The crystal and magnetic structure of Li-aegirine LiFe3+Si2O6: a temperature-dependent study

Single crystals of Li-aegirine LiFe³⁺Si₂O₆ were synthesized at 1573?K and 3?GPa, and a polycrystalline sample suitable for neutron diffraction was produced by ceramic sintering at 1223?K. LiFe³⁺Si₂O₆ is monoclinic, space group C2/c, a=9.6641(2)?Å, b= 8.6612(3)?Å, c=5.2924(2)?Å, β=110.12(1)^° at 300?K as refined from powder neutron data. At 229?K Li-aegirine undergoes a phase transition from C2/c to P2₁ /c. This is indicated by strong discontinuities in the temperature variation of the lattice parameters, especially for the monoclinic angle β and by the appearance of Bragg reflections (hkl) with h+k≠2n. In the low-temperature form two non-equivalent Si-sites with 〈SiA–O〉=1.622?Å and 〈SiB–O〉=1.624?Å at 100?K are present. The bridging angles of the SiO₄ tetrahedra O3–O3–O3 are 192.55(8)° and 160.02(9)° at 100?K in the two independent tetrahedral chains in space group P2₁ /c, whereas it is 180.83(9)° at 300?K in the high-temperature C2/c phase, i.e. the chains are nearly fully expanded. Upon the phase transition the Li-coordination changes from six to five. At 100?K four Li–O bond lengths lie within 2.072(4)–2.172(3)?Å, the fifth Li–O bond length is 2.356(4)?Å, whereas the Li–O3?A bond lengths amount to 2.796(4)?Å. From ⁵⁷Fe Mössbauer spectroscopic measurements between 80 and 500?K the structural phase transition is characterized by a small discontinuity of the quadrupole splitting. Temperature-dependent neutron powder diffraction experiments show first occurrence of magnetic reflections at 16.5?K in good agreement with the point of inflection in the temperature-dependent magnetization of LiFe³⁺Si₂O₆. Distinct preordering phenomena can be observed up to 35?K. At the magnetic phase transition the unit cell parameters exhibit a pronounced magneto-striction of the lattice. Below T _N Li-aegirine shows a collinear antiferromagnetic structure. From our neutron powder diffraction experiments we extract a collinear antiferromagnetic spin arrangement within the a–c plane.     

Eifelite,KNa3Mg4Si12O30, a new mineral of the osumilite group with octahedral sodium

Eifelite of variable composition is uniaxial positive withn ₀ near 1.543 andn _e near 1.544, a between 10.14 and 10.15 Å, andc about 14.22 Å, space groupP 6/m 2/c 2/c. There is a complete series of solid solution between the eifelite end member KNa₃Mg₄Si₁₂O₃₀ and roedderite, KNaMg₅Si₁₂O₃₀, following the 2 Na?Mg substitution. Both eifelite and roedderite have milarite-type structures, but Na is always in six-coordinated sites: In roedderite Na occupies solely a newly defined B′^[6]-position which is slightly displaced alongc from the ideal B_[9]-position lying on the (001/2)-mirror plane in K₂Mg₅Si₁₂O₃₀. In eifelite Na is located both inB′^[6] and in theA _[6]-positions, where it partially replaces Mg. Eifelite has the highest cation occupancy of all osumilite group minerals known thus far. Both eifelite and roedderite occur in vesicles of contact metamorphosed basement xenoliths ejected with the leucite tephrite lava of the Quaternary Bellerberg volcano in the Eifel, West Germany. They are considered to be precipitates from highly alkaline, MgSi-rich, but Al-deficient gas phases that originated through interaction of gaseous igneous differentiates with the xenoliths.     

Ab initio calculated geometries and charge distributions for H4SiO4 and H6Si2O7 compared with experimental values for silicates and siloxanes

