High-pressure perovskites on the join CaTiO3-FeTiO3

An exploratory high-pressure study of the join CaTiO₃-FeTiO₃ has uncovered two intermediate perovskites with the compositions CaFe₃Ti₄O₁₂ and CaFeTi₂O₆. These perovskites have ordering of Ca²⁺ and Fe²⁺ on the A sites. Both of these perovskites are unusual in that the A sites containing Fe²⁺ are either square planar or tetrahedral, due to the particular tilt geometries of the octahedral frameworks. For CaFe₃Ti₄O₁₂, the structure has been refined from a powder using the Rietveld technique. This compound is a cubic double perovskite (SG Im $\bar 3$ , a = 7.4672 Å), isostructural with NaMn₇O₁₂. Fe²⁺ is in a square-planar A site (similar to Mn³⁺ in NaMn₇O₁₂) with Fe-O = 2.042(3) Å, with distant second neighbors in a rectangle at Fe-O = 2.780(6) Å. Calcium is in a distorted icosahedron with Ca-O =2.635(5) Å. CaFeTi₂O₆ crystallizes in a unique tetragonal double perovskite structure (SG P4₂/nmc, a = 7.5157(2), c = 7.5548(2)), with A-site iron in square-planar (Fe-O = 2.097(2) Å) and tetrahedral (Fe-O = 2.084(2) Å) coordination, again with distant second neighbor oxygens near 2.8 Å. Rietveld refinement was also performed for the previously known perovskite-related form of FeTiO₃ recovered from high pressure (lithium niobate type). This compound is trigonal R3c, with a = 5.1233(1) and c = 13.7602(2). The ordered perovskites appear to be stable at 1215 GPa and CaFe₃Ti₄O₁₂ is found as low as 5 GPa. Thus these perovskites may be important to upper mantle mineralogy, particularly in kimberlites. These compounds are the first known quenchable perovskites with large amounts of A-site ferrous iron, and add greatly to the known occurrences of ferrous iron in perovskites.     

Five-coordinate Cd in the crystal structure of triploidite-type Cd2(AsO4)(OH)

This paper reports on hydrothermal synthesis and crystal structure refinement of dicadmium arsenate hydroxide, Cd₂(AsO₄)(OH), obtained at 220 °C and autogenous pressure. Its crystal structure is monoclinic, space group P2₁/a, with a = 13.097(3), b = 14.089(3), c = 10.566(2) Å, β = 108.38(3)°, V = 1850.2(6) ų (Z = 16). It is isotypic with the members of the triploidite group of minerals and synthetic compounds, and thus shows a close topological relationship with the triplite group. The complex framework contains edge- and corner-sharing CdO₄(OH) and CdO₄(OH)₂ polyhedra, linked via corner-sharing to AsO₄ tetrahedra (average As—O distances range between 1.682 and 1.688 Å). Four five-coordinated Cd sites are at the centers of distorted trigonal bipyramids (average Cd—O distances are between 2.225 and 2.251 Å), whereas the remaining four Cd sites have a distorted octahedral coordination environment (average Cd—O distances are between 2.297 and 2.320 Å). The positions of all the hydrogen atoms were located in a difference-Fourier map and refined with an isotropic displacement parameter. The hydrogen-bonds are weak to very weak. The unusual five-coordination of Cd is briefly discussed in relation to comparable minerals and compounds. Among triploidite-type compounds, Cd₂(AsO₄)(OH) is the member with the largest unit cell reported so far, and the second known arsenate member.     

Study on the Crystal of Daomanite

It was not possible to carry out a complete analyses of crystal, as the experiment by Ding and Shi et al.. It's analysis precision R=0.25 or more big than this, which value are not satisfied for single crystal study, but we through many test and found the best: [R(int)=14.5%]. The final fullmatix least-squares refinement on F2 converged to R1=0.0791 and wR2=0.1864 for 704 observed reflections [I 3 2s(I)]. Daomanite is orthorhombic system, space group Cmc21, a=3.7520(8))?, b=15.844(4) ?, c=5.8516(12) ?, α=β=γ=90°. V=347.86(14)?3, Z=4. Daomanite chemical formula is Cu Pt AsS 2. Idealized composition Me+M2+M2+S2=CuS ·PtA s S. There is no other similar mineral in the world.     

