scholarly journals Crystal Chemistry of the Microporous Zirconosilicate Na6Zr3[Si9O27], a Product of High-Temperature Transformation of Catapleiite, and Its Ag-Exchanged Form

Minerals ◽  
2020 ◽  
Vol 10 (3) ◽  
pp. 243 ◽  
Author(s):  
Natalia V. Zubkova ◽  
Dmitry A. Ksenofontov ◽  
Nikita V. Chukanov ◽  
Igor V. Pekov ◽  
Anna A. Artamonova ◽  
...  

The crystal structure of the Ag-exchanged form of the zirconosilicate with the simplified formula (Na6-2xCax▯x)Zr3[Si9O27] with x < 1 (the idealized formula Na6Zr3[Si9O27]), a product of thermal transformation of catapleiite, ideally Na2Zr[Si3O9]·2H2O, was studied using single crystal X-ray diffraction data. The crystal structure of Na6Zr3[Si9O27] is based on a heteropolyhedral framework built by nine-membered tetrahedral rings [Si9O27] and isolated [ZrO6] octahedra. This zirconosilicate demonstrates high exchange capacity to Ag (experiment with 1 M AgNO3 aqueous solution, 250 °C, 30 days). Its Ag-exchanged form with the simplified formula (Ag5Ca0.5)Zr3[Si9O27] is characterized by a significant distortion of the heteropolyhedral framework and strongly disordered arrangement of extra-framework cations (Ag) which results in the doubling of a parameter of the hexagonal unit cell [a = 23.3462(3), c = 10.10640(10) Å, V = 4770.45(13) Å3] and space group P63cm. Ag+ cations preferably occupy the sites that are close to the Na sites in Na6Zr3[Si9O27].

2018 ◽  
Vol 82 (5) ◽  
pp. 1211-1224 ◽  
Author(s):  
Oleg I. Siidra ◽  
Diana O. Nekrasova ◽  
Rick Turner ◽  
Anatoly N. Zaitsev ◽  
Nikita V. Chukanov ◽  
...  

ABSTRACTThe new mineral somersetite, has been found at Torr Works (‘Merehead quarry’) in Somerset, England, United Kingdom. Somersetite is green or white (typically it is similar visually to hydrocerussite-like minerals but with a mint-green tint), forms plates and subhedral grains up to 5 mm across and up to 2 mm thick. In bi-coloured crystals it forms very thin intergrowths with plumbonacrite. The empirical formula of somersetite is Pb8.00C5.00H4.00O20. The simplified formula is Pb8O(OH)4(CO3)5, which requires: PbO = 87.46, CO2 = 10.78, H2O = 1.76, total 100.00 wt.%.The infrared spectrum of somersetite is similar to that of plumbonacrite and, to a lesser degree, hydrocerussite. Somersetite is hexagonal, P63/mmc, a = 5.2427(7), c = 40.624(6) Å, V = 967.0(3) Å3 and Z = 2. The eight strongest reflections of the powder X-ray diffraction (XRD) pattern [d,Å(I)(hkl)] are: 4.308(33)(103), 4.148(25)(104), 3.581(40)(107), 3.390(100)(108), 3.206(55)(109), 2.625(78)(110), 2.544(98)(0.0.16) and 2.119(27)(1.0.17). The crystal structure was solved from single-crystal XRD data giving R1 = 0.031. The structure of somersetite is unique and consists of the alternation of the electroneutral plumbonacrite-type [Pb5O(OH)2(CO3)3]0 and hydrocerussite-type [Pb3(OH)2(CO3)2]0 blocks separated by stereochemically active lone electron pairs on Pb2+. There are two blocks of each type per unit cell in the structure, which corresponds to the formula [Pb5O(OH)2(CO3)3][Pb3(OH)2(CO3)2] or Pb8O(OH)4(CO3)5 in a simplified representation. The 2D blocks are held together by weak Pb–O bonds and weak interactions between lone pairs.


2015 ◽  
Vol 79 (4) ◽  
pp. 949-963 ◽  
Author(s):  
Leonid A. Pautov ◽  
Atali A. Agakhanov ◽  
Elena Sokolova ◽  
Frank C. Hawthorne ◽  
Vladimir Y. Karpenko ◽  
...  

