Machatschkiite: Crystal structure and revision of the chemical formula

Summary Single crystal X-ray investigation shows that machatschkiite crystallizes in space groupR3c witha _hex =15.127(2) Å andc _hex =22.471(3) Å. The crystal structure was determined by direct methods and Fourier syntheses; the refinement by least squares methods led toR=0.04 for 645 independent reflections. Our X-ray results, supplemented by a partial electron microprobe analysis, indicate that the chemical formula of machatschkiite is close to Ca_6–x Na _x (AsO₄)(AsO₃OH)₃(PO₄)_1–x (SO₄) _x ·15H₂O (x0.3) withZ _hex =6. The atomic arrangement of machatschkiite represents a new structure type and seems to be the first example of a crystal structure in which three oxygens of an AsO₄ group are acceptors of each one hydrogen bond from three surrounding AsO₃(OH) groups.

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Machatschkiit: Kristallstruktur und Revision der chemischen Formel

Zusammenfassung Röntgenographische Einkristalluntersuchungen zeigten, daß Machatschkiit in der RaumgruppeR3c mita _hex =15,127(2) Å undc _hex =22,471(3) Å kristallisiert. Die Kristallstruktur wurde mit direkten Methoden und mit Fourier-Synthesen bestimmt; die Verfeinerung nach der Methode der kleinsten Quadrate führte für 645 Reflexe aufR=0.04. Unser Röntgenbefund, der durch eine partielle Elektronenstrahlmikroanalyse ergänzt wird, weist darauf hin, daß die chemische Formel des Machatschkiites mit guter Näherung Ca_6–x Na _x (AsO₄)(AsO₃OH)₃ (PO₄)_1–x (SO₄) _x ·15H₂O (x0,3) mitZ _hex =6 lautet. Die Atomanordnung des Machatschkiites stellt einen neuen Strukturtyp dar und ist anscheinend das erste Beispiel, in welcher drei Sauerstoffe einer AsO₄-Gruppe Akzeptoren von je einer Wasserstoffbindung dreier benachbarter AsO₃OH-Gruppen sind.

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Dedicated to the memory of Prof. Dr.F. Machatschki, Editor of Tschermaks Mineralogische und Petrographische Mitteilungen 1948–1968.     

A bond-topological approach to theoretical mineralogy: crystal structure, chemical composition and chemical reactions

Here, I describe a theoretical approach to the structure and chemical composition of minerals based on their bond topology. This approach allows consideration of many aspects of minerals and mineral behaviour that cannot be addressed by current theoretical methods. It consists of combining the bond topology of the structure with aspects of graph theory and bond-valence theory (both long range and short range), and using the moments approach to the electronic energy density-of-states to interpret topological aspects of crystal structures. The structure hierarchy hypothesis states that higher bond-valence polyhedra polymerize to form the (usually anionic) structural unit, the excess charge of which is balanced by the interstitial complex (usually consisting of large low-valence cations and (H₂O) groups). This hypothesis may be justified within the framework of bond topology and bond-valence theory, and may be used to hierarchically classify oxysalt minerals. It is the weak interaction between the structural unit and the interstitial complex that controls the stability of the structural arrangement. The principle of correspondence of Lewis acidity–basicity states that stable structures will form when the Lewis-acid strength of the interstitial complex closely matches the Lewis-base strength of the structural unit, and allows us to examine the factors that control the chemical composition and aspects of the structural arrangements of minerals. It also provides a connection between a structure, the speciation of its constituents in aqueous solution and its mechanism of crystallization. The moments approach to the electronic energy density-of-states provides a link between the bond topology of a structure and its thermodynamic properties, as indicated by correlations between average anion coordination number and reduced enthalpy of formation from the oxides for ^[6]Mg _m ^[4] Si _n O_(m+2n) and MgSO₄(H₂O) _n .     