Ab initio STO-3G molecular orbital theory has been used to calculate energy-optimized Si-O bond lengths and angles for molecular orthosilicic and pyrosilicic acids. The resulting bond length for orthosilicic acid and the nonbridging bonds for pyrosilicic acid compare well with Si-OH bonds observed for a number of hydrated silicate minerals. Minimum energy Si-O bond lengths to the bridging oxygen of the pyrosilicic molecule show a close correspondence with bridging bond length data observed for the silica polymorphs and for gas phase and molecular crystal siloxanes when plotted against the SiOSi angle. In addition, the calculations show that the mean Si-O bond length of a silicate tetrahedron increases slightly as the SiOSi angle narrows. The close correspondence between the Si-O bond length and angle variations calculated for pyrosilicic acid and those observed for the silica polymorphs and siloxanes substantiates the suggestion that local bonding forces in solids are not very different from those in molecules and clusters consisting of the same atoms with the same coordination numbers. An extended basis calculation for H₄SiO₄ implies that there are about 0.6 electrons in the 3d-orbitals on Si. An analysis of bond overlap populations obtained from STO-3G* calculations for H₆Si₂O₇ indicates that Si-O bond length and SiOSi angle correlations may be ascribed to changes in the hybridization state of the bridging oxygen and (d – p) π-bonding involving all five of the 3d AO's of Si and the lone-pair AO's of the oxygen. Theoretical density difference maps calculated for H₆Si₂O₇ show a build-up of charge density between Si and O, with the peak-height charge densities of the nonbridging bonds exceeding those of the bridging bonds by about 0.05 e Å^?3. In addition, atomic charges (+1.3 and ?0.65) calculated for Si and O in a SiO₂ moiety of the low quartz structure conform reasonably well with the electroneutrality postulate and with experimental charges obtained from monopole and radial refinements of diffraction data recorded for low quartz and coesite.     

Crystal chemical characteristics of α-CaSi2O5, a new high pressure calcium silicate with five-coordinated silicon synthesized at 1500°C and 10 GPa

The crystal structure of α-CaSi₂O₅ synthesized at conditions of 1500°C and 10 GPa, has been solved and refined in centrosymmetric space group P , using single crystal X-ray diffraction data. The composition (Z=4) and unit cell are Ca_1.02Si_1.99O₅ by EPMA analysis and a=7.243(2) Å, b=7.546(4) Å, c=6.501(4) Å, α=81.43(5)°, β=84.82(4)°, γ=69.60(3)°, V=329.5(3) ų, yielding the density value, 3.55 g/cm³. The structure is closely related to that of titanite, CaTiSiO₅ and features the square-pyramid five-fold coordination of silicon by oxygen. The ionic radius for five-coordinated Si calculated from the bond distances is 0.33 Å. The substantial deviation of valence sum for Ca indicates the existence of local strain and the instability of α-CaSi₂O₅ at room pressure.     

Three cubic phases intergrown in a birefringent andradite-grossular garnet and their implications

The crystal chemistry across the garnet series is examined, and several systematic trends are reported. The crystal structure of three different cubic phases intergrown in a birefringent near end-member andradite from Namibia was refined by the Rietveld method, space group $ Ia\bar{3}d, $ Ia 3 ¯ d , and monochromatic synchrotron high-resolution powder X-ray diffraction data. Electron microprobe results indicate three phases with distinct compositions. The sample is birefringent, indicating that it is not cubic when observed optically. The reduced χ ² and overall R (F ²) Rietveld refinement values are 1.655 and 0.0284, respectively, so the multi-phase refinement is excellent. The composition, weight %, unit-cell parameter (Å), distances (Å), and site-occupancy factors (sofs) are as follows: phase-1, Adr₉₉, 88.5(1)  %, a = 12.06259(1), average 〈Ca–O〉 = 2.4310, Fe–O = 2.0189(4), Si–O = 1.6490(4) Å, Ca(sof) = 0.948(1), Fe(sof) = 0.934(1), and Si(sof) = 0.940(1). For phase-2: Adr₇₁Grs₂₈, 7.1(1) %, a = 12.00361(5), average 〈Ca–O〉 = 2.440, Fe–O = 1.979(3), Si–O = 1.641(3) Å, Ca(sof) = 0.913(5), Fe(sof) = 0.767(4), and Si(sof) = 0.932(5). For phase-3: Grs₇₉Adr₁₇, 4.4(1) %, a = 11.89719(4), average 〈Ca–O〉 = 2.404, Al–O = 1.935(4), Si–O = 1.667(3) Å, Ca(sof) = 0.944(6), Al(sof) = 1.069(7), and Si(sof) = 0.887(5). The dominant phase-1 (89 %; Adr₉₉) is nearly end-member andradite, Ca₃Fe ₂ ³⁺ Si₃O₁₂, which contains no cation order in the Ca(X) or Fe(Y) sites. The intergrowth of the three cubic phases causes considerable strain in the minor phases-2 and phases-3 that arise from different structural parameters and gives rise to strain-induced birefringence. For comparison, the results for an isotropic, single-phase, grossular–andradite garnet (Grs₇₆Adr₂₁) are also presented. The strain in the minor phases is about 3–5 times more than the unstrained dominant phase-1, or the unstrained single-phase grossular–andradite.     

