Crystal Structure Dynamics: Evidence by Diffraction and Spectroscopy

Bragg diffraction is a major tool to solve and refine crystal structures, though it is limited as results obtained from the bulk sample are averaged in time and space. In contrast, spectroscopy is site sensitive, and thus a probe for local structure with high time and space resolution. Combination of both methods may reveal important additional information on crystal structures such as disorder and dynamics, and may even help avoid pitfalls in structure solution. Among the given examples are three minerals, i.e., lawsonite, hemimorphite, leonite, which show phase transitions from dynamically disordered to ordered structures. Continuous evolution from order to dynamic disorder, however without a phase transition, is found in washing soda. Finally, examples of proton dynamics in a tetragonal garnet and in minerals with very strong hydrogen bonds are presented

Infrared, Raman and cathodoluminescence studies of impact glasses

We studied the infrared reflectance (IR), Raman, and cathodoluminescence (CL) spectroscopic signatures and scanning electron microscope-cathodoluminescence (SEM-CL) images of three different types of impact glasses: Aouelloul impact glass, a Muong Nong-type tektite, and Libyan desert glass. Both backscattered electron (BSE) and CL images of the Muong Nong-type tektite are featureless; the BSE image of the Libyan desert glass shows only weak brightness contrasts. For the Aouelloul glass, both BSE and CL images show distinct brightness contrast, and the CL images for the Libyan desert glass show spectacular flow textures that are not visible in any other microscopic method. Compositional data show that the SiO2 composition is relatively higher and the Al2O3 content is lower in the CL-bright areas than in the CL-dark regions. The different appearance of the three glass types in the CL images indicates different peak temperatures during glass formation: the tektite was subjected to the highest temperature, and the Aouelloul impact glass experienced a relatively low formation temperature, while the Libyan desert glass preserves a flow texture that is only visible in the CL images, indicating a medium temperature. All IR reflectance spectra show a major band at around 1040 to 1110 cm-1 (antisymmetric stretching of SiO4 tetrahedra), with minor peaks between 745 and 769 cm-1 (Si-O-Si angle deformation). Broad bands at 491 and 821 cm-1 in the Raman spectra in all samples are most likely related to diaplectic glass remnants, indicating early shock amorphization followed by thermal amorphization. The combination of these spectroscopic methods allows us to deduce information about the peak formation temperature of the glass, and the CL images, in particular, show glass flow textures that are not preserved in other more conventional petrographic images

Synthesis, crystal structure and biological activity of copper(II) complex with 4-nitro-3-pyrazolecarboxylic ligand

The reaction of 4-nitro-3-pyrazolecarboxylic acid and Cu(OAc)2⋅H2O in ethanol resulted in a new coordination compound [Cu2(4-nitro-3- -pzc)2(H2O)6]2H2O (4nitro-3pzc = 4-nitro-3-pyrazolecarboxylate). The compound was investigated by means of single-crystal X-ray diffraction and infrared spectroscopy. The biological activity of the complex was also tested. In the crystal structure of [Cu2(4nitro-3-pzc)2(H2O)6]2H2O, the Cu(II) ion is in a distorted [4+2] octahedral coordination due to the Jan–Teller effect. A survey of the Cambridge Structural Database showed that the octahedral coordination geometry is generally rare for pyrazole-bridged Cu(II) complexes. In the case of Cu(II) complexes with the 3-pyrazolecarboxylato ligands, no complexes with a similar octahedral coordination geometry have been reported. Biological research based on determination of the inhibition effect of the commercial fungicide Cabrio top and the newly synthesized complex on Ph. viticola were performed using the phytosanitary method

On hydrogen bond correlations at high pressures

In situ high pressure neutron diffraction measured lengths of O H and H O pairs in hydrogen bonds in substances are shown to follow the correlation between them established from 0.1 MPa data on different chemical compounds. In particular, the conclusion by Nelmes et al that their high pressure data on ice VIII differ from it is not supported. For compounds in which the O H stretching frequencies red shift under pressure, it is shown that wherever structural data is available, they follow the stretching frequency versus H O (or O O) distance correlation. For compounds displaying blue shifts with pressure an analogy appears to exist with improper hydrogen bonds.Comment: 12 pages,4 figure

Raman Spectroscopic and SEM Analysis of Sodium-Zippeite

Raman at 298 and 77 K and infrared spectra of two samples of sodium-zippeite were studied and interpreted. U-O bond lengths in uranyl were calculated and compared with those inferred from the X-ray single crystal structure data of a synthetic sodium-zippeite analog. Hydrogen-bonding network in the studied samples is discussed. O-H…O bond lengths were calculated and compared with those predicted from the X-ray single crystal structure analysis

Raman Spectroscopy of the Sampleite Group of Minerals

Raman and infrared spectroscopy has enabled insights into the molecular structure of the sampleite group of minerals. These minerals are based upon the incorporation of either phosphate or arsenate with chloride anion into the structure and as a consequence the spectra refect the bands attributable to these anions, namely phosphate or arsenate with chloride. The sampleite vibrational spectrum reflects the spectrum of the phosphate anion and consists of ν1 at 964, ν2 at 451 cm-1, ν3 at 1016 and 1088 and ν4 at 643, 604, 591 and 557 cm-1. The lavendulan spectrum consists of ν1 at 854, ν2 at 345 cm-1, ν3 at 878 cm-1 and ν4 at 545 cm-1. The Raman spectrum of lemanskiite is different from that of lavendulan consistent with a different structure. Low wavenumber bands at 227 and 210 cm-1 may be assigned to CuCl TO/LO optic vibrations. Raman spectroscopy identified the substitution of arsenate by phosphate in zdenekite and lavendulan

