19,351(3) A, α = 85,03(2)°, β = 86,99(2)° and γ = 68,36(2)°. Contrast ngly, the bridging thiooxalate ligand in the corresponding binuclear tetrathiooxalate complex, [{(Ph3P)2Cu}2(tto)], obviously remains unchanged. The proposed reaction pathways are supported by the results of Extended Huckel Calculations.

Methyl (Z)-2-acetylamino-3-dimethylaminopropenoate (3) was prepared from N-acetylglycine (1), which was converted with N,N-dimethylformamide and phosphorus oxychloride into 4-dimethylaminomethylene-2-methyl-5(4H)-oxazolone (2), followed by treatment with methanol in the presence of potassium carbonate, into 3. The compound 3 was shown to be a versatile reagent in the synthesis of various heterocyclic systems. With N-nucleophiles, such as heterocyclic amines 4, either methyl 2-acetylamino-3-heteroarylaminopropenoates 5 or fused pyrimidinoncs 6 were formed, dependent on the reaction conditions and/or heterocyclic substituents: C-nuclcophiles with an active or potentially active methylene group, such as 1,3-dicarbonyl compounds 7, 8 and 9, substituted phenols 10a,b, naphthols 11, 12a-c, and substituted coumarin 13a, afforded substituted pyranones 20 and 22, and fused pyranones 21, 23–26. The nitrogen containing heterocycles 14–19 produced pyranoazines 27–31 and pyranoazole 32. In all of these systems the acetylamino group is attached at position 3 of the newly formed pyranone ring. The orientation around the double bond for methyl (Z)-2-(N-methyl-N-trifluo-roacetyl)-3-dimethylaminopropenoate (36) was established by X-ray analysis.

Trans,trans-[MoX2py4][MoX4py2] (X = Cl, A; Br, B; py = pyridine, C5H5N) are the side products of reaction of between (NH4)2[MoX5 · H2O] (X = Cl,Br) with pyridine diluted with methanol. Both trans,trans-[MoX2py4][MoX4py2] are monoclinic, P21/n space group, with z = 2 and: a = 12.568(1), b = 9.430(1), c = 14.952(1) A and β = 100.81(1)° (A); a = 12.551(2), b = 9.533(2), c = 15.366(2) (A) and β = 99.35(1) (B). Cations and anions are located on the symmetry centers and have eclipsed conformation of the trans located pyridine ligands. Average MoX and MoN (pyridine) bonds are; (cation) 2.41, 2.21 A (A); 2.54, 2.21 A (B); (anion) 2.44, 2.20 A (A); 2.58, 2.20 A (B). Anionic part of the compounds can be oxidised by bromine to trans-MoX4py2, which precipitates from the solution. Cation can be isolated from the solution in the form of trans-[MoX2py4]Br3 (X = Cl, Br). The compounds were also characterised by chemical analysis, infrared spectroscopy and conductivity measurements. Darstellung von trans, trans-[MoX2py4][MoX4py2], trans-[MoX2py4]Br3 und Struktur von trans, trans-[MoX2py4][MoX4py2] (X = Cl, Br; py = Pyridin) Trans,trans-[MoX2py4][MoX4py2] (A: X = Cl; B: X = Br; py = Pyridin, C5H5N) sind die Nebenprodukte der Reaktion zwischen (NH4)2[MoX5 · H2O] (X = Cl, Br) und mit Methanol verdunntem Pyridin. Beide Verbindungen kristallisieren monoclin, P21/n mit Z = 2 und A: a = 12.568(1), b = 9.430(1), c = 14.952(1) A und β = 100.81(1)°; B: a = 12.551(2), b = 9.533(2), c = 15.366(2) (A) und β = 99.35(1)°. Die Kationen und Anionen sind Symmetriezentren. Die Ebenen der trans zueinander angeordneten Pyridin-Molekule sind planparallel. Mittlere MoX- und MoN(Pyridin)-Abstande sind: (Kation) 2.41, 2.21 A (A); 2.54, 2.21 A (B); (Anion) 2.44, 2.20 A (A); 2.58, 2.20 A (B). Der anionische Teil kann mit Brom zu trans-MoX4py2 oxydiert werden. Gleichzeitig sind Kationen als trans-[MoX2py4]Br3 isolierbar. Die Verbindungen wurden auch durch die chemische Analyse, Infrarot-Spektroskopie und Konduktometrie charakterisiert.