AbstractKhvorovite, ideally Pb42+Ca2[Si8B2(SiB)O28]F, is a new borosilicate mineral of the hyalotekite group from the Darai-Pioz alkaline massif in the upper reaches of the Darai-Pioz river, Tajikistan. Khvorovite was found in a pectolite aggregate in silexites (quartz-rich rocks). The pectolite aggregate consists mainly of pectolite, quartz and fluorite, with minor aegirine, polylithionite, turkestanite and baratovite; accessory minerals are calcite, pyrochlore-group minerals, reedmergnerite, stillwellite-(Ce), pekovite, zeravshanite, senkevichite, sokolovaite, mendeleevite-(Ce), alamosite, orlovite, leucosphenite and several unknown Cs-silicates. Khvorovite occurs as irregular grains, rarely with square or rectangular sections up to 150 μm, and grain aggregates up to 0.5 mm. Khvorovite is colourless, rarely white, transparent with a white streak, has a vitreous lustre and does not fluoresce under ultraviolet light. Cleavage and parting were not observed. Mohs hardness is 5–5.5, and khvorovite is brittle with an uneven fracture. The measured and calculated densities are 3.96(2) and 3.968 g/cm3, respectively. Khvorovite is biaxial (+) with refractive indices (λ = 589 nm) α = 1.659(3), βcalc. = 1.671(2), γ = 1.676(3); 2Vmeas. = 64(3)°, medium dispersion: r < v. Khvorovite is triclinic, space group I1¯, a = 11.354(2), b = 10.960(2), c = 10.271(2) Å, α = 90.32(3), β = 90.00(3), γ = 90.00(3)°, V = 1278(1) Å3, Z = 2. The six strongest lines in the powder X-ray diffraction pattern [d (Å), I, (hkl)] are: 7.86, 100, (110); 7.65, 90, (101); 7.55, 90, (011); 3.81, 90, (202); 3.55, 90, (301); 2.934, 90, (312, 312). Chemical analysis by electron microprobe gave SiO2 36.98, B2O3 6.01, Y2O3 0.26, PbO 40.08, BaO 6.18, SrO 0.43, CaO 6.77, K2O 1.72, Na2O 0.41, F 0.88, O=F –0.37, sum 99.35 wt.%. The empirical formula based on 29 (O+F) a.p.f.u. is (Pb2.762+Ba0.62K0.56Na0.16)Σ4.10(Ca1.86Sr0.06Y0.04Na0.04)Σ2[Si8B2(Si1.46B0.65)Σ2.11O28](F0.71O0.29), Z = 2 , and the simplified formula is (Pb2+, Ba, K)4Ca2[Si8B2(Si,B)2O28]F. The crystal structure of khvorovite was refined to R1 = 2.89% based on 3680 observed reflections collected on a four-circle diffractometer with MoKα radiation. In the crystal structure of khvorovite, there are four [4]-coordinated Si sites occupied solely by Si with <Si–O>= 1.617 Å. The [4]-coordinated B site is occupied solely by B, with <B–O> = 1.478 Å. The [4]-coordinated T site is occupied by Si and B (Si1.46B0.54), with <T–O> = 1.605 Å; it ideally gives (SiB) a.p.f.u. The Si, B and T tetrahedra form an interrupted framework of ideal composition [Si8B2(SiB)O28]11–. The interstitial cations are Pb2+, Ba and K (minor Na) [A(11–22) sites] and Ca [M site]. The two A sites are each split into two subsites ∼0.5 Å apart and occupied by Pb2+ and Ba + K. The [8]-coordinated M site is occupied mainly by Ca, with minor Sr, Y and Na. Khvorovite is a Pb2+ analogue of hyalotekite, (Ba,Pb2+,K)4(Ca,Y)2[Si8(B,Be)2(Si,B)2O28]F and a Pb2+-, Ca-analogue of kapitsaite-(Y), (Ba,K)4(Y,Ca)2[Si8B2(B,Si)2O28]F. It is named after Pavel V. Khvorov (b. 1965), a Russian mineralogist, to honour his contribution to the study of the mineralogy of the Darai-Pioz massif.


