Syntheses, structures, and spectroscopic properties of K9Nd[PS4]4, K3Nd[PS4]2, Cs3Nd[PS4]2, and K3Nd3[PS4]4

Four new quaternary alkali neodymium thiophosphates K 9Nd[PS 4] 4 ( 1), K 3Nd[PS 4] 2 ( 2), Cs 3Nd[PS 4] 2 ( 3), and K 3Nd 3[PS 4] 4 ( 4) were synthesized by reacting Nd with in situ formed fluxes of K 2S 3 or Cs 2S 3, P 2S 5 and S in appropriate molar ratios at 973 K. Their crystal structures are determined by single crystal X-ray diffraction. Crystal data: 1: space group C2/ c, a = 20.1894(16), b = 9.7679(5), c = 17.4930(15) A, beta = 115.66(1) degrees , and Z = 4; 2: space group P2 1/ c, a = 9.1799(7), b = 16.8797(12), c = 9.4828(7) A, beta = 90.20(1) degrees , and Z = 4; 3: space group P2 1/ n, a = 15.3641(13), b = 6.8865(4), c = 15.3902(13) A, beta = 99.19(1) degrees , and Z = 4; 4: space group C2/ c, a = 16.1496(14), b = 11.6357(7), c = 14.6784(11) A, beta = 90.40(1) degrees , and Z = 4. The structure of 1 is composed of one-dimensional (1) infinity{Nd[PS 4] 4} (9-) chains and charge balancing K (+) ions. Within the chains, eight-coordinated Nd (3+) ions, which are mixed with K (+) ions, are connected by [PS 4] (3-) tetrahedra. The crystal structures of 2 and 3 are characterized by anionic chains (1) infinity{Nd[PS 4] 2} (3-) being separated by K (+) or Cs (+) ions. Along each chain the Nd (3+) ions are bridged by [PS 4] (3-) anions. The difference between the structures of 2 and 3 is that in 2 the Nd (3+) ions are coordinated by four edge-sharing [PS 4] (3-) tetrahedra while in 3 each Nd (3+) ion is surrounded by one corner-sharing, one face-sharing, and two edge-sharing [PS 4] (3-) tetrahedra. The structure of 4 is a three-dimensional network with K (+) cations residing in tunnels running along [110] and [110]. The {Nd(1)S 8} polyhedra share common edges with four [PS 4] tetrahedra forming one-dimensional chains (1) infinity{Nd[PS 4] 2} (3-) running along [110] and [110]. The chains are linked by {Nd(2)S 8} polyhedra yielding the final three-dimensional network (3) infinity{Nd[PS 4] 2} (3-). The internal vibrations of both crystallographically independent [PS 4] (3-) anions of 2- 4 have been assigned in the range 200-650 cm (-1) by comparison of their corresponding far/mid infrared and Raman spectra (lambda exc = 488 nm) on account of locally imposed C 1 symmetry. In the Fourier-transform-Raman spectrum (lambda exc = 1064 nm) of 2- 4, very similar well-resolved electronic Raman (ER) transitions from the electronic Nd (3+) ground-state to two levels of the (4)I 9/2 ground manifold and to the six levels of the (4)I 11/2 manifold have been determined. Resonant Raman excitation via a B-term mechanism involving the (4)I 15/2 and (4)F 3/2 intermediate states may account for the significant intensity enhancement of the ER transitions with respect to the symmetric P-S stretching vibration nu 1. Broad absorptions in the UV/vis/NIR diffuse reflectance spectrum at 293 K in the range 5000-25000 cm (-1) of 2- 4 are attributed to spin-allowed excited quartet states [ (4)(I < F < S < G < D)] and spin-forbidden doublet states [ (2)(H < G < K < D < P)] of Nd (3+). A luminescense spectrum of 3 obtained at 15 K by excitation with 454.5 nm shows multiplets of narrow lines that reproduce the Nd (3+) absorptions. Sharp and intense luminescence lines are produced instead by excitation with 514.5 nm. Lines at 18681 ( (4)G 7/2), 16692 ( (4)G 5/2), 14489 ( (4)F 9/2), and 13186 cm (-1) ( (4)F 7/2) coincide with the corresponding absorptions. Hypersensitive (4)G 5/2 is split by 42 cm (-1). The most intense multiplet at about 16500 cm (-1) is assigned to the transition from (4)G 5/2 to the Stark levels of the ground manifold (4)I 9/2.     

