Synthesis, structure and magnetic behavior of a new three-dimensional Manganese phosphite-oxalate: [C2N2H10][Mn-2(II)(OH2)(2)(HPO3)(2)(C2O4)]

A novel manganese phosphite-oxalate, [C2N2H10][Mn-2(II)(OH2)(2)(HPO3)(2)(C2O4)] has been hydothermally synthesized and its structure determined by single-crystal X-ray diffraction. The structure consists of neutral manganese phosphite layers, [Mn(HPO3)](infinity), formed by MnO6 octahedra and HPO3 units, cross-linked by the oxalate moieties. The organic cations occupy the middle of the 8-membered one dimensional channels. Magnetic studies indicate weak antiferromagnetic interactions between the Mn2+ ions. (C) 2009 Elsevier Inc. All rights reserved.

Two- and Three-Dimensional Open-Framework Uranium Arsenates: Synthesis, Structure, and Characterization

Hydrothermal reactions between uranium salts and arsenic pentoxide in the presence of two different amines yielded six new uranium arsenate phases exhibiting open-framework structures, ethylenediamine (en): [C2N2H9]-[(UO2)(ASO(4))] I; [C2N2H10][(UO2)F(HASO(4))]2 center dot 4H(2)O, II; [C2N2H9][U2F5(HASO(4))(2)], III; [C2N2H9][UF2(ASO(4))], IV; diethylenetriamine (DETA), [C4N3H16][U2F3(ASO(4))(2)(HAsO4)] V; and [C4N3H16][U2F6(AsO4)(HAsO4)], VI. The structures were determined using single crystal studies, which revealed two- (I, II, V) and three-dimensional (III, IV, VI) structures for the uranium arsenates. The uranium atom, in these compounds, exhibits considerable variations in the coordination (6 to 9) that appears to have some correlation with the synthetic conditions. The water molecules in [C2N2H10][(UO2)F(HAsO4)](2 center dot)4H(2)O, II, could be reversibly removed, and the dehydrated phase, [C2N2H10][(UO2)F(HAsO4)](2), IIa, was also characterized using single crystal studies. The observation of many mineralogical structures in the present compounds suggests that the hydrothermal method could successfully replicate the geothermal conditions. As part of this study, we have observed autunite, Ca[(UO2)(PO4)](2)(H2O)(11), metavauxite, [Fe(H2O)(6)][Al(OH)(H2O)(PO4)](2), finarite, PbCU(SO4)(OH)(2), and tancoite, LiNa2H[Al(PO4)(2)(OH)], structures. The repeated observation of the secondary building unit, SBU-4, in many of the uranium arsenate structures suggests that these are viable building units. Optical studies on the uranium arsenate compound, [C4N3H16][U2F6(AsO4)(HASO(4))), VI, containing uranium in the +4 oxidation state indicates a blue emission through an upconversion process. The compound also exhibits antiferromagnetic behavior.

Self-assembly of a nanoscopic platinum(II) double square cage

Self-assembly of a rigid tripyridyl linker with a bidentate 90 degrees Pt(II) acceptor yielded a somewhat unusual double square cage, representing the first example of Pt(II) cage of such shape. Multinuclear NMR as well as single-crystal structure analysis characterized the cage.

Self-assembly of a nanoscopic platinum(II) double square cage

Self-assembly of a rigid tripyridyl linker with a bidentate 90 degrees Pt(II) acceptor yielded a somewhat unusual double square cage, representing the first example of Pt(II) cage of such shape. Multinuclear NMR as well as single-crystal structure analysis characterized the cage.

A Unique Nickel System having Versatile Catalytic Activity of Biological Significance