(N2H5)3[GaF6] contains GaF63− octahedra arranged in a distorted cubic close-packed manner and linked to hydrazinium(1+) ions via N—H⋯F hydrogen bonds. (N2H6)[GaF5(H2O)] contains [GaF5(H2O)]2− octahedra arranged in a similar distorted cubic close packing manner; in addition to N—H⋯F hydrogen bonds to hydrazinium(2+) ions, these octahedra are also linked directly via O—H⋯F hydrogen bonds.

Crystals of (NH3OH)3GaF6 have been isolated from aqueous solution. The compound crystallizes triclinic, with cell parametersa=6.539(5) A,b=6.924(5) A,c=9.403(1) A, α=87.01(9)°, β=83.98(8)°, γ=70.28(8)°. The thermal decomposition was studied by TG and DSC analysis.

Hydroxylammonium fluorozirconates have been investigated. Two new microcristalline phases have been isolated from aqueous solutions: (NH3OH)2ZrF6 (1) and (NH3OH)3ZrF7 (2). The crystals were prepared by slow evaporation of the solution of NH2OH, Zr, and HF. Different compositions of the crystals were achieved by varying the molar ratios of the components. They were characterized by thermal analysis, vibrational spectroscopy, and structure (single crystal x-ray methods). (NH3OH)2ZrF6 (1) crystallizes triclinic, P\(\overline 1 \) (No.: 2),a=7.400(2),b=7.609(2),c=7.887(2) A, α=57.29(3)°, β=62.16(3)°, γ=67.83(2)°. (NH3OH)3ZrF7 (2) crystallizes triclinic, P\(\overline 1 \) (No.: 2),a=7.128(1),b=7.989(1),c=8.888(1) A, α=109.72(1)°, β=91.01(1)°, γ=104.27(1)°.

We report on the synthesis and single-crystal structure of a novel cobalt-substituted aluminophosphate. Crystal data: monoclinic, space group P2 1 c (no. 14), a = 8.593(1), b = 15.540(1), c = 7.736(1)A, β = 110.65(1)°, V = 966.7(4)A3, Z = 4, R = 0.037, and Rw = 0.029 for 2280 contributing reflections and 182 variables. Refined framework-atom bond distances and angles exhibited regular tetrahedral coordination of Al and P [dave(AlO) = 1.74(1)A, dave(PO) = 1.54(2)A] and distorted Co-centered octahedra. The Co substituted every second aluminum in the ordered AlP distribution and was coordinated to five framework oxygen atoms and to one nitrogen atom from a template ethylenediamine molecule located in an eight-member ring opening. Structure collapsed in the absence of template.

The compounds ethyl (E)-2-benzoyl-3-(dimethylamino)propenoate, C 14 H 17 NO 36 (I), ethyl (Z)-2-benzoyl-3-[(3nitrophenyl)amino]propenoate, C 18 H 16 N 2 O 5 (II), and methyl (Z)-3-[(4,6-dimethyl-2-pyrimidinyl)amino]-2[(methoxy)(methylthio)methyleneamino]propenoate, C 13 H 18 N 4 O 3 S (III), are propenoates with different substituents at the C(2) = C(3) double bond. C(2) bears benzoyl and ethoxycarbonyl groups in (I) and (II) and (methoxy)(methylthio)methyleneamino and methoxycarbonyl groups in (III), whereas C(3) is substituted with dimethylamino in (I), 3-nitrophenylamino in (II) and 4,6-dimethyl-2-pyrimidinylamino in (III). The configuration with respect to the C(2) = (3) double bond is E in (I) and Z in (II) and (III). Bulky substituents such as the benzoyl and (methoxy) (methylthio) methyleneamino groups are turned out of the best plane through the rest of molecule