2021 ◽  
Vol 4 ◽  
pp. 3-9
Author(s):  
R. K. Rastsvetaeva ◽  
◽  
N. V. Chukanov ◽  
D. V. Lisitsin ◽  
M. V. Voronin ◽  
...  

Odikhinchaite, a Sr-Mn-Nb-CO3-dominant eudialyte-group mineral from the Khibiny alkaline complex has been investigated using the methods of electron probe microanalysis, X-ray diffraction, infrared and Mössbauer spectroscopy. The crystal structure was refined to R = 3.4 % in the anisotropic approximation of atomic displacements using 3815 independent reflections with F > 3(F). The unit-cell parameters are: a = 14.2709(1), c = 30.023(1) Å, V = 5295.33(7) Å3; the space group is R3m. The simplified formula of the mineral is (Z = 3): Na11Sr3(Mn2+,Fe2+,Fe3+)Ca6Zr3Nb[Si25O72(OH)](CO3)Cl(OH,O)4. The studied sample is the second find of this rare mineral worldwide, represented by a variety with high Fe content in the M2 micro-region, belonging to the taseqite — odikhinchaite solid-solution series. The significance of odikhinchaite as an indicator of a stage corresponding to maximum Sr activity in specific ultraagpaitic pegmatites is discussed.


Author(s):  
Atali A. Agakhanov ◽  
Anatoly V. Kasatkin ◽  
Sergey N. Britvin ◽  
Oleg I. Siidra ◽  
Leonid A. Pautov ◽  
...  

Abstract Cesiokenopyrochlore is a new mineral belonging to the pyrochlore group. It was discovered in a specimen of granitic pegmatite collected at Tetezantsio, Betafo region, Madagascar. The mineral forms rough equant crystals up to 0.05 mm in size intergrown with béhierite and rynersonite. Cesiokenopyrochlore is light-brown, translucent, with resinous luster. Dcalc. = 5.984 g/cm3. In reflected light it is light gray, isotropic, with strong light-brown internal reflections. The crystal structure was refined to R1 = 0.0212. The mineral is cubic, , a = 10.444(1) Å, V = 1139.5(2) Å3, and Z = 8. The strongest lines of the powder X-ray diffraction pattern [d, Å, (I, %) (hkl)] are: 6.03 (37) (111), 3.70 (9) (220), 3.15 (100) (311), 3.02 (36) (222), 2.012 (17) (511, 333), 1.848 (19) (440), 1.576 (11) (622). The chemical composition is (wt.%; electron microprobe): Cs2O 22.66, Na2O 1.74, CaO 0.64, Nb2O5 20.87, Ta2O5 21.27, WO3 30.67, H2O (calc) 0.12, total 97.97. The empirical formula of the holotype specimen calculated on the basis of (Nb+Ta+W) = 2 apfu and (O+OH) = 6 apfu and written according to the pyrochlore-supergroup nomenclature is Na0.29Ca0.06(Nb0.81W0.69Ta0.50)Σ2[O5.93(OH)0.07]Σ6Cs0.83. The simplified formula of the holotype specimen is □2(Nb,W,Ta)Σ2O6Cs. Cesiokenopyrochlore is the first natural niobate to adopt the inverse pyrochlore structure.


Minerals ◽  
2019 ◽  
Vol 9 (7) ◽  
pp. 420 ◽  
Author(s):  
Natalia V. Zubkova ◽  
Rositsa P. Nikolova ◽  
Nikita V. Chukanov ◽  
Vladislav V. Kostov-Kytin ◽  
Igor V. Pekov ◽  
...  