Phase E: A high pressure hydrous silicate with unique crystal chemistry

The unique cation-disordered crystal structures of two samples of phase E, a non-stoichiometric, hydrous silicate synthesized in a uniaxial, split-sphere, multi-anvil apparatus at conditions above 13 GPa and 1000° C, have been solved and refined in space group $\bar 3$ . The compositions and unit cells for the two materials, assuming six oxygens per cell, are Mg_2.08Si_1.16H_3.20O₆, a=2.9701(1) Å, c=13.882(1) Å V = 106.05(4) ų for sample 1, and Mg_2.17Si_1.01H_3.62O₆, a=2.9853(6) Å, c=13.9482(7) Å, V= 107.65(4) ų for sample 2. The structure contains layers with many features of brucite-type units, with the layers stacked in a rhombohedral arrangement. The layers are cross linked by silicon in tetrahedral coordination and magnesium in octahedral coordination, as well as hydrogen bonds. Interlay er octahedra share edges with intralayer octahedra. Interlayer tetrahedra would share faces with intralayer octahedra. To avoid this situation, there are vacancies within the layers. There is, however, no long-range order in the occupation of these sites, as indicated by the lack of a superstructure. Selected-area electron diffraction patterns show walls of diffuse intensity similar in geometry and magnitude to those observed in short-range-ordered alloys and Hågg phases. Phase E thus appears to represent a new class of disordered silicates, which may be thermodynamically metastable.     

Structure and Mössbauer spectroscopy of barbosalite Fe2+Fe3+ 2 (PO4)2(OH)2 between 80 K and 300 K

Natural barbosalite Fe²⁺Fe³⁺ ₂ (PO₄)₂(OH)₂ from Bull Moose Mine, South Dakota, U.S.A., having ideal composition, was investigated with single crystal X-ray diffraction techniques, Mössbauer spectroscopy and SQUID magnetometry to redetermine crystal structure, valence state of iron and evolution of ⁵⁷Fe Mössbauer parameter and to propose the magnetic structure at low temperatures. At 298?K the title compound is monoclinic, space group P2₁/n, a _o ?= 7.3294(16)?Å, b _o ?=?7.4921(17)?Å, c _o ?=?7.4148 (18)?Å, β?=?118.43(3)°, Z?=?2. No crystallographic phase transition was observed between 298?K and 110?K. Slight discontinuities in the temperature dependence of lattice parameters and bond angles in the range between 150?K and 180?K are ascribed to the magnetic phase transition of the title compound. At 298?K the Mössbauer spectrum of the barbosalite shows two paramagnetic components, typical for Fe²⁺ and Fe³⁺ in octahedral coordination; the area ratio Fe³⁺/Fe²⁺ is exactly two, corresponding to the ideal value. Both the Fe²⁺ and the Fe³⁺ sublattice order magnetically below 173?K and exhibit a fully developed magnetic pattern at 160?K. The electric field gradient at the Fe²⁺ site is distorted from axial symmetry with the direction of the magnetic field nearly perpendicular to V_zz, the main component of the electric field gradient. The temperature dependent magnetic susceptibility exhibits strong antiferromagnetic ordering within the corner-sharing Fe³⁺-chains parallel to [101], whereas ferromagnetic coupling is assumed within the face-sharing [1?1?0] and [?1?1?0] Fe³⁺-Fe²⁺-Fe³⁺ trimer, connecting the Fe³⁺-chains to each other.     

Structure of Cu-bearing orthopyroxene, Mg(Cu.56,Mg.44)Si2O6, and behavior of Cu2+ in the orthopyroxene structure

Cu-bearing pyroxene, Mg(Cu.₅₆,Mg.₄₄)Si₂O₆, has been synthesized by a flux method and crystal structure refinement has been performed by single crystal X-ray diffraction. It is found that the crystal structure is orthorhombic (space group Pbca) with unit cell dimensions of a=18.221(4), b=8.890(1), c=5.2260(7)Å and the cell volume of 846.5( )3ų. In the M2-site one of the M-O bonds(M-O3B) is extremely expanded from 2.444(2) in enstatite to 2.732(2), thus the coordination polyhedron around M2-site is regarded as square pyramidal rather than square planar or octahedral. It is also found that the M1-site in the pyroxene structure is occupied almost exclusively by Mg, while the M2-site is almost evenly occupied by Mg and Cu. The observed extreme site preference shown by Cu²⁺ is unusual among the divalent cations with similar ionic sizes.     

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.     