Hydroxylammonium fluoride was prepared in aqueous solution by the reaction of hydroxylamine with aqueous hydrogen fluoride. The solubility in water (148.7 g/100 g) and ethanol (0.146 g/100 g), the density (1.621±0.005 g/cm3) and the metling point (97.8±2 °C) of the compound have been determined. [NH3OH]F crystallizes orthorombic, Pabc,a=6.490(1) A,b=9.799(1) A,c=13.519(2) A.

The compound methyl (1'S,8S,10S)-6-chloro-9,10-dihydro-12,12-dimethyl-10-(D-erythritol-1-yl)-8H,12H-pyrazolo[1',2':1,2]pyrazolo[4,3-d]tetrazolo[1,5-b]pyridazine-8-carboxylate, C 16 H 22 ClN 7 O 6 , (1), is an example of a new C-nucleoside. Both (1) and dimethyl (6-chloro-9,10-dihydro-12,12-dimethyl-10-phthalimidomethyl-8H,12H-pyrazolo[1',2':1,2]pyrazolo[4,3-d]tetrazolo[1,5-b]pyridazine-8,9-dicarboxylate, C 23 H 21 ClN 8 O 6 , (II), contain heterocyclic systems consisting of four condensed fused rings. In each compound, the tetrazole ring is planar to within experimental error; the pyridazine ring and the pyrazole ring, which is fused to the pyridazine ring, deviate slightly from planarity, as does the phthalimido group of (II)

The molecular structures of three substituted 3-amino-2-benzoylaminopropenoic acid derivatives, methyl (Z)-2-benzoylamino-3-dimethylaminopropenoate (A), methyl (Z)-2-benzoylamino-3-(4,6-dimethyl-2-pyrimidinylamino)propenoate (B) and N-[(Z)-2-benzoylamino-3-(4,6-dimethyl-2-pyrimidinylamino)propenoyl]-L-proline monohydrate (C), show that the configuration around the exocyclic C=C double bond is Z. The mechanisms of syntheses of (B) and (C) from (A) are confirmed as the Z configuration is preserved in the title compounds

Heterocyclic amines were acetoacetylated with 2,2,6-trimethyl-1,3-dioxen-4-one and the obtained compounds reacted on the reactive methylene group to give C-substituted products. Nitrosation, followed by reduction afforded a pyrazine derivative. Azido- or chloroacetamide were also acetoacetylated, with heterocyclic amines, the corresponding enamines were prepared and reduction of the azido group of 15 afforded compounds 22 and/or amides of substituted 3-oxobutanoic acid 23. An X-ray structural determination of compound 23a revealed that the orientation about the double bond is Z.

It was shown by some chemical transformations that β-heteroaryl-α,β-dehydro-α-amino acid derivatives 3 and 7, obtained from pyrazolone derivatives 1 or 6 and 2, exist in Z-forms. The structure of 7 was confirmed by X-ray analysis.

The molecular structures of three substituted 3-amino-2-benzoylaminopropenoic acid derivatives, methyl (Z)-2-benzoylamino-3-dimethylaminopropenoate (A), methyl (Z)-2-benzoylamino-3-(4,6-dimethyl-2-pyrimidinylamino)propenoate (B) and N-[(Z)-2-benzoylamino-3-(4,6-dimethyl-2-pyrimidinylamino)propenoyl]-L-proline monohydrate (C), show that the configuration around the exocyclic C=C double bond is Z. The mechanisms of syntheses of (B) and (C) from (A) are confirmed as the Z configuration is preserved in the title compounds