Redetermination of eveite, Mn2AsO4(OH), based on single-crystal X-ray diffraction data

The crystal structure of eveite, ideally Mn2(AsO4)(OH) [dimanganese(II) arsenate(V) hydroxide], was refined from a single crystal selected from a co-type sample from Långban, Filipstad, Varmland, Sweden. Eveite, dimorphic with sarkinite, is structurally analogous with the important rock-forming mineral andalusite, Al2OSiO4, and belongs to the libethenite group. Its structure consists of chains of edge-sharing distorted [MnO4(OH)2] octa­hedra (..2 symmetry) extending parallel to [001]. These chains are cross-linked by isolated AsO4 tetra­hedra (..m symmetry) through corner-sharing, forming channels in which dimers of edge-sharing [MnO4(OH)] trigonal bipyramids (..m symmetry) are located. In contrast to the previous refinement from Weissenberg photographic data [Moore & Smyth (1968 ▶). Am. Mineral. 53, 1841–1845], all non-H atoms were refined with anisotropic displacement param­eters and the H atom was located. The distance of the donor and acceptor O atoms involved in hydrogen bonding is in agreement with Raman spectroscopic data. Examination of the Raman spectra for arsenate minerals in the libethenite group reveals that the position of the peak originating from the O—H stretching vibration shifts to lower wavenumbers from eveite, to adamite, zincolivenite, and olivenite

Scanning electron microscopy, cathodoluminescence, and Raman spectroscopy of experimentally shock metamorphosed quartzite

We studied unshocked and experimentally (at 12, 25, and 28 GPa, with 25, 100, 450, and 750°C pre-shock temperatures) shock-metamorphosed Hospital Hill quartzite from South Africa using cathodoluminescence (CL) images and spectroscopy and Raman spectroscopy to document systematic pressure or temperature-related effects that could be used in shock barometry. In general, CL images of all samples show CL-bright luminescent patchy areas and bands in otherwise non-luminescent quartz, as well as CL-dark irregular fractures. Fluid inclusions appear dominant in CL images of the 25 GPa sample shocked at 750°C and of the 28 GPa sample shocked at 450°C. Only the optical image of our 28 GPa sample shocked at 25°C exhibits distinct planar deformation features (PDFs). Cathodoluminescence spectra of unshocked and experimentally shocked samples show broad bands in the near-ultraviolet range and the visible light range at all shock stages, indicating the presence of defect centers on, e.g., SiO4 groups. No systematic change in the appearance of the CL images was obvious, but the CL spectra do show changes between the shock stages. The Raman spectra are characteristic for quartz in the unshocked and 12 GPa samples. In the 25 and 28 GPa samples, broad bands indicate the presence of glassy SiO2, while high-pressure polymorphs are not detected. Apparently,some of the CL and Raman spectral properties can be used in shock barometry

The crystal structure of bis[4-bromo-2-(1H-pyrazol-3-yl) phenolato-κ2N,O] copper(II), C18H12Br2CuN4O2

C 18 H 12 Br 2 CuN 4 O 2 , monoclinic, P 2 1 / c (no. 14), a  = 11.5165(11) Å, b  = 5.4369(5) Å, c  = 14.4872(14) Å, V  = 873.52(14) Å 3 , Z  = 2, R gt ( F ) = 0.0232, wR ref ( F 2 ) = 0.0559, T  = 200 K

Pyrosmalite-(Fe), Fe8Si6O15(OH,Cl)10

Pyrosmalite-(Fe), ideally FeII 8Si6O15(OH,Cl)10 [refined composition in this study: Fe8Si6O15(OH0.814Cl0.186)10·0.45H2O, octa­iron(II) hexa­silicate deca­(chloride/hydroxide) 0.45-hydrate], is a phyllosilicate mineral and a member of the pyrosmalite series (Fe,Mn)8Si6O15(OH,Cl)10, which includes pyrosmalite-(Mn), as well as friedelite and mcgillite, two polytypes of pyrosmalite-(Mn). This study presents the first structure determination of pyrosmalite-(Fe) based on single-crystal X-ray diffraction data from a natural sample from Burguillos del Cerro, Badajos, Spain. Pyrosmalite-(Fe) is isotypic with pyrosmalite-(Mn) and its structure is characterized by a stacking of brucite-type layers of FeO6-octa­hedra alternating with sheets of SiO4 tetra­hedra along [001]. These sheets consist of 12-, six- and four-membered rings of tetra­hedra in a 1:2:3 ratio. In contrast to previous studies on pyrosmalite-(Mn), which all assumed that Cl and one of the four OH-groups occupy the same site, our data on pyrosmalite-(Fe) revealed a split-site structure model with Cl and OH occupying distinct sites. Furthermore, our study appears to suggest the presence of disordered structural water in pyrosmalite-(Fe), consistent with infrared spectroscopic data measured from the same sample. Weak hydrogen bonding between the ordered OH-groups that are part of the brucite-type layers and the terminal silicate O atoms is present