High-pressure single-crystal X-ray diffraction study of jadeite and kosmochlor

The crystal structures of natural jadeite, NaAlSi₂O₆, and synthetic kosmochlor, NaCrSi₂O₆, were studied at room temperature, under hydrostatic conditions, up to pressures of 30.4 (1) and 40.2 (1) GPa, respectively, using single-crystal synchrotron X-ray diffraction. Pressure–volume data have been fit to a third-order Birch–Murnaghan equation of state yielding V ₀ = 402.5 (4) Å³, K ₀ = 136 (3) GPa, and K ₀ ^′  = 3.3 (2) for jadeite and V ₀ = 420.0 (3) Å³, K ₀ = 123 (2) GPa and K ₀ ^′  = 3.61 (9) for kosmochlor. Both phases exhibit anisotropic compression with unit-strain axial ratios of 1.00:1.95:2.09 for jadeite at 30.4 (1) GPa and 1:00:2.15:2.43 for kosmochlor at 40.2 (1) GPa. Analysis of procrystal electron density distribution shows that the coordination of Na changes from 6 to 8 between 9.28 (Origlieri et al. in Am Mineral 88:1025–1032, 2003) and 18.5 (1) GPa in kosmochlor, which is also marked by a decrease in unit-strain anisotropy. Na in jadeite remains six-coordinated at 21.5 (1) GPa. Structure refinements indicate a change in the compression mechanism of kosmochlor at about 31 GPa in both the kinking of SiO₄ tetrahedral chains and rate of tetrahedral compression. Below 31 GPa, the O3–O3–O3 chain extension angle and Si tetrahedral volume in kosmochlor decrease linearly with pressure, whereas above 31 GPa the kinking ceases and the rate of Si tetrahedral compression increases by greater than a factor of two. No evidence of phase transitions was observed over the studied pressure ranges.     

Crystal Structure of Natural Non-metamict Ti- and Fe~(2+)-rich Chevkinite-(Ce)

1 Introduction Chevkinite groups can be assigned to the chevkinite-(Ce) subgroup and perrierite-(Ce) subgroup in accord with the angle β : β ≈ 100o for the chevkinite subgroup and β ≈ 113o for the perrierite subgroup. Chevkinite-(Ce), polykovite-(Ce) and Maoniupingite (new mineral No. 017 of 2003) belong to the former subgroup, while renjeite and matsubaraite belong to the latter group. As strontio-chevkinite is a Sr-analogue of perrierite, usually the natural chevkinite-(Ce) group min…     

Sodium trisilicate: A new high-pressure silicate structure (Na2Si[Si2O7])

Crystals of sodium trisilicate (Na₂Si₃O₇) have been grown in the presence of melt at 9 GPa, 1200 °C using the MA6/8 superpress at Edmonton, and the X-ray structure determined at room pressure (R=2.0%). Na₂Si₃O₇ is monoclinic with a=8.922(2) Å, b= 4.8490(5) Å, c=11.567(1) Å, β=102.64(1)° (C2/c), D _x = 3.295 g·cm^-3. Silicon occurs in both tetrahedral and octahedral coordination (^[6]Si∶^[4]Si = l∶2). The SiO₄ tetrahedra form a diorthosilicate [Si₂O₇] group and are linked by the isolated SiO₆ octahedra via shared corners into a framework of 6-membered (^[4]Si-^[4]Si-^[6]Si^[4]Si-^[4] Si-^[6]Si) and 4-membered (^[4]Si-^[6]Si-^[4]Sr-^[6]Si) rings: 〈^[6]Si-O〉=1.789 Å, 〈^[4]Si-O〉= 1.625 Å, ^[4]Si-O-^[4]Si=132.9° and the bridging oxygen is overbonded (s = 2.22). Channels parallel to b-axis and [110] accommodate Na in irregular 6-fold coordination: 〈Na-O〉 = 2.511 Å.     

