Crystal structures of two ancylite modifications

The crystal structures of two ancylite specimens from Khibiny massif (the Kola Peninsula, Russia)—ancylite-(Ce) from alkali hydrothermalites (Sr_1.01Ca_0.02Ba_0.01)_Σ1.04(Ce_0.52La_0.28Nd_0.11Pr_0.04 Sm_0.01)_Σ0.96(CO₃)₂(OH_0.83F_0.13)_Σ0.96 · 0.9H₂O and ancylite-(Ce) from carbonatites—have (Sr_0.80Ca_0.05Ba_0.01)_Σ0.86(Ce_0.62La_0.40Nd_0.09Pr_0.03) _Σ1.14(CO₃)₂(OH_0.99F_0.15)_Σ1.14 · 1.0H₂O been refined by the Rietveld method. A focusing STOE-STADIP diffractometer with a bent Ge(111) primary monochromator was used (λ MoK _{α 1} radiation, 2.16° < 2θ < 54.98°; reflection number 237–437). All the computations for ancylite from alkali hydrothermalites were performed within the sp. gr. Pmc2₁, a = 5.0634(1) Å, b = 8.5898(1) Å, c = 7.2781(1) Å, V = 316.55(1) ų, R _wp = 1.90; the computations for ancylite from carbonatites were performed within the sp. gr. Pmcn, a = 5.0577(1) Å, b = 8.5665(2) Å, c = 7.3151(2) Å, V = 316.94(1) ų, R _wp = 2.38 in the anisotropic approximation of thermal vibrations of cations and oxygen atoms.     

Refinement of the crystal structure of sanidine-like feldspar

The crystal structure of sanidine-like feldspar of the composition KAlSi₃O₈ from the Khibiny alkaline massif (the Kola Peninsula) has been refined (X-ray diffraction analysis; automated Syntex $P\bar 1$ diffractometer; 2θ: θ scanning technique; 2320 reflections; R _(hkl) = 0.0409; anisotropic refinement; AREN program package). The data obtained for KAlSi₃O₈ are: a = 8.615(9), b = 13.030(7), c = 7.200(5) Å, α = 89.99(5)°, β = 116.01(6)°, γ = 89.98(7)°, Z = 4, sp. gr. $C\bar 1$ . Microtwinning revealed in the crystal structure of the mineral explains the simultaneous existence of two structural-optical types in one sample—“high” and “low” sanidines.     

Refined crystal structure of iron-rich triclinic astrophyllite

Crystal structure of Fe-rich triclinic astrophyllite K₂NaFe₇ [Ti₂Si₈O₂₆F](OH)₄ is refined (a Syntex P $\bar 1$ automatic diffractometer, 3809 reflections, 2θ/θ scan, R = 0.041): a = 5.365(2), b = 11.88(1), c = 21.03(2) Å, α = 84.87(6)°, β = 92.25(5)°, γ = 103.01(4)°, sp. gr. A $\bar 1$ , Z = 2, d _calcd = 3.29 g/cm³. The refined structure is identical to that reported earlier. The structure is built by three-layer TOT sheets in which an O layer of Fe-octahedra is sandwiched between the T layers consisting of Si-tetrahedra and Ti-octahedra. It is established that differently chosen unit cells of the mineral are interrelated.     

Refined crystal structure of Ca[B<Subscript>8</Subscript>O<Subscript>11</Subscript>(OH)<Subscript>4</Subscript>]—A synthetic calcium analog of strontioborite

A calcium analog of strontioborite, namely, Ca[B₈O₁₁(OH)₄], is synthesized under hydrothermal conditions (T = 270°C, P = 20 atm) within the framework of the study of the phase formation in the CaCl₂ · Rb₂CO₃ · B₂O₃ system. The crystal structure of the synthetic calcium borate [a = 7.4480(5) Å, b = 8.2627(5) Å, c = 9.8102(6) Å, β = 108.331(1)°, V = 573.09(6) ų, space group P2₁, Z = 2, ρ_calcd = 2.15 g/cm³; Brucker SMART CCD automated diffractometer, 5506 reflections, λMoK_α] is refined by the least-squares procedure in the anisotropic approximation of thermal atomic vibrations to R₁ = 0.050. The calcium borate studied has a crystal structure identical to the structure of the natural strontium borate (strontioborite) Sr[B₈O₁₁(OH)₄] and its calcium analog synthesized earlier. The crystal structure is built up of stacks consisting of skeleton layers (formed by boron-oxygen polyanions) and isolated strontium (calcium) polyhedra located in trigonal holes of the skeleton layers. Through channels that can contain H₂O molecules are formed between the stacks. The structure refinement and analysis of the IR spectrum of the synthetic calcium analog of strontioborite do not confirm the previously proposed hypothesis that water molecules are involved in the channels of the structure. A comparative crystal chemical analysis of the calcium borate under investigation and its formula analog, namely, the lead borate Pb[B₈O₁₁(OH)₄], is performed.     