金云母—蛭石间层矿物分晶层晶体化学式的计算及意义

金云母－蛭石间层矿物由金云母晶层与蛭石晶层交叠排列而成,采用一般计算方法得出的晶体化学式不能充分揭示结构中金云母晶层与蛭石晶层各自的晶体化学特征。本文以化学成分分析与阳离子容量为基础,假定可交换性阳离子均为蛭石晶层层间阳离子,非交换性阳离子为金云母晶层层间阳离子,金云母晶层与蛭石晶层具有相同的八面体层等,计算出了结构中两种晶层的分晶层晶体化学式,确定了结构中两种晶层的比例和蛭石晶层的电荷数。并在此基础上讨论了新疆尉犁蛭石矿金云母－蛭石间层矿物的晶体化学特征。结果表明该方法设计合理,符合晶体化学原理,所计算的数据可靠。利用该方法计算出的两种晶层的比例为金云母－蛭石1：1规则间层矿物的确定提供了必要的依据。也为其它类似间层矿物的研究提供了一种计算分晶层晶体化学式的可行方法。     

The crystal structure of cualstibite-1M (formerly cyanophyllite), its revised chemical formula and its relation to cualstibite-1T

The crystal structure of the rare secondary mineral cualstibite-1M (formerly cyanophyllite), originally reported to have the chemical formula 10CuO·2Al₂O₃·3Sb₂O₃·25H₂O and orthorhombic symmetry, was solved from single-crystal intensity data (Mo-Kα X-radiation, CCD area detector, 293 K, 2θ_max?=?80) collected on a twinned crystal containing very minor Mg. The mineral is monoclinic, P2₁/c (no. 14), with a?=?9.938(1), b?=?8.890(1), c?=?5.493(1) Å, β?=?102.90(1)°, V?=?473.05(11) ų; R1(F)?=?0.0326. All crystals investigated turned out to be non-merohedric twins. The atomic arrangement has a distinctly layered character. Brucite-like sheets composed of two [4?+?2]-coordinated (Cu,Al,Mg) sites are linked by weak hydrogen-bonding (O···O?~?2.80 Å) to isolated regular Sb(OH)₆ octahedra (<Sb-O>?=?1.975 Å). The layered, pseudotrigonal character explains the perfect cleavage and the proneness to twinning. The Sb site is fully occupied and the two (Cu,Al,Mg) sites have occupancies of Cu_0.79Al_0.17Mg_0.04 and Cu_0.72Al_0.23Mg_0.05. The Cu-richer site shows a slightly stronger Jahn-Teller-distortion. The resulting empirical formula, which necessitates a H₂O-for-OH substitution to obtain charge balance, is (Cu_2.23Al_0.63Mg_0.14)(OH)_5.63(H₂O)_0.37[Sb⁵⁺(OH)₆]. The ideal chemical formula is (Cu,Al)₃(OH)₆[Sb⁵⁺(OH)₆], with Cu:Al = 2:1. The structure is closely related to those of trigonal cualstibite-1T [Cu₂AlSb(OH)₁₂, P-3, with ordered Cu-Al distribution in the brucite sheets], and its Zn analogue zincalstibite-1T [Zn₂AlSb(OH)₁₂]. Cualstibite-1M and cualstibite-1T are polytypes and, together with zincalstibite-1T, zincalstibite-9R and omsite, belong to the cualstibite group within the hydrotalcite supergroup, which comprises all natural members of the large family of layered double hydroxides (LDH).     

Vertumnite: Its crystal structure and relationship with natural and synthetic phases

Summary Vertumnite, Ca₄Al₄Si₄O₆(OH)₂₄·3H₂O, is metrically monoclinic, strongly pseudohexagonal;a=5.744 (5),b=5.766(5),c=25.12(1) Å, =119.72(5)°; space groupP2 ₁ /m. The crystal structure was determined from X-ray intensities and refined in both the monoclinic and the hexagonal space group [P6 ₃/m; a=(a _mon +b _mon )/2]. The monoclinic refinement did not lead to significant deviations from hexagonal symmetry. The atomic arrangement consists of modified brucite-layers Ca ₂ ^VII Al^VI(OH, H₂O)₈, atz=0 andz=1/2, alternating with tetrahedral double layers and connected only by hydrogen bridges. TheT sites are statistically and only partly occupied by Si and Al. The distances from theT sites to the three basal (O, OH) measure 1.80 Å; this large distance is probably caused by local deformations in connection with the disorder in theT sites. Water molecules occupy statistically the double rings. A comparison with the previously reported powder patterns of gehlenite hydrate and strätlingite is given.