Structure-composition relations and Raman spectroscopy of high-pressure sodium silicates

?-Na₂Si₂O₅, ζ-Na₂Si₂O₅, Na₂Si[Si₂O₇], and Na₆Si₃[Si₉O₂₇] have been synthesized using an MA6/8 superpress. Densification in high-pressure sodium silicates is effected largely by changes in packing. In the relaxed (1 bar) structures, cation polyhedra and thermal/displacement parameters are similar to those of low-pressure silicates, but the extra-framework cation positions are oversized. The two mixed ^[4]Si and ^[6]Si framework silicates of known structure (Na₂Si[Si₂O₇] and Na₆Si₃[Si₉O₂₇]) belong to the limited homologous series Na_2mSi_m[Si_n–mO_2n+m], with m<n. The structure-composition relationships of wadeite-type, A₂Ge₄O₉-type, and Na₆Si₃[Si₉O₂₇] silicates and germanates depend on T-O distance and size of the large extra-framework cation. Characteristic features of the SiO₄ tetrahedral units are present in micro-Raman spectra of mixed ^[4]Si and ^[6]Si framework silicates, but bands uniquely attributable to SiO₆ octahedra are weak or obscured. However, ^[6]Si has a profound indirect influence on the Raman spectra, resulting in intense and complex low-frequency bands, assigned to symmetric bending modes with coupled displacements at both bridging oxygens and nonbridging oxygens bonded to ^[6]Si, and a shift to higher frequency and reduction in intensity of the high-frequency bands assigned to symmetric ^[4]Si-O_nbr stretching vibrations. Raman spectroscopy does not appear to be a useful structural probe for small amounts of ^[6]Si in silicate glasses and melts.     

Structural characterization of high-pressure C–Na<Subscript>2</Subscript>Si<Subscript>2</Subscript>O<Subscript>5</Subscript> by single-crystal diffraction and <Superscript>29</Superscript>Si MAS NMR

Single crystals of C–Na₂Si₂O₅ have been synthesized from the hydrothermal recrystallization of a glass. The title compound is monoclinic, space group P2₁/c with Z= 8 and unit-cell parameters a= 4.8521 (4)Å, b=23.9793(16)Å, c=8.1410(6)Å, β=90.15(1)° and V=947.2(2)ų. The structure has been determined by direct methods and belongs to the group of phyllosilicates. It is based on layers of tetrahedra with elliptically six-membered rings in chair conformation. The sequence of directedness within a single ring is UDUDUD. The sheets are parallel to (010) with linking sodium cations in five- and sixfold coordination. Concerning the shape and the conformation of the rings, C–Na₂Si₂O₅ is closely related to β-Na₂Si₂O₅. However, both structures differ in the stacking sequences of the layers. A possible explanation for the frequently observed polysynthetic twinning of phase C is presented. In the ²⁹Si MAS-NMR spectrum of C–Na₂Si₂O₅ four well-resolved lines of equal intensity are observed at ?86.0, ?86.3, ?87.4, and ?88.2?ppm. The narrow range of isotropic chemical shifts reflects the great similarity of the environments of the different Si sites. This lack of pronounced differences in geometry renders a reliable assignment of the resonance lines to the individual sites on the basis of known empiric correlations and geometrical features impossible.     

Disorder and successive structure transitions in the tridymite forms of SiO2

Disorder models of oxygen positions in P6₃/ mmc, C222₁ and P2₁2₁2₁ tridymites were given in applying geometrical and lattice dynamical calculations. Sixmembered rings of rigid SiO₄ units are all collapsed in these forms; with silicon atoms fixed, SiO₄ units can take six different orientations in forming tridymite frameworks in both the P6₃/mmc and C222₁ forms, and three orientations in the P2₁2₁2₁ form. Atomic distances and angles obtained from the distance least-squares method are about equal for the three forms: 〈Si-O〉 (mean Si-O) = 1.611 Å, 〈O-O〉 = 2.629 Å, and 〈Si-O-Si〉 = 147°. Domain formation models are given for the three forms. The tridymite framework structures may possibly undergo lattice vibrations with low frequencies in two kinds of pair-wise rotational modes of SiO₄ units joined by the apical oxygen atoms, at the Γ-point: one is around 〈100〉 (or 〈210〉 for the hexagonal case), and the other is around 〈010〉. As temperature approaches the hexagonal-orthorhombic transition from below, the rotational mode around 〈100〉 remarkably softens at the Γ-point. The behavior of the atoms at the hexagonal-orthorhombic transition is explained in terms of a coupled softening of the two rotational modes of neighboring local domains in different orientations.     

