Hydrogen bonding in 2-hydroxy-benzhydrazide and 2-hydroxy-thiobenzhydrazide. Structural and spectroscopic study

Summary X-ray structural data are reported for 2-hydroxy-benzhydrazide(monoclinic; P2₁/n-C _2h ⁵ ;a=10.569(2) Å,b=11.264(2) Å,c=6.074(1) Å, =98.80(1)°;Z=4;R=0.054) and 2-hydroxy-thiobenzhydrazide (monoclinic; P2₁/n-C _2h ⁵ ;a=14.598(6) Å,b=5.975(2) Å,c=9.286(4) Å, =107.80(3)°;Z=4;R=0.044). In both compounds the phenolic OH groups are intramolecularly hydrogen bonded to the (thio)carbonyl oxygens and sulfurs, respectively; the basic intermolecular association patterns consist of closed six-membered hydrogen bonded dimers which are connected via N-H ... NH₂ hydrogen bonds. The spectral characteristics of the intramolecular O-H...O/S hydrogen bonds (solid state (OH)=2800/2700 cm^–1, CCl₄ solution (OH)=3035/3100 cm^–1, CDCl₃ solution (OH)=11.62/10.56 ppm) are similar to those of corresponding primary and secondary amides. The solid state IR spectra are consistent with hydrogen bonded NH groups and free NH₂ groups, the solution IR spectra indicate free NH₂ as well as free NH groups.

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Wasserstoffbrückenbindung in 2-Hydroxy-benzhydrazid und 2-Hydroxy-thiobenzhydrazid. Strukturelle und spektroskopische Untersuchungen

Zusammenfassung Es werden Röntgenstrukturdaten für 2-Hydroxy-benzhydrazid (monoklin; P2₁/n- C _2h ⁵ ;a=10.569(2) Å,b=11.264(2)Å,c=6.074(1)Å, =98.80(1)°;Z=4;R=0.054) und 2-Hydroxy-thiobenzhydrazid (monoklin; P2₁/n - C _2h ⁵ ;a=14.598(6)Å,b=5.975(2)Å,c=9.286(4)Å, =107.80(3)°;Z=4;R=0.044) berichtet. In beiden Verbindungen bilden die phenolischen OH-Gruppen intramolekulare Wasserstoffbrücken mit den Carbonyl-Sauerstoff-, bzw. den Thiocarbonyl-Schwefel-Atomen. Das intermolekulare Assoziationsmuster wird durch N-H...NH₂ Wasserstoffbrücken bestimmt, die jeweils zwei Moleküle über sechszählige Ringe zu Dimeren verbinden. Die IR- und NMR-spektroskopischen Charakteristika der intramolekularen O-H...O/S Wasserstoffbrücken (kristallin: (OH)=2800/2700 cm^–1, CCl₄-Lösungen: (OH)=3035/3100 cm^–1, CDCl₃-Lösungen: (OH)=11.62/10.56 ppm) sind sehr ähnlich zu denen entsprechender primärer und sekundärer Amide. Die Festkörper-IR-Spektren stehen in Einklang mit assoziierten NH- und freien NH₂-Gruppen, während die Lösungs-IR-Spektren auch auf das Vorliegen freier NH-Gruppen schließen lassen.

     