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Vertumnit: Seine Kristallstruktur und seine Beziehungen zu anderen natürlichen und künstlichen Phasen

Zusammenfassung Vertumnit, Ca₄Al₄Si₄O₆(OH)₂₄·3 H₂O, ist metrisch monoklin, ausgeprägt pseudohexagonal;a ₀=5,744(5),b ₀=5,766(5),c ₀=25,12(1) Å, =119,72(5)°; RaumgruppeP2 ₁/m. Die Kristallstruktur wurde aus Röntgenintensitäten bestimmt und sowohl in der monoklinen wie in der hexagonalen Raumgruppe [P6 ₃/m; a ₀=(a _0,mon +b _0,mon )/2] verfeinert. Die monokline Verfeinerung führte auf keine wesentlichen Abweichungen von hexagonaler Symmetrie. Die Atomanordnung besteht aus modifizierten Brucit-Schichten, Ca ₂ ^VII Al^VI(Oh, H₂O)₈, die mit Doppeltetraederschichten abwechseln und mit diesen nur über Wasserstoffbrücken verbunden sind. DieT-Positionen sind durch Si und Al statistisch und nur partiell besetzt. Die Abstände von denT-Positionen zu den drei basalen (O, OH) messen 1,80 Å; dieser große Abstand wird wahrscheinlich durch lokale Verzerrungen im Zusammenhang mit der Unordnung in denT-Lagen verursacht. Wassermoleküle füllen statistisch die Doppelringe. Das Pulverdiagramm wird mit den publizierten Diagrammen von Gehlenit-Hydrat und Strätlingit verglichen.

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With 2 Figures     

Kyzylkumite: a finding in the southern Baikal region, Russia and refinement of its crystal chemical formula

Kyzylkumite has been found in Cr-V-bearing metamorphic rocks of the Sludyanka Complex, Southern Baikal region; it has been identified by X-ray powder diffraction method. This is a late secondary mineral developed after Ti-V-oxides (schreyerite, berdesinskiite) and V-bearing rutile and titanite. Kyzylkumite represents a new structural type with composition Ti₄V ₂ ³⁺ O₁₀(OH)₂ corresponding to octahedral coordination of Ti⁴⁺ and V³⁺. Its unit-cell dimensions are: a = 8.4787(1), b = 4.5624(1), c = 10.0330(1) Å, β = 93.174(1)°. The ideal formula of kyzylkumite Ti₄V ₂ ³⁺ O₁₀(OH)₂ corresponds to composition, wt %: 65.56 TiO₂, 30.75 V₂O₃, 3.69 H₂O. Indeed, the contents (wt %) of these constituents range from 62 to 70 TiO₂ and from 23 to 33 V₂O₃. Variations in contents and the Ti/V value are caused by partial substitution V³⁺ for V⁴⁺, isovalent substitutions Ti⁴⁺ and V³⁺ for V⁴⁺ and Cr³⁺, respectively, and coupled substitution V³⁺ + OH^? ? Ti⁴⁺ + O^2?. Smyslova et al. (1981)—the discovereres of kyzylkumite—assumed its composition to be the same as for schreyerite V ₂ ³⁺ Ti₃O₉ that principally different from kyzylkumite from the Sludyanka Complex. Therefore, re-examination of the kyzylkumite holotype or cotype from its type locality is needed.     