High pressure single-crystal synthesis, structure and compressibility of the garnet Mn2+ 3Mn3+ 2[SiO4]3

Single crystals of the garnet Mn²⁺ ₃Mn³⁺ ₂[SiO₄]₃ and coesite were synthesised from MnO₂-SiO₂ oxide mixtures at 1000°C and 9 GPa in a multianvil press. The crystal structure of the garnet [space group Ia3¯d, a=11.801(2) Å] was refined at room temperature and 100 K from single-crystal X-ray data to R1=2.36% and R1=2.71%, respectively. In contrast to tetragonal Ca₃Mn³⁺ ₂[GeO₄]₃ (space group I4₁/a), the high-pressure garnet is cubic and does not display an ordered Jahn-Teller distortion of octahedral Mn³⁺. A disordered Jahn-Teller distortion either dynamic or static is evidenced by unusual high anisotropic displacement parameters. The room temperature structure is characterised by following bond lengths: Si-O=1.636(4) Å (tetrahedron), Mn³⁺-O=1.995 (4) Å (octahedron), Mn²⁺-O=2.280(5) and 2.409(4) Å (dodecahedron). The cubic structure was preserved upon cooling to 100 K [a=11.788(2) Å] and upon compressing up to 11.8 GPa in a diamond-anvil cell. Pressure variation of the unit cell parameter expressed by a third-order Birch-Murnaghan equation of state led to a bulk modulus K ₀=151.6(8) GPa and its pressure derivatives K′=6.38(19). The peak positions of the Raman spectrum recorded for Mn²⁺ ₃Mn³⁺ ₂[SiO₄]₃ were assigned based on a calderite Mn²⁺ ₃Fe³⁺ ₂[SiO₄]₃ model extrapolated from andradite and grossular literature data.     

Structural characterisation of the high-pressure phase CaAl4Si2O11

Single crystals of CaAl₄Si₂O₁₁ were synthesised at 1,500?°C and 14 GPa in a multi-anvil press, and the structure of the phase determined by single-crystal X-ray diffraction at room conditions. The structure-type is that of the “hexagonal barium ferrites”. The space group of the average structure is P6 ₃ /mmc and the cell parameters are a?=?5.4223(4) Å, c?=?12.7041(6) Å, V?=?323.28(5) ų, with Z?=?2, and its density is 3.905?g?cm^?3, which is reasonable for a high-pressure alumino-silicate phase. The 22 oxygen and two calcium atoms within the unit-cell form an approximate hexagonal-close-packed array. Ten of the twelve octahedral interstices within this array that have only oxygen atoms for apices are filled with Si and/or Al. M1 octahedra share edges to form a spinel-like sheet of octahedra. The average bond length ?=?1.833 Å suggests mixed occupancy by Si and Al. The M1 octahedral sheets are linked by shared corners to pairs of face-sharing M2 octahedra containing Al, with ?= 1.918 Å. The remaining two cations of the unit-cell contents statistically occupy four tetrahedrally-coordinated interstices, which occur as face-sharing pairs. The average bond length for these sites (1.742 Å) suggests that they are occupied by Al, although Si occupancy cannot be excluded by the data. It is proposed that only one interstice of each pair is locally occupied, with the possibility of some short-range ordering of such occupancies. Complete long-range order leading to the acentric space group P6 ₃ mc is excluded by the data, as is the possibility of the average structure being comprised of merohedral (0?0?0?1) twins of P6 ₃ mc symmetry.     