Ruthenium Cluster Chemistry with Ph2PC6H4-4-C≡CH

The new phosphines Ph₂PC₆H₄-4-CCR [R=SiMe₃ (1), H (2)] have been used to prepare Ru₃(CO)₉(Ph₂PC₆H₄-4-CCSiMe₃)₃ (4) and Ru(CCC₆H₄-4-PPh₂)(PPh₃)₂(-C₅H₅) (3), respectively, the latter with a pendent phosphine. Reaction of 4 with carbonate or fluoride affords Ru₃(CO)₉(Ph₂PC₆H₄-4-CCH)₃ (5) with pendent terminal alkynyl groups, the identity of which was confirmed by a structural study. Reaction of 5 with [Ru(NCMe)(PPh₃)₂(-C₅H₅)]PF₆ or reaction of Ru₃(CO)₁₂ with 3 gives Ru₃(CO)₉{(Ph₂PC₆H₄-4-CC)Ru(PPh₃)₂(-C₅H₅)}₃ (6). Complexes 3–6 have been studied by cyclic voltammetry. Proceeding from Ru₃(CO)₁₂ to 4 or 5 shifts the cluster-centred reduction to more negative potential and affords facile cluster-centred oxidation. Proceeding from 4/5 and 3 to 6 results in similarly-located cluster-centred reduction and peripheral ruthenium-centred oxidation, but results in a lack of observable cluster-centred oxidation. Crystal data for 5·C₆H₁₄: space group P¯1, a=12.760(1) Å, b=17.077(1) Å, c=17.924(2) Å, =108.656(5)°, =96.344(5)°, =93.523(5)°, V=3658.4(6) ų, Z=2, R=0.078, R_w=0.105 for 5008 reflections [I>2.00(I)].     

The Thermal Reaction of the Tris(μ-Hydrido)-Dodecacarbonyltrirhenium (o) Cluster with Triphenylphosphine and Triphenylphosphite

The thermal reaction between the tris(μ-hydrido)dodecacarbonyltrirhenium (o) cluster and triphenylphosphine or triphenylphosphite results in a trisubstituted rhenium cluster as the major product. The results of an X-ray structural analysis of H₃Re₂(CO)₉(PPh₃) are: Mr=1597.57, Monoclinic, P₂₁/n, a=15.598(1), b=9.530(2), c=41.685(3) Å, β=80.60(1)°, V=6113.(1) ų, Z=4, D_c=1.736 g/cm³, CuK_e, λ-1.54056 Å, μ-121.23 cm^?1, F(000)=3059.17, room temperature, R=0.049 for 7361 reflections with I≥2.5σ(I). The molecule has a triangular Re₂ core coordinated propellerwise by three PPh₃ ligands in the molecular plane with virtual C_3k symmetry.     

Synthesis and Crystal Structure of Bis(nitrate)- bis(N,N''''-dimethyl-N,N''''-dibenzenyl-urea)uranyl(Ⅱ)

1 INTRODUCTION Tri-butyl phosphate (TBP) has been widely used as the extraction reagent in U-Th fuel to separate uranium from thorium. But di-butyl phos- phate (DBP) and butyl phosphate (MBP), the radio- lytic products of TBP, exhibit some coordinated ability to the fission elements, such as Zr and Nb. The substitutes for TBP have being studied for several decades[1～4]. The physical and chemical properties of amides are similar to those of TBP and they selectively extract U(Ⅵ…     

Formation of sol-gel nanostructured mullite by additions of fluoride ion

Summary The subject of this study was to investigate the effect of fluoride ions addition on the temperature of sol gel mullite formation based on the hypotheses that the presence of fluoride ions can decrease the temperature of mullite formation (in respect to common 980°C, in sol-gel processing). Polymeric sols were prepared by mixing TEOS and aluminum nitrate nanohydrate and by adding fluoride ions (from 2 to 5 mass%). DTA, TG, XRD and SEM were used for characterisation of mullite gel and crystalline mullite. The experimental results confirmed that the addition of fluoride ions decrease the temperature of mullite formation up to 890°C for the fluorine concentration of 3.5 mass%. Experimental results showed that the temperature of mullite formation is not a simple function of the fluoride ion content. The mechanism of fluorine effect was discussed in terms of the gelling process, gel structure and the phase separation before the mullite formation.     

