Triggering redox activity in a thiophene compound: radical stabilization and coordination chemistry

The synthesis, metalation, and redox properties of an acyclic bis(iminothienyl)methene L− are presented. This π-conjugated anion displays pronounced redox activity, undergoing facile one-electron oxidation to the acyclic, metal-free, neutral radical L* on reaction with FeBr2. In contrast, reaction of L− with CuI forms the unique, neutral Cu2I2(L*) complex of a ligand-centered radical, whereas reaction with the stronger oxidant AgBF4 forms the metal-free radical dication L*2+

New structural data reveal benleonardite to be a member of the pearceite-polybasite group

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A new triclinic modification of the pyrochlore-type KOs2O6 superconductor

A new modification of KOs2O6, the representative of a new structural type (Pearson symbol aP18, a=5.5668(1)A, b=6.4519(2)A, c=7.2356(2)A, space group P-1, no.2) was synthesized employing high pressure technique. Its structure was determined by single-crystal X-ray diffraction. The structure can be described as two OsO6 octahedral chains relating to each other through inversion and forming big voids with K atoms inside. Quantum chemical calculations were performed on the novel compound and structurally related cubic compound. High-pressure X-ray study showed that cubic KOs2O6 phase was stable up to 32.5(2) GPa at room temperature.Comment: 23 pages, 9 figures,6 tables. Accepted for J. Solid State Che

End-to-end thiocyanato-bridged helical chain polymer and dichlorido-bridged copper(II) complexes with a hydrazone ligand: synthesis, characterisation by electron paramagnetic resonance and variable- temperature magnetic studies, and inhibitory effects on human colorectal carcinoma cells

The reactions of the tridentate hydrazone ligand, N’-[1-(pyridin-2-yl)ethylidene]acetohydrazide (HL), obtained by condensation of 2-acetylpyridine with acetic hyadrazide, with copper nitrate trihydrate in the presence of thiocyanate, or with CuCl2 produce two distinct coordination compounds, namely a one-dimensional helical coordination chain of [CuL(NCS)]n (1) units, and a doubly chlorido-bridged dinuclear complex [Cu2L2Cl2] (2) (where L=CH3C(O)=N − N=CCH3C5H4N). Single-crystal X-ray structural determination studies reveal that in complex 1, a deprotonated hydrazone ligand L- coordinates a copper(II) ion that is bridged to two neighbouring metal centres by SCN- anions, generating a one-dimensional helical coordination chain. In complex 2, two symmetry-related, adjacent copper(II) coordination entities are doubly chlorido-bridged, producing a dicopper entity with a Cu···Cu distance of 3.402 (1). The two coordination compounds have been fully characterised by elemental analysis, spectroscopic techniques including IR, UV– vis and electron paramagnetic resonance, and variable-temperature magnetic studies. The biological effects of 1 and 2 on the viability of human colorectal carcinoma cells (COLO-205 and HT-29) were evaluated using an MTT assay, and the results indicate that these complexes induce a decrease in cell-population growth of human colorectal carcinoma cells with apoptosis

Crystal structure of [butane-2,3-dione bis(4-methylthiosemicarbazonato](pyridine)zinc(II)

In the structure of the title complex, [Zn(C8H14N6S2)(C5H5N)], the ZnII ion has a pseudo-square-pyramidal coordination environment and is displaced by 0.490 Å from the plane of best fit defined by the bis­(thio­semicarbazonate) N2S2 donor atoms. Chains sustained by intermolecular N-H...N and N-H...S hydrogen-bonding interactions extend parallel to [10-1]

5-Amino-1-methyl-1H-benzimidazole

The structure of the title compound, C8H9N3, a potential anti­tumour drug, was determined in order to give more insight into its structure–function relationships. The benzimidazole core of the mol­ecule was found to be exactly planar, while the substituents are displaced slightly from the mol­ecular plane [C—C—N—C and C—C—C—N torsion angles of 0.8 (3) and 179.0 (1)° for the methyl and amino groups, respectively]. The bond lengths are analysed in detail and compared with those of the parent unsubstituted analogues. The results show that the lone-pair electrons on the amino N atom are involved in conjugation with the adjacent π system and hence affect the charge distribution in the heterocycle. Two inter­molecular N—H⋯N and C—H⋯N hydrogen bonds have been identified

MgB2 single crystals substituted with Li and with Li-C: Structural and superconducting properties

The effect of Li substitution for Mg and of Li-C co-substitution on the superconducting properties and crystal structure of MgB2 single crystals has been investigated. It has been found that hole doping with Li decreases the superconducting transition temperature Tc, but at a slower rate than electron doping with C or Al. Tc of MgB2 crystals with simultaneously substituted Li for Mg and C for B decreases more than in the case where C is substituted alone. This means that holes introduced by Li cannot counterbalance the effect of decrease of Tc caused by introduction of electrons coming from C. The possible reason of it can be that holes coming from Li occupy the pi band while electrons coming from C fill the sigma band. The temperature dependences of the upper critical field Hc2 for Al and Li substituted crystals with the same Tc show a similar dHc2/dT slope at Tc and a similar Hc2(T) behavior, despite of much different substitution level. This indicates that the mechanism controlling Hc2 and Tc is similar in both hole and electron doped crystals. Electrical transport measurements show an increase of resistivity both in Li substituted crystals and in Li and C co-substituted crystals. This indicates enhanced scattering due to defects introduced by substitutions including distortion of the lattice. The observed behavior can be explained as a result of two effects, influencing both Tc and Hc2. The first one is doping related to the changes in the carrier concentration, which may lead to the decrease or to the increase of Tc. The second one is related to the introduction of new scattering centers leading to the modification of the interband and/or intraband scattering and therefore, to changes in the superconducting gaps and to the reduction of Tc.Comment: 22 pages, 17 figures, submitted to PR

Single-crystal quality data from polycrystalline samples: finding the needle in the haystack

Multi-grain crystallography, traditionally performed at synchrotron sources in association with high-pressure studies, has new relevance with respect to laboratory single-crystal X-ray diffraction, in which crystals can be grown rapidly in situ, and a preliminary dataset analysed and solved in a matter of minutes. Subsequently, a full-sphere of IUCr-quality data can then be collected in a few hours. To demonstrate the applicability of laboratory multi-grain crystallography with Cu Kα X-rays, co-crystals of hexafluorobenzene and pyrrole were grown rapidly by cooling a 1:1 liquid mixture in an X-ray capillary on the diffractometer. The software is able to identify a single unit cell from as few as 10% of the diffraction spots from a small number of diffraction frames. Once a unit cell is identified, a full crystal structure solution is rapidly obtained by collecting a small amount of data to a resolution of ca 1 Å. The co-crystal obtained from the 1:1 mixture showed that hexafluorobenzene and pyrrole crystallize in a 3:4 ratio, in contrast to the columnar 1:1 adduct structures typified by hexafluorobenzene and benzene. The generality of our multi-grain approach for samples that are liquid at room temperature (and form a polycrystalline solid mass on cooling) is further demonstrated by investigating and solving the 1:1 co-crystal formed between hexafluorobenzene and pyridine