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.     

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.     

Thio- und Selenomercurate(II). K6[HgS4], K6[HgSe4], Rb6[HgS4] und Rb6[HgSe4]

Thio- and Selenomercurates(II). K₆[HgS₄], K₆[HgSe₄], Rb₆[HgS₄] and Rb₆[HgSe₄] We prepared by annealing intimate mixture of pure samples of K₂S, K₂Se, Rb₂S, and Rb₂Se with HgS or HgSe [360–380°C, 7d, Duran-glass-seal with Argon] with hexagonal Na₆ZnO₄ isotypic new mercurates: K₆[HgS₄] [bright citronic yellow a = 9.98₅, c = 7.65₂ Å], K₆[HgSe₄] [light orange yellow a = 10.3₆, c = 7.88₃ Å], Rb₆[HgS₄] [bright yellow a = 10.3₄, c = 7.94₂ Å], Rb₆[HgSe₄] [orange-red a = 10.7₂, c = 8.19₂ Å]. The crystal structure of K₆ Hgs₄ is elucidated by using diffractometer data of single crystals: P63mc, C⁴_6v, it is R = 6.6% for 304 reflexes [h k o–h k 4, anisotropic refinement MoKα]; for position and parameters see text d_rö = 2.83₅, d_pyk = 2.99 g · cm^?3. The Madelung Part of Lattice Energy, MAPLE, and Effective Coordination Numbers, ECoN, are calculated and discussed.     

Cs4[IrO4], ein neues Iridat mit planarem Anion [IrO4]4−

Cs₄[IrO₄], a New Iridate with Planar Anion [IrO₄]^4? For the first time we obtained black single crystals of Cs₄[IrO₄] by heating intimate mixtures of CsO_0.52 and IrO₂ (molar ratio Cs : Ir = 4.30 : 1.00; “Ag-bomb”, 740°C/86 d). Cs₄[IrO₄] crystallizes monocline, C 2/m, with a = 1031.66(8) pm, b = 671.61(4) pm, c = 660.44(6) pm, b? = 108.118(7)° and Z = 2 in the K₄[IrO₄]-type. The structure has been determined by four-circle-diffractometer data (PW 1100 from Phillips, Ag? Kα , graphite) with 841 I₀(hkl) with I ≥ 3s?(F) (from 947 I₀(hkl) out of 3529 measured reflexes). The Madelung Part of Lattice Energy, MAPLE, Effective Coordination Numbers, ECoN, these via Mean Fictive Ionic Radii, MEFIR, are calculated and discussed.     

Calix[4]azulene

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

Porphyrin-Calix[4]arenes

The review deals with the synthesis, chemical modification, and complexing properties of a new class of molecular receptors, porphyrin-calix[4]arene conjugates.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 6, 2005, pp. 807–826.Original Russian Text Copyright © 2005 by Mamardashvili, Koifman.     

4-tert-butylcalix[4]arene-based porous structures

Microporous material with a large surface area is obtained through the controlled desolvation of 4-tert-butylcalix[4]arene complex with acetonitrile.     

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.     

PPh4[As3S3Cl4] und PPh4[As3S3Br4]

PPh₄[As₃S₃Cl₄] and PPh₄[As₃S₃Br₄] When As₂S₃ reacts with PPh₄X and HX in 1,2-C₂H₄X₂ (X = Cl, Br), the title compounds are obtained as minor products; the main products are PPh₄[As₂SX₅]. Their crystal structures were determined by X-ray diffraction. PPh₄[As₃S₃Cl₄]: a = 1187.7, b = 1090.9, c = 1191.8 pm, α = 82.91, β = 88,93, γ = 88.52°; twins with twin plane (100); R = 0.109 for 1618 observed reflexions of one twin crystal. PPh₄[As₃S₃Br₄]: a = 1119.7, b = 1177.5, c = 1204.1 pm, α = 81.59, β = 85.88, γ = 88.25°; R = 0.061 for 2331 observed reflexions. Both compounds crystallize in the space group P1 , Z = 2, and can be considered to be isotypic. Nevertheless, PPh₄[As₃S₃Br₄] does not form twins as PPh₄[As₃S₃Cl₄]. The crystals consist of PPh₄⁺ and [As₃S₃X₄]^? ions. In the anions, the three As atoms of an As₃S₃ ring in the chair conformation are commonly joined to an X atom and each As atom is bonded to one further terminal X atom. Cations and anions are packed in alternating layers.     

Structural features of Ag[AuF4] and Ag[AuF6] and the stuctural relationship of Ag[AgF4]2 and Au[AuF4]2 to Ag[AuF4]2

Synchrotron radiation X-ray powder diffraction data (SPDD) have been obtained for Ag[AgF4]2, Au[AuF4]2, Ag[AuF4], and Ag[AuF6]. Ag[AgF4]2 and Au[AuF4]2 are isostructural with Ag[AuF4]2, space group (SG) P2(1)/n, Z = 2, with the following: for Ag[AgF4]2 a = 5.04664(8), b = 11.0542(2), c = 5.44914(9) A, beta = 97.170(2) degrees; for Au[AuF4]2 a = 5.203(2), b = 11.186(3), c = 5.531(2) A, beta = 90.55(2) degrees. The structure of Ag[AgF4]2 was refined successfully (SPDD) applying the Rietveld method, yielding the following interatomic distances (A): AgII-F = 2.056(12), 2.200(13), 2.558(13); AgIII-F = two at 1.846(12), others = 1.887(12), 1.909(13), 2.786-(12), 2.796(12), 2.855(12). AgAuF4, like other AA'F4 salts (A = Na-Rb; A' = Ag, Au), crystallizes in the KBrF4 structure type, SG I4/mcm (140), Z = 4 with a = 5.79109(6), c = 10.81676(7) A. SPDD gave (in A) four AuIII-F = 1.89(1) and eight AgI-F = 2.577(7). SPDD for AgAuF6 confirmed that it has the LiSbF6 structure, SG R3, Z = 3, with a = 5.2840(2), c = 15.0451(6) A.     

Microwave-assisted synthesis of resorcin[4]arene and pyrogallol[4]arene macrocycles

A series of resorcin[4]arene and pyrogallol[4]arene macrocycles have been synthesized efficiently within 5 min, affording crystalline products suitable for single crystal X-ray diffraction, utilising microwave irradiation in a ‘one-pot’ reaction whilst controlling the selective formation of the rccc cone stereoisomer.