Elpidite from the Lovozero alkaline complex, Kola Peninsula, Russia, and Ag-exchanged forms of elpidite from two different localities (Lovozero and Khan Bogdo, Mongolia) were studied by means of single-crystal X-ray diffraction, electron microprobe analysis, thermogravimetry and IR spectroscopy. All studied samples retain the heteropolyhedral framework consisting of double Si6O15 chains (ribbons) and isolated ZrO6 octahedra. Zeolitic cavities in the initial elpidite from Lovozero (space group Pbm2, a = 14.6127(7), b = 7.3383(4), c = 7.1148(3) Å, V = 762.94(6) Å3) are occupied by Na+ cations and H2O molecules. Both Ag-exchanged forms are characterized by evident distortions of the heteropolyhedral framework and a strongly disordered arrangement of extra-framework cations which results in the appearance of the 14-14-14 Å unit cell (a = 14.1755(7), b = 14.6306(9), c = 14.2896(7) Å, V = 2963.6(3) Å3 for the Ag-exchanged form of elpidite from Lovozero and a = 14.1411(5), b = 14.5948(4), c = 14.3035(5) Å, V = 2952.04(17) Å3 for the Ag-exchanged form of elpidite from Khan Bogdo) and space group Cmce. Elpidite from both localities demonstrates a high exchange capacity to Ag. Exchanged Ag+ cations preferably occupy the sites that are close to the Na sites in the initial elpidite. The paper also contains a review of crystal chemical data on elpidite and its laboratory-modified forms.


Author(s):  
Süheyla Özbey ◽  
F. B. Kaynak ◽  
M. Toğrul ◽  
N. Demirel ◽  
H. Hoşgören

AbstractA new type of inclusion complex, S(–)-1 phenyl ethyl ammonium percholorate complex of R-(–)-2-ethyl - N - benzyl - 4, 7, 10, 13 - tetraoxa -1- azacyclopentadecane, has been prepared and studied by NMR, IR and single crystal X-ray diffraction techniques. The compound crystallizes in space group


2002 ◽  
Vol 67 (4) ◽  
pp. 479-489 ◽  
Author(s):  
Michal Hušák ◽  
Bohumil Kratochvíl ◽  
Ivana Císařová ◽  
Ladislav Cvak ◽  
Alexandr Jegorov ◽  
...  

Two new structures of semisynthetic ergot alkaloid terguride created by unusual number of symmetry-independent molecules were determined by X-ray diffraction methods at 150 K. Form A (monoclinic, P212121, Z = 12) contains three symmetry-independent terguride molecules and two molecules of water in the asymmetric part of the unit cell. The form CA (monoclinic, P21, Z = 8) is an anhydrate remarkable by the presence of four symmetry-independent molecules in the crystal structure. Conformations of twelve symmetry-independent molecules that were found in four already described terguride structures are compared with torsion angles obtained by ab initio quantum-mechanical calculations for the simplified model of N-cyclohexyl-N'-diethylurea.


2019 ◽  
Vol 74 (4) ◽  
pp. 357-363
Author(s):  
Daniela Vitzthum ◽  
Hubert Huppertz

AbstractThe mixed cation triel borate Ga4In4B15O33(OH)3 was synthesized in a Walker-type multianvil apparatus at high-pressure/high-temperature conditions of 12.5 GPa and 1300°C. Although the product could not be reproduced in further experiments, its crystal structure could be reliably determined via single-crystal X-ray diffraction data. Ga4In4B15O33(OH)3 crystallizes in the tetragonal space group I41/a (origin choice 2) with the lattice parameters a = 11.382(2), c = 15.244(2) Å, and V = 1974.9(4) Å3. The structure of the quaternary triel borate consists of a complex network of BO4 tetrahedra, edge-sharing InO6 octahedra in dinuclear units, and very dense edge-sharing GaO6 octahedra in tetranuclear units.


1985 ◽  
Vol 63 (6) ◽  
pp. 1166-1169 ◽  
Author(s):  
John F. Richardson ◽  
Ted S. Sorensen

The molecular structures of exo-7-methylbicyclo[3.3.1]nonan-3-one, 3, and the endo-7-methyl isomer, 4, have been determined using X-ray-diffraction techniques. Compound 3 crystallizes in the space group [Formula: see text] with a = 15.115(1), c = 7.677(2) Å, and Z = 8 while 4 crystallizes in the space group P21 with a = 6.446(1), b = 7.831(1), c = 8.414(2) Å, β = 94.42(2)°, and Z = 2. The structures were solved by direct methods and refined to final agreement factors of R = 0.041 and R = 0.034 for 3 and 4 respectively. Compound 3 exists in a chair–chair conformation and there is no significant flattening of the chair rings. However, in 4, the non-ketone ring is forced into a boat conformation. These results are significant in interpreting what conformations may be present in the related sp2-hybridized carbocations.


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