Modification of polysulfone membranes 4. Ammonia plasma treatment

The effect of NH₃ and NH₃/Ar plasma on ultrafiltration polysulfone membranes have been studied. Results of contact angle, FTIR-ATR and X-ray photoelectron spectroscopy experiments clearly showed that both plasmas introduced hydrophilic, nitrogen- and oxygen-containing moieties on the polymer surface and that NH₃/Ar plasma was more efficient. That plasma was also more aggressive--signs of strong etching could be seen on the SEM pictures. Redeposition of etched material seemed to take place inside the pores. On the contrary, ammonia plasma was soft and caused cleaning the surface and pores enlargement. Performance of ammonia plasma modified membranes was greatly improved and independent on solution pH. The last observation proved amphoteric character of the surface. NH₃/Ar plasma treatment gave membranes of acidic surface and filtration indices not so good as for ammonia plasma.     

Combined application of 2D NMR correlation methods and ab initio chemical shift calculations to the structure determination of new heterocyclic compounds

The combined use of 2D NMR correlation methods and ab initio chemical shift calculations is efficient and, in some cases, virtually the only way to determine the structures of new organic compounds. This approach enabled us to establish the structure of the major unusual product of the three-component reaction of imidazo[1,5-a]quinoxalin-4-one, bis(2-chloroethyl)amine hydrochloride, and potassium carbonate in DMF. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2172–2179, December, 2006. Dedicated to Professor A. V. Il’yasov on the occasion of his 70th birthday.     

苯腙基乙酰基二取代乙酸乙酯的合成和晶体结构

报道了标题化合物C12H14N2O3(Mr=234.25)的合成和晶体结构.晶体属单斜晶系,P21/c空间群.晶胞参数:浕=0.84589(17)nm,b=1.7597(4)nm,c=0.82599(17)nm,α=90°,β=91.21(3)°,γ=90°,V=1.2292(4)nm3,Z=4,Dc=1.266g/cm3,μ=0.092mm-1,F(000)=496;偏离因子R=0.0760,Rw=0.1932.     

Corrugated single-layer graphite sheet as a model of stepped surface of a crystal

Electronic structure calculations have been performed for flat graphite sheets and periodically distorted sheets with different values of deformation angle and hydrogen adsorption. These characteristics do not all behave monotonically with increasing deformation angle. At small deformation angles, the electrons pass from the atoms of terraces to those of edges, while at larger angles the reverse pattern is observed. The position of the Fermi level also varies nonmonotonically. The binding energy of hydrogen depends significantly on the adsorption site, and the difference can be doubled. Based on the ata obtained, it was concluded that a priori statements derived from the “general concepts” on the difference in the physicochemical properties of, for example, terrace and edge atoms on high-index facets are unreliable.     

Molecular Recognition and Crystal Energy Landscapes: An X‐ray and Computational Study of Caffeine and Other Methylxanthines

We introduce a new approach to crystal‐packing analysis, based on the study of mutual recognition modes of entire molecules or of molecular moieties, rather than a search for selected atom–atom contacts, and on the study of crystal energy landscapes over many computer‐generated polymorphs, rather than a quest for the one most stable crystal structure. The computational tools for this task are a polymorph generator and the PIXEL density sums method for the calculation of intermolecular energies. From this perspective, the molecular recognition, crystal packing, and solid‐state phase behavior of caffeine and several methylxanthines (purine‐2,6‐diones) have been analyzed. Many possible crystal structures for anhydrous caffeine have been generated by computer simulation, and the most stable among them is a thermodynamic, ordered equivalent of the disordered phase, revealed by powder X‐ray crystallography. Molecular recognition energies between two caffeine molecules or between caffeine and water have been calculated, and the results reveal the largely predominant mode to be the stacking of parallel caffeine molecules, an intermediately favorable caffeine–water interaction, and many other equivalent energy minima for lateral interactions of much less stabilization power. This last indetermination helps to explain why caffeine does not crystallize easily into an ordered anhydrous structure. In contrast, the mono‐ and dimethylxanthines (theophylline, theobromine, and the 1,7‐isomer, for which we present a single‐crystal X‐ray study and a lattice energy landscape) do crystallize in anhydrous form thanks to the formation of lateral hydrogen bonds.