Selenium heterocycles. XXXIX. Synthesis of thieno[3, 4-d]thiazole,thieno[3, 4-d]selenazole,selenolo[3, 4-d]thiazole and selenolo[3, 4-d]selenazole

Starting from readily available methyl 2-substituted4-methyl-5-thiazolyl ketone and methyl 4-methyl-2-phenyl-5-selenazolyl ketone, thieno[3, 4-d]thiazole, thieno[3, 4-d]selenazole, selenolo[3, 4-d]thiazole and selenolo[3, 4-d]selenazole were prepared. The structures of all compounds were confirmed by analytical and spectroscopic methods.     

31P solid state NMR studies of metal selenophosphates containing [P2Se6]4-, [P4Se10]4-, [PSe4]3-, [P2Se7]4-, and [P2Se9]4- ligands

31P solid-state nuclear magnetic resonance (NMR) spectra of 12 metal-containing selenophosphates have been examined to distinguish between the [P(2)Se(6)](4-), [PSe(4)](3-), [P(4)Se(10)](4-), [P(2)Se(7)](4-), and [P(2)Se(9)](4-) anions. There is a general correlation between the chemical shifts (CSs) of anions and the presence of a P[bond]P. The [P(2)Se(6)](4-) and [P(4)Se(10)](4-) anions both contain a P[bond]P and resonate between 25 and 95 ppm whereas the [PSe(4)](3-), [P(2)Se(7)](4-), and [P(2)Se(9)](4-) anions do not contain a P[bond]P and resonate between -115 and -30 ppm. The chemical shift anisotropies (CSAs) of compounds containing [PSe(4)](3-) anions are less than 80 ppm, which is significantly smaller than the CSAs of any of the other anions (range: 135-275 ppm). The smaller CSAs of the [PSe(4)](3-) anion are likely due to the unique local tetrahedral symmetry of this anion. Spin-lattice relaxation times (T(1)) have been determined for the solid compounds and vary between 20 and 3000 s. Unlike the CS, T(1) does not appear to correlate with P-P bonding. (31)P NMR is also shown to be a good method for impurity detection and identification in the solid compounds. The results of this study suggest that (31)P NMR will be a useful tool for anion identification and quantitation in high-temperature melts.     

Structure of 2, 4-dimercapto[4,2,1]triazolo [3, 4-b][1,3,4]-thiadiazole

A thione-thiol structure was established for 2-mercapto-5-thiono[4,2,1]triazolino[3,4-b] [1,3,4]thiadiazole in accordance with calculations of the π-bonding and solvation energies by the Pariser-Parr-Pople method and also on the basis of a study of the IR and UV spectra. It follows from a determination of the ionization constants that this compound is a strong acid.     

Organic clays. Synthesis and structure of Na5[calix[4] arene sulfonate] · 12 H2O,K5[calix[4]arene sulfonate]·8 H2O,Rb5[calix[4]arene sulfonate]·5 H2O,and Cs5[calix[4] arene sulfonate] ·4 H2O

