ABSTRACT
Reinvestigation of more than 40 samples of minerals belonging to the wagnerite group (Mg, Fe, Mn)2(PO4)(F,OH) from diverse geological environments worldwide, using single-crystal X-ray diffraction analysis, showed that most crystals have incommensurate structures and, as such, are not adequately described with known polytype models (2b), (3b), (5b), (7b) and (9b). Therefore, we present here a unified superspace model for the structural description of periodically and aperiodically modulated wagnerite with the (3+1)-dimensional superspace group C2/c(0ß0)s0 based on the average triplite structure with cell parameters a ≃ 12.8, b ≃ 6.4, c ≃ 9.6â Å, ß ≃ 117° and the modulation vectors q = ßb*. The superspace approach provides a way of simple modelling of the positional and occupational modulation of Mg/Fe and F/OH in wagnerite. This allows direct comparison of crystal properties.
ABSTRACT
Recent research has shown that certain Li-oxide garnets with high mechanical, thermal, chemical, and electrochemical stability are excellent fast Li-ion conductors. However, the detailed crystal chemistry of Li-oxide garnets is not well understood, nor is the relationship between crystal chemistry and conduction behavior. An investigation was undertaken to understand the crystal chemical and structural properties, as well as the stability relations, of Li(7)La(3)Zr(2)O(12) garnet, which is the best conducting Li-oxide garnet discovered to date. Two different sintering methods produced Li-oxide garnet but with slightly different compositions and different grain sizes. The first sintering method, involving ceramic crucibles in initial synthesis steps and later sealed Pt capsules, produced single crystals up to roughly 100 µm in size. Electron microprobe and laser ablation inductively coupled plasma mass spectrometry (ICP-MS) measurements show small amounts of Al in the garnet, probably originating from the crucibles. The crystal structure of this phase was determined using X-ray single-crystal diffraction every 100 K from 100 K up to 500 K. The crystals are cubic with space group Ia3Ì d at all temperatures. The atomic displacement parameters and Li-site occupancies were measured. Li atoms could be located on at least two structural sites that are partially occupied, while other Li atoms in the structure appear to be delocalized. (27)Al NMR spectra show two main resonances that are interpreted as indicating that minor Al occurs on the two different Li sites. Li NMR spectra show a single narrow resonance at 1.2-1.3 ppm indicating fast Li-ion diffusion at room temperature. The chemical shift value indicates that the Li atoms spend most of their time at the tetrahedrally coordinated C (24d) site. The second synthesis method, using solely Pt crucibles during sintering, produced fine-grained Li(7)La(3)Zr(2)O(12) crystals. This material was studied by X-ray powder diffraction at different temperatures between 25 and 200 °C. This phase is tetragonal at room temperature and undergoes a phase transition to a cubic phase between 100 and 150 °C. Cubic "Li(7)La(3)Zr(2)O(12)" may be stabilized at ambient conditions relative to its slightly less conducting tetragonal modification via small amounts of Al(3+). Several crystal chemical properties appear to promote the high Li-ion conductivity in cubic Al-containing Li(7)La(3)Zr(2)O(12). They are (i) isotropic three-dimensional Li-diffusion pathways, (ii) closely spaced Li sites and Li delocalization that allow for easy and fast Li diffusion, and (iii) low occupancies at the Li sites, which may also be enhanced by the heterovalent substitution Al(3+) â 3Li.
ABSTRACT
Yellowish elongated crystals of the two new compounds Pb6LaO7Br (1) and Pb6LaO7Cl (2) have been obtained by the method of solid-state reactions. Both structures can be described in the terms of oxo-centered tetrahedra. The structures of 1 and 2 consist of [O7Pb6La]+ chains that are built from oxocentered OA4 (A = Pb, La) tetrahedra. The halogen ions connect the chains through weak Pb-X bonds. An arrangement of eight OA4 tetrahedra that all share the same central La atom forms a [O8Pb10La3]13+ cluster. The clusters are linked into chains, and additional OPb4 tetrahedra are attached to the chains. Incorporation of Cl atoms instead of Br atoms into the structure causes a lowering of the symmetry from Cmcm to C2/m.
Subject(s)
Halogens/chemistry , Lead/chemistry , Metals, Rare Earth/chemistry , Crystallography, X-Ray , Models, MolecularABSTRACT
Starting from dehydroepiandrosterone (1) 17-picolyl (2), 17-picolinylidene (7), 17-picolinylidene-16-one (10 and 11), and 17-picolyl-16-one (15) derivatives of androst-5-ene were synthesized in one, two, four and five steps respectively. By the Oppenauer oxidation or dehydration of 2, 7, 10, and 11 with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), the corresponding A and B ring modified derivatives 3, 5, 6, 8, 9, and 12-14 were obtained. The structure of 2 was unambiguously proved by the appropriate X-ray structural analysis. Compounds 3, 5, 9, 12-14 showed inhibitory activity against the enzyme aromatase. Antibacterial activity, toxicity to brine shrimp Artemia salina, antitumor activity against three tumor cell lines (human cervix carcinoma HeLa cells, human melanoma FemX cells, and human myelogenous leukemia K562 cells) and toxicity against peripheral blood mononuclear cells were evaluated. Three tested compounds, namely 11, 13, and 15, showed strong activity against all three cell lines, the IC(50) values being in the range of 4-10 microM.