A crystal chemical study of protoanthophyllite: orthoamphiboles with the protoamphibole structure

Two new protoamphibole-type amphiboles with space group type Pnmn, have been found in nature: protoferro-anthophyllite (Fe_0.80Mn_0.20)₂ (Fe_0.98Mg_0.02)₅ (Si₄O₁₁)₂(OH)₂, and protomangano-ferro-anthophyllite, (Mn_0.70Fe_0.30)₂ (Fe_0.82Mg_0.18)₅ (Si₄O₁₁)₂(OH)₂. Protoferro-anthophyllite (PFA) occurs in pegmatites at both Gifu Prefecture, Japan and at Cheyenne Mountain, El Paso County, Colorado, USA. Protomangano-ferro-anthophyllite, (PMFA) occurs in pegmatites at Fukushima Prefecture and in a Mn mine at Tochigi Prefecture, Japan. Structure determinations of the two amphiboles show that both are isostructural with the synthetic fluorian-amphibole, protoamphibole (= protofluorian-lithian-anthophyllite). A calculation of the procrystal electron density distributions, the bond paths and the bond critical point properties of PFA, PMFA, grunerite and protoamphibole indicates that the M4 cation in these amphiboles is 4-coordinated. A calculation of the electron density distributions at the Becke3LYP/6-311G(2d,p) level for model silicate tetrahedra for these amphiboles and anthophyllite reveals that the value of the electron density at the bond critical points, ρ(r _c ), for the SiO(nbr) bonds is larger, on average (0.93 e/ų), than that for the SiO(br) bonds (0.90 e/ų). The observed SiO bond lengths decrease linearly with increasing ρ(r _c ) while the magnitudes of the curvatures of ρ(r _c ) both perpendicular and parallel to the bonds and the Laplacian of ρ(r _c ) each increases. These trends are associated with an increase in the electronegativity of the Si cation, a possible increase in the covalent character of the SiO bond and a tendency for SiO(nbr) bonds to be involved in wider OSiO angles than SiO(br) bonds. It is possible, if not likely, that protoanthophyllite has often been misidentified as anthophyllite.     

Niocalite revised: Twinning and crystal structure

Summary Niocalite (monoclinicPa, a=10.863(3),b=10.431(3),c=7.370(2) Å, =110.1(1)°) belongs to the cuspidine group. Its crystal structure has been refined toR ₁=0.069 andR _w=0.046, using 2411 independent reflections. Niocalite is isostructural with cuspidine and lavenite, but topologically distinct from the related mineral wöhlerite.The present model differs, from the structure proposed byLi Te Yü et al. (1966) because of the different choice of space group (Pa instead ofP2₁). The previous erroneous space group identification was due to neglecting the usual twinning of niocalite. In fact, the X-ray diffraction patterns and the electron optical images show that the mineral occurs as a dense intergrowth of twinned lamellae, having (100) as the twin composition plane and 100–1000 Å thickness.The chemical analysis, together with the results of the structure refinement, gives the crystal chemical formula Nb₂Ca₁₄(Si₂O₇)₄O₆F₂.The structure refinement seemed to indicate disordered distribution of niobium and calcium atoms within two different sites. In any case, this apparent disorder is supposed to be fictitious and would be due to the occurrence of twinning. Namely, the crystal structure would consist of twin related domains, each of them being characterized by ordered distribution of calcium and niobium atoms.

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Zur Kristallstruktur und Verzwillingung von Niocalit