Crystal chemistry of selenates with mineral-like structures. IV. Crystal structure of Zn(SeO<Subscript>4</Subscript>)(H<Subscript>2</Subscript>O)<Subscript>2</Subscript>, a new compound with a mixed framework of the variscite type

The crystal structure of a new compound Zn(SeO₄)(H₂O)₂ (orthorhombic, Pbca, a = 9.0411(13), b = 10.246(2), c = 10.3318(15) Å, V = 957.1(3) ų) has been solved by direct methods and refined to R ₁ = 0.033 on the basis of 1076 observed reflections with |F _hkl | ≥ 4σ|F _hkl |. The structure contains one independent Zn²⁺ cation coordinated by two water molecules and four oxygen atoms of selenate group. The only independent (SeO₄)^2? tetrahedral oxoanion is tetradentate, sharing its corners with four adjacent [Zn²⁺O₂(H₂O₄)]²⁺ octahedrons. The structure can be described as consisting of heteropolyhedral sheets parallel to the (001) plane and linked together into a three-dimensional network. The compound belongs to the variscite structure type and is the first structurally characterized selenate of this group.     

Crystal chemistry of natural and synthetic lead oxohalides: II. Crystal structure of Pb7O4(OH)4Br2

Crystals of lead oxobromide Pb₇O₄(OH)₄Br₂ have been synthesized by hydrothermal method. The structure of the new compound has been studied with X-ray single-crystal diffraction analysis. The compound is monoclinic, space group C112₁; unit-cell dimensions are a = 5.852(4), b = 13.452(7), c = 19.673(9) Å, γ = 90.04°, V = 1548.7(15) ų. The structure has been solved by direct methods and refined to R ₁ = 0.1138 for 1847 observed Pb₇O₄(OH)₄Br₂ unique reflections. The structure contains seven symmetrically independent bivalent Pb atoms. The coordination polyhedrons of Pb are strongly distorted due to stereochemical activity of unshared electron pair 6s ². Oxygen atoms are tetrahedrally coordinated by four Pb²⁺ cations with the formation of oxocentered tetrahedrons OPb₄. The compound is based on [O₂Pb₃]²⁺ double chains formed by OPb₄ tetrahedrons. (OH)Pb₂ dimers combine the [O₂Pb₃]²⁺ chains into 3D framework. Channels in the framework are parallel to [100] and are occupied by Br anions.     

Theoretical studies of the electronic structure of copper in tetrahedral and triangular coordination with sulfur

Molecular orbital calculations are presented for the copper-sulfur polyhedral clusters CuS ₄ ^7? , CuS ₄ ^6? , CuS ₃ ^5? and CuS ₃ ^4? , which occur in many minerals. Calculated and experimental optical and X-ray energies are found to be in good agreement. The crystal field orbitals of Cu⁺ in tetrahedrally coordinated sulfides are found to be less tightly bound than the S3p nonbonding orbitals by about 2–3 eV whereas the e and t ₂ crystal field orbitals are split by about 1 eV. The crystal field splitting of Cu²⁺ in tetrahedral coordination is about 0.7–0.8 eV while the separation of the S3p nonbonding orbitals and the partially filled t ₂ crystal field orbital is about 2 eV. In triangular coordination both the Cu⁺ and Cu²⁺ crystal field orbitals are more stable than in tetrahedral coordination, more widely split and more strongly mixed with the S3p orbitals. CuS is shown to be unstable as the mixed oxidation state compound Cu^2+III (Cu^+IV)₂S^2?(S ₂ ^2? ); rather each Cu is predicted to have a fractional oxidation state and partially-empty crystal field orbitals.     

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.     

Crystal chemistry, surface morphology and X-ray photoelectron spectroscopy of Fe-rich osumilite from Mt. Arci, Sardinia (Italy)

Microprobe analysis, single crystal X-ray diffraction, X-ray photoelectron spectroscopy, atomic force microscopy, and X-ray absorption spectroscopy were applied on Fe-rich osumilite from the volcanic massif of Mt. Arci, Sardinia, Italy. Osumilite belongs to the space group P6/mcc with unit cell parameters a = 10.1550(6), c = 14.306(1) Å and chemical formula (K_0.729)_C (Na_0.029)_B (Si_10.498 Al_1.502)_T1 (Al_2.706 Fe _0.294 ²⁺ )_T2 (Mg_0.735 Mn_0.091 Fe _1.184 ²⁺ )_AO₃₀. Structure refinement converged at R = 0.0201. Unit cell parameter a is related to octahedral edge length as well as to Fe²⁺ content, unlike the c parameter which does not seem to be affected by chemical composition. The determination of the amount of each element on the mineral surface, obtained through X-ray photoelectron spectroscopy high-resolution spectra in the region of the Si_2p, Al_2p, Mg_1s and Fe_2p core levels, suggests that Fe presents Fe²⁺ oxidation state and octahedral coordination. Two peaks at 103.1 and 100.6 eV can be related to Si⁴⁺ and Si¹⁺ components, respectively, both in tetrahedral coordination. The binding energy of Al_2p, at 74.5 eV, indicates that Al is mostly present in the distorted T2 site, whereas the Mg peak at 1,305.2 eV suggests that this cation is located at the octahedral site. X-ray absorption at the Fe L_2,3-edges confirms that iron is present in the mineral structure, prevalently in the divalent state and at the A octahedral site.     