Friedrichbeckeite, K (□0.5Na0.5)2 (Mg0.8Mn0.1Fe0.1)2 (Be0.6 Mg0.4)3 [Si12O30], a new milarite-type mineral from the Bellerberg volcano, Eifel area, Germany

Friedrichbeckeite is a new milarite-type mineral. It was found in a single silicate-rich xenolith from a quarry at the Bellerberg volcano near Ettringen, eastern Eifel volcanic area, Germany. It forms thin tabular crystals flattened on {0001}, with a maximum diameter of 0.6 mm and a maximum thickness of 0.1 mm. It is associated with quartz, tridymite, augite, sanidine, magnesiohornblende, enstatite, pyrope, fluorapatite, hematite, braunite and roedderite. Friedrichbeckeite is light yellow, with white to light cream streak and vitreous lustre. It is brittle with irregular fracture and no cleavage, Mohs hardness of 6, calculated density is 2.686 gcm^?3. Optically, it is uniaxial positive with n_ω = 1.552(2) and n_ε = 1.561(2) at 589.3 nm and a distinct pleochroism from yellow (//ω) to light blue (//ε). Electron microprobe analyses yielded (wt.%): Na₂O 2.73, K₂O 4.16, BeO 4.67, MgO 11.24, MnO 2.05, FeO 1.76, Al₂O₃ 0.15, SiO₂ 73.51, (Σ CaO, TiO₂ = 0.06) sum 100.33 (BeO determined by LA-ICP-MS). The empirical formula based on Si = 12 is K_0.87 Na_0.86 (Mg_1.57Mn_0.28Fe_0.24)_Σ2.09 (Be_1.83?Mg_1.17)_Σ3.00 [Si₁₂O₃₀], and the simplified formula can be given as K (□_0.5Na_0.5)₂ (Mg_0.8Mn_0.1Fe_0.1)₂ (Be_0.6?Mg_0.4)₃ [Si₁₂O₃₀]. Friedrichbeckeite is hexagonal, space-group P6/mcc, with a = 9.970(1), c = 14.130(3) Å, V = 1216.4(3) ų, and Z = 2. The strongest lines in the X-ray powder diffraction pattern are (d in Å / I _obs / hkl): 3.180 / 100 / 121, 2.885 / 70 / 114, 4.993 / 30 / 110, 4.081 / 30 / 112, 3.690 / 30 / 022. A single-crystal structure refinement (R1 = 3.62 %) confirmed that the structure is isotypic with milarite and related ^[12] C ^[9] B ₂ ^[6] A ₂ ^[4] T2₃ [^[4] T1₁₂O₃₀] compounds. The C-site is dominated by potassium, the B-site is almost half occupied by sodium, and the A-site is dominated by Mg. The site-scattering at the T2-site can be refined to a Be/(Be?+?Mg) value close to 0.61; the T1-site is occupied by Si. Micro-Raman spectroscopy reveals an increasing splitting of scattering bands around 550 cm^?1 for friedrichbeckeite. The mineral can be classified as an unbranched ring silicate or as a beryllo-magnesiosilicate. With respect to the end-member formula K (□0.5Na0.5)₂ Mg₂ Be₃ [Si₁₂O₃₀] friedrichbeckeite represents the Mg-dominant analogue of almarudite, milarite or oftedalite. The mineral and its paragenesis were formed during pyrometamorphic modifications of the silicate-rich xenoliths enclosed in Quaternary leucite-tephritic lava of the Bellerberg volcano. Holotype material of friedrichbeckeite has been deposited at the mineral collection of the Naturhistorisches Museum Wien, Austria. The mineral is named friedrichbeckeite in honour of the Austrian mineralogist and petrographer Friedrich Johann Karl Becke (1855–1931).     

The crystal chemistry of mordenites

Mordenite is a zeolite whose approximate composition is (Na₂, K₂,Ca)₄[Al₈Si₄₀O₉₆] 28 H₂O. Unit cell dimensions, determined by X-ray powder diffractometry for 35 natural samples, fell within the following ranges: a=18.052–18.168, b=20.404–20.527, c=7.501–7.537 Å. The indexed powder pattern of a typical sample is reported. Complete wet chemical analyses of 12 samples, partial analyses of three others, and 6 analyses from the literature reveal that mordenites vary only slightly in chemical composition. Si occupies 80 to 85% of the tetrahedra, and the exchangeable cations are mainly Na and Ca, with minor K. The lattice constant b is negatively correlated to the ratio Si/(Si+Al+Fe?).     