The title calixarenes all exist in the solid state as bilayers of anionic calixarenes in the cone configuration. These layers alternate with inorganic regions which contain the cations and the water molecules. The overall structures bear a close resemblance to those found for clay minerals. The sodium salt crystallizes in the triclinic space groupP witha = 10.998(6),b = 13.582(5),c = 14.472(5) Å, = 74.01(3), = 89.09(4), = 86.50(4)°, andZ = 2 forD _calc = 1.72 g cm^–3. Refinement based on 4727 observed reflections led to a conventionalR = 0.050. The potassium salt crystallizes in the triclinic space groupP witha = 11.815(9),b = 13.636(6),c = 14.040(9) Å, = 100.24(5), = 111.86(9), = 95,14(9)°, andZ = 2 forD _calc = 1.77 g cm^–3. Refinement based on 2977 observed reflections led toR = 0.15. The rubidium and cesium salts are isostructural and crystallize in the monoclinic space groupP2₁/n with parameters for Rb[Cs]a = 11.603(5) [11.704(3)],b = 28.607(8) [29.747(9)],c = 12.512(5) [12.604(4)] Å, = 91.70(4) [91.63(2)°], andZ = 4 forD _calc = 2.01 [2.24] g cm^–3. Refinement based on 1750 [4257] observed reflections led toR = 0.108 [0.075]. Disorder of the cations was observed for the rubidium and cesium salts. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82074 (95 pages).     

4-Substituted-4H-pyrrolo[2,1-c] [1,4]benzoxazines

The condensations of 1-(2-hydroxyphenyl) pyrroles with a variety of carbonyl compounds are shown to give new 4-substituted-4H-4-methylpyrrolo[2,1-c][1,4]benzoxazines. Some of the products were further functionalized. The ir, uv, and pmr spectra of the title heterocyclic system are discussed. Reaction of 1-(2-hydroxyphenyl) pyrrole with dimethyl acetylenedicarboxylate yielded dimethyl 3-(2-hydroxyanilino) phthalale; a mechanistic rationale which accounts for the result involves a rearrangement of the hypothetical Diels-Alder adduct.     

Zur Kenntnis der Na5[GaO4]-Verwandtschaft: KNa4[GaO4] und CsK4[GaO4]

About the Na₅[GaO₄]-Relationship: KNa₄[GaO₄] and CsK₄[GaO₄] KNa₄[GaO₄] was newly prepared from binary oxides (powders) and also from KGaO₂/Na₂O/K₂O (colourless columnar single crystals) in a closed Ag-cylinder at 600 and 650°C. Space group Pbca with a = 1046.1(2), b = 596.3(1), c = 1871.1(3) pm, Z = 8 [Four-circle-diffractometer data, 1138 I₀(hkl), MoKα, R = 8.29, R_w = 6.76%, anisotropic refinement] (Parameter s. text). Colourless cubic single crystals of hitherto unknown CsK₄[GaO₄] are formed by reaction of K₂O, CsGaO₂, and Cs₂O (surplus) in a closed Au-tube at 580°C. Space group Pbca with a = 1154.7, b = 667.7, c = 2096.6 pm, Z = 8 [Four-circle-diffractometer data, 1798 I₀(hkl), MoKα, R = 7.62, R_w = 7.68%, anisotropic refinement] (Parameter s. text). Both crystal structures belong to the Na₅[GaO₄] type. Structural aspects, ECoN, and MAPLE of KNa₄[GaO₄] and CsK₄[GaO₄] in relation with Na₅[GaO₄] are discussed.     

Mannich reactions. Synthesis of 4,5-dihydropyrrolo[l,2-a]quinoxalines, 2,3,4,5-tetrahydro-lH-pyrrolo[l,2-a] [l,4]diazepines and 5,6-dihydro-4H-pyrrolo[ 1,2-a] [ 1,4]benzodiazepines

l-(2-Aminophenyl)pyrrole (I) and l-[2-(aminomethyl)]phenylpyrrole hydrochloride (III) undergo cyclization reactions with aldehydes and ketones to form 4,5-dihydropyrrolo[l,2-a]- quinoxalines and 5,6-dihydropyrrolo[l,2-a][l,4]benzodiazepines, respectively. It was also found that the use of the free base of compounds corresponding to III do not cyclize directly but lead instead to the intermediate Schiff bases which are subsequently cyclized to the desired benzodiazepines by treatment with hydrochloric acid.     

1, 4-Diazabicyclo [2.2.2] octanes

1,4-Diazabicyclo[2.2.2]octane hydrochloride methylchloride was obtained from N-benzoylpiperazine through 1-(2-hydroxyethyl)-4-benzoylpiperazine, 1-(2-acetoxyethyl)-4-benzoylpiperazine methyltosylate, 1-(2-hydroxyethyl)piperazine methylchloride, and 1-(2-chloroethyl)piperazine methylchloride.See [1] for communication I.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 845–847, June, 1976.     