A new dinuclear nickel(II) complex, [Ni-2(LH2)(H2O)(2)(OH)(NO3)](NO3)(3) (1), of an ``end-off'' compartmental ligand 2,6-bis(N-ethylpiperazine-iminomethyl)-4-methyl-phenolato, has been synthesized and structurally characterized. The X-ray single crystal structure analysis shows that the piperazine moieties assume the expected chair conformation and are protonated. The complex 1 exhibits versatile catalytic activities of biological significance, viz. catecholase, phosphatase, and DNA cleavage activities, etc. The catecholase activity of the complex observed is very dependent on the nature of the solvent. In acetonitrile medium, the complex is inactive to exhibit catecholase activity. On the other hand, in methanol, it catalyzes not only the oxidation of 3,5-di-tert-butylcatechol (3,5-DTBC) but also tetrachlorocatechol (TCC), a catechol which is very difficult to oxidize, under aerobic conditions. UV vis spectroscopic investigation shows that TCC oxidation proceeds through the formation of an intermediate. The intermediate has been characterized by an electron spray ionizaton-mass spectrometry study, which suggests a bidentate rather than a monodentate mode of TCC coordination in that intermediate, and this proposition have been verified by density functional theory calculation. The complex also exhibits phosphatase (with substrate p-nitrophenylphosphate) and DNA cleavage activities. The DNA cleavage activity exhibited by complex 1 most probably proceeds through a hydroxyl radical pathway. The bioactivity study suggests the possible applications of complex 1 as a site specific recognition of DNA and/or as an anticancer agent.

A Unique Nickel System having Versatile Catalytic Activity of Biological Significance

A new dinuclear nickel(II) complex, [Ni-2(LH2)(H2O)(2)(OH)(NO3)](NO3)(3) (1), of an "end-off" compartmental ligand 2,6-bis(N-ethylpiperazine-iminomethyl)-4-methyl-phenolato, has been synthesized and structurally characterized. The X-ray single crystal structure analysis shows that the piperazine moieties assume the expected chair conformation and are protonated. The complex 1 exhibits versatile catalytic activities of biological significance, viz. catecholase, phosphatase, and DNA cleavage activities, etc. The catecholase activity of the complex observed is very dependent on the nature of the solvent. In acetonitrile medium, the complex is inactive to exhibit catecholase activity. On the other hand, in methanol, it catalyzes not only the oxidation of 3,5-di-tert-butylcatechol (3,5-DTBC) but also tetrachlorocatechol (TCC), a catechol which is very difficult to oxidize, under aerobic conditions. UV vis spectroscopic investigation shows that TCC oxidation proceeds through the formation of an intermediate. The intermediate has been characterized by an electron spray ionizaton-mass spectrometry study, which suggests a bidentate rather than a monodentate mode of TCC coordination in that intermediate, and this proposition have been verified by density functional theory calculation. The complex also exhibits phosphatase (with substrate p-nitrophenylphosphate) and DNA cleavage activities. The DNA cleavage activity exhibited by complex 1 most probably proceeds through a hydroxyl radical pathway. The bioactivity study suggests the possible applications of complex 1 as a site specific recognition of DNA and/or as an anticancer agent.

Chain structures in alkali metal borophosphates: synthesis and characterization of K3[BP3O9(OH)3] and Rb3[B2P3O11(OH)2]

Two new alkali metal borophosphates, K-3[BP(3)o(9)(OH)(3)] and Rb-3[B2P3O11(OH)(2)], were synthesized by applying solvothermal techniques using ethanol as solvent. The crystal structures were solved by means of single-crystal X-ray diffraction (K-3[BP3O9(OH)(3)], monoclinic, C2/c (No. 15), a = 2454.6(8) pm, b = 736.3(2) pm, c = 1406.2(4) pm, beta = 118.35(2)degrees, Z = 8; Rb-3[B2P3O11(OH)(2)], monoclinic, P2(1)/c (No. 14), a = 781.6(2) pm, b:= 667.3(2) pm, c = 2424.8(5) pm, beta = 92.88(1)degrees, Z = 4). Both crystal structures comprise borophosphate chain anions. While for the rubidium compound a loop-branched chain motif is found as common for most of the chain anions in alkali metal borophosphates, the crystal structure of the potassium phase comprises the first open-branched chain with the highest phosphate content found so far in this group of compounds. Both chain anions are Closely related to known anhydrous or hydrated phases, and the structural relations are discussed in terms of how the presence of OH groups and hydrogen bonds as well as number, charge, and size of charge balancing cations influence the 3D structural arrangement. The anionic entities are classified in terms of general principles of structural systematics for borophosphates.