Chromium solubility in anhydrous Phase B

The crystal structure and chemical composition of a crystal of (Mg_14?x Cr _x )(Si_5?x Cr _x )O₂₄ (x ≈ 0.30) anhydrous Phase B (Anh-B) synthesized in the model system MgCr₂O₄–Mg₂SiO₄ at 12 GPa and 1600 °C have been investigated. The compound was found to be orthorhombic, space group Pmcb, with lattice parameters a = 5.900(1), b = 14.218(2), c = 10.029(2) Å, V = 841.3(2) Å³ and Z = 2. The structure was refined to R ₁ = 0.065 using 1492 independent reflections. Chromium was found to substitute for both Mg at the M3 site (with a mean bond distance of 2.145 Å) and Si at the octahedral Si1 site (mean bond distance: 1.856 Å), according to the reaction Mg²⁺ + Si⁴⁺ = 2Cr³⁺. Such substitutions cause a reduction in the volume of the M3 site and an increase in the volume of the Si-dominant octahedron with respect to the values typically observed for pure Anh-B and Fe²⁺-bearing Anh-B. Taking into account that Cr³⁺ is not expected to be Jahn–Teller active, it appears that both the Cr³⁺–for–Mg and Cr³⁺–for–Si substitutions in the Anh-B structure decrease the distortion of the octahedra. Electron microprobe analysis gave the Mg_13.66(8)Si_4.70(6)Cr_0.62(4)O₂₄ stoichiometry for the studied phase. The successful synthesis of this phase provides new information for the possible mineral assemblages occurring in the Earth’s deep upper mantle and shed new light on the so-called X discontinuity that has been observed at 275–345 km depth in several subcontinental and subduction zone environments.     

Ab initio calculation of interatomic force constants in H6Si2O7 and the bulk modulus of α quartz and α cristobalite

Ab initio force constants calculated for Si-O stretch and Si...Si non-bonded interactions in H₆Si₂O₇ are found comparable with experimental values derived from the lattice dynamics of α quartz. The bulk moduli of α quartz and α cristobalite are calculated using the molecular Si...Si force constant and assuming rigid regular SiO₄ tetrahedra. In the case (α quartz) where data are available the calculation agrees well with experiment.     

The thermal expansion of synthetic aluminosilicate-sodalites,M 8(Al6Si6O24)X 2

Thermal expansion data, determined by powder X-ray diffraction methods are presented for 11 members of the (Li,Na,K,Rb)₈(Al₆Si₆O₂₄)Cl₂ solid solution series, 3 members of the (Na,K)₈(Al₆Si₆O₂₄)Br₂ solid solution series and Na₈(Al₆Si₆O₂₄)I₂. Only the latter showed a discontinuity in its expansion curve at 810° C wigh a mean linear expansion coefficient of 22.0×10^?6 °C^?1 below and 7.7×10^?6 °C^?1 above the discontinuity. The mean expansion coefficients from 0° to 500° C decrease gradually over the range of room temperature cell edges from 8.4 to 8.89 Å, then increase up to a cell edge of 9.01 Å above which they decrease sharply and extrapolate to a zero coefficient at 9.4 Å. These variations may be related to the expansion characteristics of the bonds between the cavity cations and cavity anions in different sodalites. The aluminosilicate-sodalites which show a discontinuity in their thermal expansion curves are those with large cavity anions, I^? or SO ₄ ^2? ; the discontinuity is believed to occur at the point when the x-coordinate of the cavity cation becomes 0.25.     

On the crystal chemistry and elastic behavior of a phlogopite 3<Emphasis Type="Italic">T</Emphasis>