Refinement of the mangan-neptunite crystal structure

The crystal structure of mangan-neptunite, a manganese analogue of neptunite, has been refined in two space groups (Cc and C2/c). The mineral is monoclinic, with the correct space group Cc; the unit-cell dimensions are: a = 16.4821(6), b = 12.5195(4), c = 10.0292(3) Å, β = 115.474(1)°, and V = 1868.31 ų. The crystal structure has been refined to R ₁ = 0.0307 (wR ₂ = 0.0901) on the basis of 4892 observed reflections with |F _hkl | ≥ 4σ|F _hkl |. The most plausible acentric model is caused by the Ti- and (Fe, Mn, Mg)-ordering in the structure. Ti-octahedrons are strongly distorted and consist of short bond Ti-O (1.7 Å), one long bond (2.2 Å), and four equal bonds (2.0 Å). Fe-octahedrons are regularly shaped, with all Fe-O bonds being approximately identical.     

A study of speciation of Sb in bisulfide solutions by X-ray absorption spectroscopy.

Direct evidence of the structure of thioantimonide species in alkaline aqueous solutions is provided by X-ray absorption spectroscopy. Twenty solutions containing thioantimonide species were prepared by dissolving stibnite (Sb₂S₃) in deoxygenated aqueous NaHS solutions; the solution pH range was 8–14, the [Sb_tot] 1–100 mM and the [HS⁻] 0.009–2.5 M. The structural environment of the dissolved Sb was determined by EXAFS analysis of the Sb K-edge over the temperature range 80–473 K.Many of the solutions contain a species with Sb bonded to four S atoms at 2.34 Å, consistent with the presence of a [Sb(V)S₄³⁻] species, demonstrating that oxidation of Sb(III) to Sb(V) has occurred on dissolution. There is evidence that the complementary reduced phase is H₂. In three solutions, the Sb has three nearest neighbor S atoms and two of these solutions have an additional S shell of two atoms at 2.9Å, with one showing evidence of an Sb shell at 4.15 Å. This provides evidence of the presence of multimeric Sb(V) thioantimonide species. Analysis of several solutions reveals the presence of a species with three Sb–S interactions of 2.41–2.42 Å, supporting the presence of a Sb(III) species such as Sb₂S₂(SH)₂. Six solutions have S coordination numbers from 2.7–4 Å and Sb–S distances of 2.37–2.39 Å, and are likely to contain mixtures of at least two species in concentrations such that each make a significant contribution to the EXAFS. There was no clear relationship between either [Sb_tot] or [HS⁻] and the type of species present, but Sb(III) species were only present in the solutions with high pH. The effect of temperature was most significant in one solution, where at 423 K partial hydrolysis occurred and the presence of a species such as Sb₂S₂(OH)₂, with an Sb–O distance of 1.91 Å, is indicated.The study provides new information on the coordination environment of thioantimonide species, complementary to previous studies and provides a basis for a better understanding of Sb speciation in aqueous solutions found in hydrothermal systems, anoxic basins and man-made, high pH environments. In particular it demonstrates the need for Sb(V) to be considered in theoretical and experimental studies of such systems. However, more definitive interpretation of some of the data is inhibited by the presence of mixtures of species and the lack of information on the outer coordination shells that would confirm the presence of multimeric species.     

Structural variation of babingtonite depending on cation distribution at the octahedral sites