Hybrid peptide hairpins containing alpha- and omega-amino acids: Conformational analysis of decapeptides with unsubstituted beta-, gamma-, and delta-residues at positions 3 and 8

The effects of inserting unsubstituted omega-amino acids into the strand segments of model beta-hairpin peptides was investigated by using four synthetic decapeptides, Boc-Lcu-Val-Xxx-Val-D-Pro-Gly-Leu-Xxx-Val-Val- OMe: pepticle 1 (Xxx=Gly), pepticle 2 (Xxx=beta Gly=beta hGly=homoglycine, beta-glycine), pepticle 3 (Xxx=gamma Abu=gamma-aminobutyric acid), pepticle 4 (Xxx= delta Ava=delta-aminovaleric acid). H-1 NMR studies (500 MHz, methanol) reveal several critical cross-strand NOEs, providing evidence for P-hairpin conformations in peptides 2-4. In peptide 3, the NMR results support the formation of the nucleating turn, however, evidence for cross-strand registry is not detected. Single-crystal X-ray diffraction studies of peptide 3 reveal a beta-hairpin conformation for both molecules in the crystallographic asymmetric unit, stabilized by four cross-strand hydrogen bonds, with the gamma Abu residues accommodated within the strands. The D-Pro-Gly segment in both molecules (A,B) adopts a type II' beta-turn conformation. The circular dichroism spectrum for peptide 3 is characterized by a negative CD band at 229 rim, whereas for peptides 2 and 4, the negative band is centered at 225 nm, suggesting a correlation between the orientation of the amide units in the strand segments and the observed CD pattern.

Synthesis, Structure, Spirocyclization Mechanism, and Glutathione Peroxidase-like Antioxidant Activity of Stable Spirodiazaselenurane and Spirodiazatellurane

The first examples of stable spirodiazaselenurane and spirodiazatellurane were synthesized by oxidative spirocyclization of the corresponding diaryl selenide and telluride and were structurally characterized. X-ray crystal structures of the spirodiazaselenurane and spirodiazatellurane suggest that the structures are distorted trigonal bipyramidal (TBP) with the electronegative nitrogen atoms occupying the apical positions and two carbon atoms and the lone pair of Se/Te occupying the equatorial positions. Interestingly, the spirodiazatellurane underwent spontaneous chiral resolution during crystallization, and the absolute configurations of its enantiomers were confirmed by single-crystal X-ray analyses. A detailed mechanistic study indicates that the cyclization to spirodiazaselenurane and spirodiazatellurane occurs via selenoxide and telluroxide intermediates. The chalcogenoxides cyclize to the corresponding spiro compounds in a stepwise manner via the involvement of hydroxyl chalcogenurane intermediates, and the activation energy for them spirocyclization reaction decreases in the order S > Se > Te. In addition to the synthesis, characterization, and mechanism of cyclization, the glutathione peroxidase (GPx) mimetic activity of the newly synthesized compounds was evaluated. These studies suggest that the tellurium compounds are more effective as GPx mimics than their selenium counterparts due to the fast oxidation of the tellurium center in the presence of peroxide and the involvement of an efficient redox cycle between the telluride and telluroxide intermediate.

N-H center dot center dot center dot O and C-H center dot center dotcenter dot O interaction mimicry in the 1:1 molecular complexes of 5,5-diethylbarbituric acid with urea and acetamide

The analogy between N-H center dot center dot center dot O and C-H center dot center dot center dot O intermolecular interactions is studied with variable temperature (180-100 K) single crystal X-ray diffraction analysis.5,5-Diethylbarbituric acid (barbital) forms isostructural molecular complexes (co-crystals) with urea (1) and acetamide (2) that respectively contain these analogous interactions.The behaviour of these two interactions as a function of temperature is very similar. This indicates that the C-H center dot center dot center dot O bond in barbital acetamide plays a similar chemical and structural role as does the N-H center dot center dot center dot O bond in barbital urea. The close relationship between these interactions and their comparable nature is further adduced from the formation of a ternary solid solution (3) of barbital, urea and acetamide. The fact that the C-H center dot center dot center dot O interaction in barbital acetamide is weaker than the N-H center dot center dot center dot O interaction in barbital urea is shown by the fact that acetamide is under expressed and urea is over expressed with respect to the quantities of these substances present in solution prior to crystallization of these ternary crystals.