Crystal structure of a new synthetic Ca,Li pentaborate: CaLi<Subscript>4</Subscript>[B<Subscript>5</Subscript>O<Subscript>8</Subscript>(OH)<Subscript>2</Subscript>]<Subscript>2</Subscript>

When studying the phase formation in the CaO-Li₂O-B₂O₃-H₂O system, a new Ca,Li pentaborate was synthesized under hydrothermal conditions. The structure of a new compound with the crystallochemical formula CaLi₄[B₅O₈(OH)₂]₂ (sp. gr. Pb2n, a = 8.807(7), b = 9.372(7), c = 8.265(6) Å, V = 682.2(9) ų, Z = 2, d_calcd = 2.43 g/cm³, automated SYNTEX-\(P\bar 1\) diffractometer, 2690 reflections, 2θ/θ scan, λMo) is refined up to R_hkl = 0.0557 in the anisotropic approximation of atomic thermal vibrations with allowance for the localized H atoms. The structure of the Ca,Li pentaborate is formed by (010) open boron—oxygen layers formed by two independent [B₅O₈(OH)₂]^3? pentagroups, with each of them being formed by three B tetrahedra and two B triangles. The structure framework consists of the above boron—oxygen layers bound by isolated Li tetrahedra. The Ca cations are localized in the centers of eight-vertex polyhedra located in the [001] channels of the Li,B,O framework. Comparative crystallochemical analysis of the new Ca,Li pentaborate and Li pentaborate of the composition Li₃[B₅O₈(OH)₂]-II showed that the anionic matrices of both compounds are completely identical, whereas some of the cationic positions are different.     

Crystal structure of new synthetic calcium pentaborate Ca[B5O8(OH)] · H2O and its relation to pentaborates with similar boron-oxygen radicals

A new representative of pentaborates with the composition Ca[B₅O₈(OH)] · H₂O was synthesized under hydrothermal conditions within the framework of the study of phase formation in the CaCl₂-Na₂CO₃-B₂O₃ system. The crystal structure of the new pentaborate was established (a = 6.5303(9) Å, b = 19.613(3) Å, c = 6.5303(9) Å, β = 119.207(2)°, V = 2513(2) ų, sp. gr. P2₁/c, Z = 4, d _calcd = 2.74 g/cm³, automated Brucker SMART CCD diffractometer, 6871 reflections, λMo radiation, anisotropic refinement by least-squares, R _hkl = 0.076). The structure of calcium pentaborate is built by isolated B-Ca-B stacks parallel to the (010) plane. The central fragments of these stacks consists of nine-vertex Ca polyhedra. The Ca layers are located between loose B-O networks composed of [B ₂ ^t B ₃ ^Δ O₈(OH)]^2? pentaborate groups. The arrangement of the polyhedra around large cations in pentaborates with groups of two B tetrahedra and three B triangles was analyzed in terms of crystal chemistry. It is established that the structures of these compounds consist of large isolated polyhedra, columns, layers, and three-dimensional frameworks.     

Crystal structure of tisinalite Na2(Mn,Ca)1 − x (Ti,Zr,Nb,Fe3+)[Si6O8(O,OH)10]

Crystal structure of tisinalite from the Lovozero alkaline massif (the Kola Peninsula) was established by single-crystal X-ray diffraction analysis (SYNTEX $\bar P1$ diffractometer, λMoK_α radiation, 2θ/θ scanning mode). The structure solution (SHELX97 program package, R _hkl = 0.0565, 951 independent reflections, anisotropic refinement of thermal atomic displacements) confirmed that tisinalite belongs to the lovozerite structure type (sp. gr., $\bar P1$ , a = 10.036(5) Å, c = 12.876(9) Å, Z = 3). The difference between the structure of tisinalite and the structures of the minerals of the lovozerite group established earlier consists in the nature of the occupancy of both cation and anion positions.     

Crystal structure of new synthetic Ca,Na,Li-carbonate-borate

In the process of studying the phase formation in the Li₂CO₃-CaO-B₂O₃-NaCl system, new Ca,Na, Li-carbonate-borate has been synthesized under hydrothermal conditions. The crystal structure of carbonate-borate with the crystallochemical formula Ca₄(Ca_0.7Na_0.3)₃(Na_0.7□ _0.3)Li₅[B ₁₂ ^t B ₁₀ ^Δ O₃₆(O,OH)₆](CO₃)(OH) · (OH,H₂O) was refined to R _hkl = 0.0716 by the least squares method in the isotropic approximation of atomic thermal vibrations without the preliminary knowledge of the chemical composition and the formula (sp. gr. R3, a _rh = 13.05(2) Å, α = 40.32(7)]°, V = 838(2) ų, a _h = 8.99(2), c _h = 35.91(2) Å, V = 2513(2) ų, Z = 3, d _calcd = 2.62 g/cm³, Syntex P $\bar 1$ diffractometer, 3459 reflections, 2θ-θ method, λMo). The structure has a new boron-oxygen radical [B ₁₂ ^t B ₁₀ ^Δ O₃₆(O,OH)₆] _∞∞ ^15? , a double layer of nine-membered [B ₆ ^t B ₃ ^Δ O₁₅(O,OH)₃]^7.5?-rings bound by BO₃-triangles, and twelve-membered [B ₆ ^t B ₆ ^Δ O_19.5(O,OH)₃]^7.5? rings. This allows one to relate this compound to megaborates with complex boron-oxygen radicals. The structure is built from two types of blocks consisting of Ca,Na,B-and Li,B-polyhedra alternating along the c-axis, which explains the perfect cleavage of the crystals along the (0001) plane.     

New Data on Astrophyllite Supergroup Minerals: Crystall Chemical Mechanisms of the Formation of Triclinic and Monoclinic Structures

Crystallography Reports - Crystall chemical mechanisms of the formation of triclinic and monoclinic species of astrophyllite supergroup minerals have been considered using the concept of mixed...