Ethyl (Z)-2-[2,2-bis(ethoxycarbonyl)vinyl]amino-3-dimethylaminopropenoate (5), a new reagent in the synthesis of heteroaryl substituted β-amino- α,β- -dehydro—amino acid derivatives and some fused hetero-cyclic systems, was prepared from ethyl N-2,2-bis(ethoxycarbonyl)vinylglycinate (3) and N,N-dimethyl-formamide dimethyl acetal (4). The substitution of the dimethylamino group in the compound 5 with heterocyclic amines produced ethyl 2-[2,2-bis(ethoxycarbonyl)vinyl]amino-3-heteroarylaminopropenoates 7a-f and, in some instances, [2,2-bis-(ethoxycarbonyl)vinyl]aminoazolo- or -azinopyrimidine derivatives 8g-k.

(N2H5)3[GaF6] contains GaF63− octahedra arranged in a distorted cubic close-packed manner and linked to hydrazinium(1+) ions via N—H⋯F hydrogen bonds. (N2H6)[GaF5(H2O)] contains [GaF5(H2O)]2− octahedra arranged in a similar distorted cubic close packing manner; in addition to N—H⋯F hydrogen bonds to hydrazinium(2+) ions, these octahedra are also linked directly via O—H⋯F hydrogen bonds.

In connection with our studies on potential bioactive compounds some new polysubstituted 3-thiocarbamoylthiazolidines 5, 6, 7, 9 and 10 were prepared in the reaction between 2-(2-methoxy-phenyl)iminothiazolidine (2) and sulfamoylphenyl isothiocyanates 3 and 4a-c. The structures for compounds 2 and 5 were established by X-ray analyses, showing that the reaction is taking place at the endo-cyclic nitrogen atom of thiazolidine ring.

Alkyl (E,Z)-2-(2-benzoyl-2-ethoxycarbonyl-1-ethenyl)amino-3-dimethylaminopropenoates 1a,b react with het-eroarylamines 2 to give alkyl 2-(2-benzoyl-2-ethoxycarbonyl-1-ethenyl)amino-3-heteroarylaminopropenoates 3-13. These were cyclized into fused 3-(2-benzoyl-2-ethoxycarbonyl-1-ethenyl)amino-4H-azolo- (or azino)-pyrim-idin-4-ones 14-18. 2-Benzoyl-2-ethoxycarbonyl-1-ethenyl group can be easily removed from 3-(2-benzoyl-2-ethoxycarbonyl-1-emenyl)amino-8-memyl-4H-pyrido[1,2-a]pyrimidin-4-one (14) to give 3-amino-8-methyl-4H-pyrido[1,2-a]pyrimidin-4-one (19). The structure of 1a was confirmed by X-ray analysis.

The synthesis of ethyl 2-(2-acetyl-2-benzoyl-1-ethenyl)amino-3-dimethylarninopropenoate (4) from benzoylacetone (1) via 3-dimethylarninomethylenebenzoylacetone (2) and ethyl N-(2-acetyl-2-benzoyl-1-ethenyl)glycinate (3) and its transformation into 4-benzoyl-2-ethoxycarbonyl-3-methylpyrrole (9) is described. Cyclization of 4 into 9 represents a new synthesis of polysubstituted pyrroles.

4(R)-(6-Chloro-s-triazolo[4,3-b]pyridazinyl-3)-1,4-furanoses 10 and 11, 5(R)-(6-chloro-s-triazolo[4,3-b]pyridazinyl-3)-1,5-pyranose 13, and 2(S),3(R)-dihydro-5-(6-chloro-s-triazolo[4,3-b]pyridazinyl-3)-2,3-O-isopropylidenefuran (12) were prepared by cyclization of hydrazones 6–9 obtained from 6-chloro-3-hydrazinopyridazine (1) and aldofuranoses 2, 3 and 4, and aldopyranose 5.