NMR study of internal motions in certain iron group fluosilicates

NMR study of ferrous fluosilicate hexahydrate indicated the presence of motion of both proton and fluorine nuclei. Only a single narrow line was observed for protons for any arbitrary orientation of a single crystal with respect to the applied magnetic field. This can be interpreted in terms of a phase-correlated flip motion of the interproton vectors between two disordered orientations or in terms of a hindered rotation of the Fe(H2O) 6 octahedron about the fourfold axes, together with the flip motion. The fluorine second moment indicated that the SiF6 octahedron also is undergoing reorientation. The temperature variation of the powder linewidth showed a transition around 195°K and led to rather low values for the potential barriers hindering the motions. No significant temperature variation of the linewidth was observed for hexahydrated cobalt fluosilicate in the temperature range between 90°K and room temperature. Similar observations in a powder sample of tetrahydrated copper fluosilicate also showed the presence of internal motions. The linewidth transition in this case took place at about 220°K and was found to be rather abrupt. The potential barrier for the motion was found to be relatively high.

2(n)-SEMA-a robust solid state nuclear magnetic resonance experiment for measuring heteronuclear dipolar couplings in static oriented systems using effective transverse spin-lock

Separated local field (SLF) spectroscopy is a powerful technique to measure heteronuclear dipolar couplings. The method provides site-specific dipolar couplings for oriented samples such as membrane proteins oriented in lipid bilayers and liquid crystals. A majority of the SLF techniques utilize the well-known Polarization Inversion Spin Exchange at Magic Angle (PISEMA) pulse scheme which employs spin exchange at the magic angle under Hartmann-Hahn match. Though PISEMA provides a relatively large scaling factor for the heteronuclear dipolar coupling and a better resolution along the dipolar dimension, it has a few shortcomings. One of the major problems with PISEMA is that the sequence is very much sensitive to proton carrier offset and the measured dipolar coupling changes dramatically with the change in the carrier frequency. The study presented here focuses on modified PISEMA sequences which are relatively insensitive to proton offsets over a large range. In the proposed sequences, the proton magnetization is cycled through two quadrants while the effective field is cycled through either two or four quadrants. The modified sequences have been named as 2(n)-SEMA where n represents the number of quadrants the effective field is cycled through. Experiments carried out on a liquid crystal and a single crystal of a model peptide demonstrate the usefulness of the modified sequences. A systematic study under various offsets and Hartmann-Hahn mismatch conditions has been carried out and the performance is compared with PISEMA under similar conditions.

Infrared spectrum of ferroelectric lithium hydrazinium sulphate [Li (N2H5) SO4]

Dielectric observations on lithium hydrazinium sulphate have shown earlier that it is ferroelectric over a range of temperatures from below −15° C. to above 80° C. and a new type of hydrogen bond rearrangement which would allow the protons to migrate along the chain has also been suggested by others. The infrared spectrum of LiH z S in the form of mull and as single crystal sections parallel and perpendicular to the ‘C’ axis exhibit about 21 well-defined absorption maxima. The position and the width of the maxima agree with the known structure of the crystal according to which the hydrazine group exists in the form of the hydrazinium ion, NH2·NH3+ and the observed N+-H frequencies agree better with the new correlation curve given by R. S. Krishnan and K. Krishnan (1964). However it has been pointed out that from a comparative study of the new infrared spectra of hydrazonium sulphate and lithium ammonium sulphate that the absorption band at 969 cm.−1 is due to N-N stretching vibration and that the fairly intense band between 2050–2170 cm.−1 is due to the bending vibrations of the NH3+ group.

Raman and infra-red spectra of crystalline ammonium sulphamate

Raman spectrum of a single crystal of ammonium sulphamate has been recorded for the two different orientations using λ 2537 resonance radiation of the mercury as the exciter. Thirty-four Raman lines have been observed of which eight belong to the lattice oscillations. Weak hydrogen bonding of NH2 group in the crystal was predicted. The infra-red absorption spectrum of the substance was taken in the powder form in potassium bromide disc, using Carl Zeiss UR10 IR spectrometer. Thirty-five absorption maxima could be identified.

Raman and infra-red spectra of crystalline potassium sulphamate

Raman spectrum of a single crystal of potassium sulphamate has been recorded for the first time using λ 2536 radiation of mercury as the exciter. Thirty-three Raman lines have been observed of which nine belong to the lattice oscillations. The infra-red absorption spectrum of the substance was taken in the powder form in potassium bromide disc using Carl Zeiss UR 10 IR spectrometer. Thirty-six absorption maxima could be identified of which twenty-five have been recorded for the first time. The analysis clearly shows that the N-H bond in the crystalline potassium sulphamate is not hydrogen-bonded to any appreciable extent.