The crystal chemistry and the elastic behavior under isothermal conditions up to 9 GPa of a natural, and extremely rare, 3T-phlogopite from Traversella (Valchiusella, Turin, Western Alps) [(K_0.99Na_0.05Ba_0.01)(Mg_2.60Al_0.20Fe _0.21 ²⁺ )[Si_2.71Al_1.29O₁₀](OH)₂, space group P3₁12, with a = 5.3167(4), c = 30.440(2) Å, and V = 745.16(9) ų] have been investigated by electron microprobe analysis in wavelength dispersion mode, single-crystal X-ray diffraction at 100 K, and in situ high-pressure synchrotron radiation powder diffraction (at room temperature) with a diamond anvil cell. The single-crystal refinement confirms the general structure features expected for trioctahedral micas, with the inter-layer site partially occupied by potassium and sodium, iron almost homogeneously distributed over the three independent octahedral sites, and the average bond distances of the two unique tetrahedra suggesting a disordered Si/Al-distribution (i.e., 〈T1-O〉 ~ 1.658 and 〈T2-O〉 ~ 1.656 Å). The location of the H-site confirms the orientation of the O–H vector nearly perpendicular to (0001). The refinement converged with R ₁(F) = 0.0382, 846 unique reflections with F _O > 4σ(F _O) and 61 refined parameters, and not significant residuals in the final difference-Fourier map of the electron density (+0.77/?0.37 e ^?/ų). The high-pressure experiments showed no phase transition within the pressure range investigated. The P–V data were fitted with a Murnaghan (M-EoS) and a third-order Birch-Murnaghan equation of state (BM-EoS), yielding: (1) M-EoS, V ₀ = 747.0(3) ų, K _T0 = 44.5(24) GPa, and K′ = 8.0(9); (2) BM-EoS, V ₀ = 747.0(3) ų, K _T0 = 42.8(29) GPa, and K′ = 9.9(17). A comparison between the elastic behavior in response to pressure observed in 1M- and 3T-phlogopite is made.     

Ion exchange between tectosilicates with the nepheline-kalsilite framework and molten MNO3 or MO (M = Li,Na, K,Ag)

Natural nepheline, a synthetic Na-rich nepheline, and synthetic kalsilite were ion exchanged in molten MNO₃ or MCl (M = Li, Na, K, Ag) at 220–800° C. Crystalline products were characterized by wet chemical and electron microprobe analysis, single crystal and powder X-ray diffraction, and transmission electron microscopy and diffraction. Two new compounds were obtained: Li-exchanged nepheline with a formula near (Li,K_0.3,□)Li₃[Al₃(Al,Si)Si₄O₁₆] and a monoclinic unit cell with a = 951.0(6) b = 976.1(6) c = 822.9(5)pm γ = 119.15°, and Ag-exchanged nepheline with a formula near (K,Na,□)Ag₃[Al₃(Al,Si)Si₄O₁₆] and a hexagonal unit cell with a = 1007.4(8) c = 838.2(1.0) pm. Both compounds apparently retain the framework topology of the starting material. Ion exchange isotherms and structural data show that immiscibility between the end members is a general feature in the systems Na-Li, Na-Ag, and Na-K. For the system Na-K, a stepwise exchange is observed with (K,D)Na₃[Al₃(Al,Si)Si₄O₁₆] as an intermediate composition which has the nepheline structure and is miscible with the sodian end member (Na,□)Na₃[Al₃(Al,Si)Si₄O₁₆], but not with the potassian end member (K,□)₄[Al₃(Al,Si)Si₄O₁₆] which shows the kalsilite structure; there was no indication for the formation of trior tetrakalsilite (K/(K + Na)≈0.7) at the temperatures studied (350 and 800° C). The exact amount of vacancies □ on the alkali site depends upon the starting material and was found to be conserved during exchange, with ca 0–0.2 and 0.3–0.4 vacancies per 16 oxygen atoms for the synthetic and natural precursors, respectively. Thermodynamic interpretation of the Na-K exchange isotherms shows, as one important result, that the sodian end member is unstable with respect to the intermediate at K/(K+Na)≈0.25 by an amount of ca 45 kJ/mol Na in the large cavity at 800° C (52 kJ/mol at 350° C).     

Tatarinovite Са<Subscript>3</Subscript>Al(SO<Subscript>4</Subscript>)[В(ОH)<Subscript>4</Subscript>](ОH)<Subscript>6</Subscript> · 12H<Subscript>2</Subscript>O,a new ettringite-group mineral from the Bazhenovskoe deposit,Middle Urals,Russia, and its crystal structure