Calix[4]azacrown and 4-aminophthalimide-appended calix[4]azacrown: synthesis, structure, complexation and fluorescence signaling behaviour

The synthesis and single crystal structure of 25,27-(diamidomonoazacrown-5)-calix[4]arene (L), calix[4]arene capped by a diamide bridge in the 1,3-position on the lower rim, which forms a supramolecular dimer in the solid state via intermolecular hydrogen bonding, are described. A 4-aminophthalimide (AP) fluorophore has been regioselectively linked to the secondary amino function of the azacrown unit with a dimethylene spacer to construct N-(4-aminophthalimidoethyl)calix[4]azacrown (APL), a fluorescent sensor, via a fluorophore-spacer-receptor architecture. Fluorescence quantum yield and lifetime of APL have been measured to be lower than those of the bare fluorophore (AP) due to the photoinduced intramolecular electron transfer (PIET) between the fluorophore and the receptor moieties of the molecule. In the presence of transition metal ions, fluorescence enhancement of is observed suggesting the binding of the metal ion to the sensor. Complexation properties of APL with transition metal ions are investigated using UV-vis spectroscopy. A 1 : 1 stoichiometry of the complex is determined from a Job plot and the corresponding association constants for the various metal ions are evaluated. Fe(3+) and Cu(2+) ions have the largest association constants (K= 2.3 x 10(5) M(-1) and 1.6 x 10(5) M(-1) respectively) compared to other metal ions indicating that they form complexes selectively with APL.     

Properties of 4H-[1]benzopyrano[3,4-c]-[1,2,5]-selenodiazol-4-one

4H-[1]benzopyrano[3,4-c][1,2,5]selenodiazol-4-one has been synthesized by the reaction of 3,4-diaminocoumarin with selenous acid and its reaction with several nucleophiles (alkali, ammonia, amines, hydrazine hydrate) and its nitration have been studied. Using PMR spectroscopy, a comparative kinetic study of the opening of the lactone ring in 6,8-dinitro-4H-[1]benzopyrano[3,4-c][1,2,5]seleno- and thiadiazol-4-ones has been carried out.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 128–133, January, 1991.     

Synthesis of novel imidazo[1,2-a][3,1]benzothiazines 4, imidazo[1,2-a]-[1,2,4]benzotriazines 5, and 4H-imidazo[2,3-c]pyrido[2,3-e][1,4]oxazines 6

Starting from the readily available 2-aminobenzhydrols ( 7 ), 3-amino-1,2,4-benzotriazine ( 11 ) and 2-amino-3-pyridinol ( 12 ), novel derivatives of 5-phenyl-5H-imidazo[1,2-a][3,1]benzothiazine-2-carboxylic acid, ethyl ester ( 4 ), imidazo[2,1-c][1,2,4]benzotriazine-2-carboxylic acid, ethyl ester ( 5 ) and 4H-imidazo[2,3-c]pyrido-[2,3-e][1,4]oxazine ( 6 ) were prepared.     

Polymethyl derivatives of furo[3,4-c]pyran4-one,furo[3,4-c] pyridin-4-one and pyrrolo[3,4-c]pyran-4-one

The: title compounds were prepared from Michael adducts, obtained from acetoacetic esters and trans-3-hexene-2,5-dione, and from the corresponding dehydration products, by direct cyclization to oxygen rings or by reaction with ammonia (or methylamine) to give nitrogen rings.     

The properties and some reactions of 4-oxo-1, 5-diazabicyclo[4, 4, 0]decane and 5-oxo-1, 4-diazabicyclo[4, 4, 0]decane

The chemical properties of 1,4- and 1,5-diazabicyclo[4, 4, 0]decanes and their 5- and 4-oxo derivatives, respectively, have been studied.     

Calix[4]azulene

Azulene reacts with paraformaldehyde in the presence of florisil to give excellent yields of calix[4]azulene.