Babingtonite, Ca₂Fe²⁺Fe³⁺[Si₅O₁₄(OH)] (Z?=?2, space group $ P\overline{1} $ ) from Yakuki mine (Japan), Grönsjöberget (Sweden), Kandivali Quarry (India), Baveno Quarry (Italy), Bråstad Mine (Norway), and Kouragahana (Japan), and manganbabingtonite, Ca₂(Mn²⁺, Fe²⁺)Fe³⁺[Si₅O₁₄(OH)], from Iron Cap mine (USA) were studied using electron-microprobe analysis (EMPA), ⁵⁷Fe Mössbauer analysis and single-crystal X-ray diffraction methods to determine the cation distribution at M1 and M2 and to analyze its effect on the crystal structure of babingtonite. Although all studied babingtonite crystals are relatively homogeneous, chemical zonation due to mainly Fe ? Mn substitution is observed in manganbabingtonite. Mössbauer spectra consist of two doublets with isomer shift (I.S.)?=?1.16–1.22 mm/s and quadrupole splitting (Q.S.)?=?2.33–2.50 mm/s and with I.S.?=?0.38–0.42 mm/s and Q.S.?=?0.82–0.90 mm/s, assigned to Fe²⁺ and Fe³⁺ at the M1 and M2 octahedral sites, respectively. The determined ratio of Fe²⁺/total Fe in manganbabingtonite (0.26) was smaller than that in the others (0.35–0.44) because of high Mn²⁺ content instead of Fe²⁺. The unit-cell parameters of babingtonite are a?=?7.466–7.478, b?=?11.624–11.642, c?=?6.681–6.690 Å, α?=?91.53–91.59, β?=?93.86–93.94, γ?=?104.20–104.34º, and V?=?560.2–562.3 Å³, and those of manganbabingtonite are a?=?7.4967(3), b?=?11.6632(4), c?=?6.7014(2) Å, α?=?91.602(2), β?=?93.989(2), γ?=?104.574(3)º, and V =565.09(5) ų. Structural refinements converged to R ₁ values of 1.64–3.16 %. The <M1-O> distance was lengthened due to the substitution of large octahedral cations such as Mn²⁺ for Fe²⁺. The increase of the M1-O8, M1-O8’ and M1-O13 lengths with mean ionic radii is slightly more pronounced than of the other M1-Oi lengths. The lengthened M1-O13 distance leads the positive correlation between Si5-O15-Si1 angle and M1-O13 distance. The increase of Si2-O3-Si1 and Si5-O12-Si4 angles due to the increase of mean ionic radius of M2 is also observed.     

Crystal chemistry of tremolite–tschermakite solid solutions

Tremolite–tschermakite solid solutions have been synthesized between 700 and 850 °C and 200 and 2000 MPa. The starting materials were oxide–hydroxide mixtures and an additional 0.1–1.8 molal CaBr₂ solution. The run products were characterized using SEM, HRTEM, EMP, XRD and FTIR. The synthesized Al tremolites formed needles and lath-shaped crystals of up to 300 × 20 μm. HRTEM investigations showed that the majority of the amphiboles were well ordered. The EMP analysis revealed that the Al tremolites were solid solutions in the ternary tremolite–tschermakite–cummingtonite. The highest observed Al content was close to the composition of magnesiohornblende (X_ts=0.54). Different cummingtonite concentrations (X_cum=0.00–0.18) were observed, which generally increased with Al content. Rietveld refinements of the lattice constants showed a linear decrease of the cell parameters a and b with increasing Al content, whereas c and β increased. Small deviations from the linear behaviour were caused by variable amounts of the cummingtonite component. For pure tschermakite lattice parameters of a=9.7438(11) Å, b=17.936(14) Å, c=5.2995(3) Å, β=105.68(9)° and V=891.7 ± 1.4 ų were extrapolated by least-squares regression. Using the a and β lattice parameters for tremolite, tschermakite and cummingtonite, it was possible to derive amphibole compositions using powder XRD. IR spectra of the Al tremolites showed a total of 12 individual bands. The FWHMs of all bands increased with increasing Al content. According to their FWHMs, these bands were grouped into three band systems at 3664–3676 cm^?1 (I), 3633–3664 cm^?1 (II) and 3526–3633 cm^?1 (III). Assuming ^[6]Al substitution at M2 and/or M3 and ^[4]Al at T1, three principal different configurational groups could be assigned as local environments for the proton. I: only Si⁴⁺ at T1 and one or two Al³⁺ at M2 and/or M3_far, II: one Al³⁺ at T1 and one to three Al³⁺ at M2 and/or at M3_far, III: either Al³⁺ on M3_near and/or two Al³⁺ on T1 and additional one to four Al³⁺ at M2. It is assumed that these three configurational groups correspond to the three groups of observed bands. This was quantitativly supported by Monte-Carlo simulations. A model with random distribution at M2 and M3 including Al avoidance at tetrahedral and octahedral sites yielded the best agreement with the spectroscopical results.     

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.