A new mineral, tatarinovite, ideally Са₃Аl(SO₄)[В(ОН)₄](ОН)₆ · 12Н₂O, has been found in cavities of rhodingites at the Bazhenovskoe chrysotile asbestos deposit, Middle Urals, Russia. It occurs (1) colorless, with vitreous luster, bipyramidal crystals up to 1 mm across in cavities within massive diopside, in association with xonotlite, clinochlore, pectolite and calcite, and (2) as white granular aggregates up to 5 mm in size on grossular with pectolite, diopside, calcite, and xonotlite. The Mohs hardness is 3; perfect cleavage on (100) is observed. D _meas = 1.79(1), D _calc = 1.777 g/cm³. Tatarinovite is optically uniaxial (+), ω = 1.475(2), ε = 1.496(2). The IR spectrum contains characteristic bands of SO₄ ^2?, CO₃ ^2?, B(OH)₄ ^?, B(OH)₃, Al(OH)₆ ^3-, Si(OH)₆ ^2-, OH^–, and H₂O. The chemical composition of tatarinovite (wt %; ICP-AES; H₂O was determined by the Alimarin method; CO₂ was determined by selective sorption on askarite) is as follows: 27.40 CaO, 4.06 B₂O₃, 6.34 A1₂O₃, 0.03 Fe₂O₃, 2.43 SiO₂, 8.48 SO₃, 4.2 CO₂, 46.1 H₂O, total is 99.04. The empirical formula (calculated on the basis of 3Ca apfu) is H_31.41Ca_3.00(Al_0.76Si_0.25)_Σ1.01 · (B_0.72S_0.65C_0.59)Σ_1.96O_24.55. Tatarinovite is hexagonal, space gr. P6₃, a = 11.1110(4) Å, c = 10.6294(6) Å, V = 1136.44(9) A³, Z = 2. Its crystal chemical formula is Са₃(Аl_0.70Si_0.30) · {[SO₄]_0.34[В(ОН)₄]_0.33[СO₃]0.₂₄}{[SO₄]_0.30[В(ОН)₄]_0.34[СО₃]_0.30[В(ОН)₃]_0.06}(ОН_5·73О_0.27) · 12Н₂O. The strongest reflections of the powder X-ray diffraction pattern [d, Å (I, %) (hkl)] are 9.63 (100) (100), 5.556 (30) (110), 4.654 (14) (102), 3.841 (21) (112), 3.441 (12) (211), 2.746 (10) (302), 2.538 (12) (213). Tatarinovite was named in memory of the Russian geologist and petrologist Pavel Mikhailovich Tatarinov (1895–1976), a well-known specialist in chrysotile asbestos deposits. Type specimens have been deposited at the Fersman Mineralogical Museum of the Russian Academy of Sciences, Moscow.     

Thermal expansion of hydrated six-coordinate silicon in thaumasite,Ca<Subscript>3</Subscript>Si(OH)<Subscript>6</Subscript>(CO<Subscript>3</Subscript>)(SO<Subscript>4</Subscript>)·12H<Subscript>2</Subscript>O

Thaumasite, Ca₃Si(OH)₆(CO₃)(SO₄)12H₂O, occurs as a low-temperature secondary alteration phase in mafic igneous and metamorphic rocks, and is recognized as a product and indicator of sulfate attack in Portland cement. It is also the only mineral known to contain silicon in six-coordination with hydroxyl (OH)^? that is stable at ambient P–T conditions. Thermal expansion of the various components of this unusual structure has been determined from single-crystal X-ray structure refinements of natural thaumasite at 130 and 298 K. No phase transitions were observed over this temperature range. Cell parameters at room temperature are: a= 11.0538(6) Å, c=10.4111(8) Å and V=1101.67(10) ų, and were measured at intervals of about 50 K between 130 and 298 K, resulting in mean axial and volumetric coefficients of thermal expansion (×10^?5K^?1); α _a =1.7(1), α _c =2.1(2), and α _V =5.6(2). Although the unit cell and ^VIIICaO₈ polyhedra show significant positive thermal expansion over this temperature range, the silicate octahedron, sulfate tetrahedron, and carbonate group show zero or negative thermal expansion, with α _V (^VISiO₆) = ?0.6 ± 1.1, α _V (^IVSO₄)=?5.8 ± 1.4, and α _R (C–O)= 0.0 ± 1.8 (×10^?5 K^?1). Most of the thermal expansion is accommodated by lengthening of the R(O...O) hydrogen bond distances by on average 5σ, although the hydrogen bonds involving hydroxyl sites on ^VISi expand twice as much as those on molecular water, causing the [Ca₃Si(OH)₆(H₂O)₁₂]⁴⁺ columns to expand in diameter more than they move apart over this temperature range. The average Si–OH bond length of the six-coordinated Si atom 〈R(^VISi–OH)〉 in thaumasite is 1.783(1) Å, being about 0.02 Å (?20σ) shorter than ^VISi–OH in the dense hydrous magnesium silicate, phase D, MgSi₂H₂O₆.