Zusammenfassung Niocalit (monoklinPa, a=10,863(3),b=10,431(3),c=7,370(2) Å, =110,1(1)°) gehört zur Cuspidin-Gruppe. Seine Kristallstruktur wurde verfeinert aufR ₁=0.069 undR _w=0,046, auf der Basis von 2411 unabhängigen Reflexen. Niocalit ist isotrukturell mit Cuspidin und Låvenit, aber topologisch verschieden von dem verwandten Mineral Wöhlerit.Das vorgelegte Modell unterscheidet sich von der Struktur, dieLi Te Yu et al. (1966) vorgeschlagen haben, vor allem wegen der verschiedenen Wahl der Raumgruppe (Pa anstatt vonP2₁). Die Tatsache, daß die Raumgruppe früher nicht korrekt bestimmt werden konnte, geht darauf zurück, daß die verbreitete Verzwillingung von Niocalit nicht beachtet wurde. Diffraktometeraufnahmen und elektronenoptische Bilder zeigen, daß das Mineral als eine enge Verwachsung von verzwillingten Lamellen, mit (100) als Verwachsungsebene und 500–1000 Å Durchmesser auftritt.Die chemische Analyse, zusammen mit den Ergebnissen der Strukturverfeinerung geben die kristallchemische Formel Nb₂Ca₁₄(Si₂O₇)₄O₆F₂.Die Strukturverfeinerung schien anzudeuten, daß eine ungeordnete Verteilung von Niobium- und Kalzium-Atomen innerhalb von zwei verschiedenen Positionen vorliegt. Diese scheinbare Unordnung ist nicht reell und ist dieser Verzwillingung zuzuschreiben. Die Kristallstruktur besteht aus zwillingsbezogenen Bereichen, jeder von ihnen wird durch eine geordnete Verteilung der Kalzium- und Niobium-Atome charakterisiert.

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With 7 Figures     

Tantalum-bearing titanite: synthesis and crystal structure data

Synthetic titanite, CaTiOSiO₄, and the series of (Ca_1−x Na _x )(Ti_1−x Ta _x )OSiO₄ and Ca(Ti_1−2x Ta _x Al _x )OSiO₄ solid solutions have been prepared by ceramic methods, and their crystal structure determined by the Rietveld analysis. At ambient conditions, titanite can contain up to 20 mol% NaTaOSiO₄ or 60 mol% Ca(Al_0.5Ta_0.5)OSiO₄. These limits might differ in natural samples due to combination with substitutions involving fluorine and/or hydroxyl replacing oxygen together with vacancies at cationic sites. All cations located at the ^vii X- and ^vi Y-sites in the structures of tantalian titanite are disordered. Expansion of the <Si–O> bond from 1.618 to 1.621 Å in CaTi_0.8Ta_0.1Al_0.1OSiO₄ and CaTi_0.6Ta_0.2Al_0.2OSiO₄ to 1.644 Å in the CaTi_0.4Ta_0.3Al_0.3OSiO₄ titanite suggests the possible presence of some Al³⁺ in the tetrahedral site replacing Si⁴⁺ in the latter. All tantalian titanites crystallize in the space group A2/a. This implies that both single-site and complex double-site substitutional schemes induce P2₁/a → A2/a phase transition(s). The (Ca_1−x Na _x )(Ti_1−x Ta _x )OSiO₄ substitution scheme incorporates larger cations at both the ^vii X and ^vi Y sites, whereas the Ca(Ti_1−2x Ta _x Al _x )OSiO₄ scheme involves only ^vi Y-site (Al³⁺,Ta⁵⁺) cations with a slightly smaller “average” radius. Unit cell dimensions change insignificantly or increase incrementally with increase of average cationic radii in the (Ca_1−x Na _x )(Ti_1−x Ta _x )OSiO₄ series, and with an insignificant decrease in the ^viR _Y average cationic radii in the Ca(Ti_1−2x Ta _x Al _x )OSiO₄ series. Both Ta-doped titanite and CaTiOSiO₄ consist of distorted polyhedra with the XO₇, YO₆ coordination polyhedra and the SiO₄ tetrahedron in tantalian titanite being less distorted compared to those of the pure CaTiOSiO₄.     

Kerogen: chemical structure and formation conditions

The available data on the composition of the pyrolysis products of kerogen from the Mesozoic carbonaceous strata of the Russian Plate evidence that changes in the contents of total organic carbon (TOC) lead to a regular change of the mechanisms of organic-matter (OM) conservation in sediments. Each mechanism prevails for particular TOC contents. The initial increase in the TOC content of rocks is accounted for by the fact that the higher is the biologic productivity of the basin, the higher is the portion of nonmineralized organic matter. This is due mainly to the mechanism of selective accumulation of the most stable biochemical components such as algaenan. The appearance of H₂S first in the pore waters of sediment and then in the water column increases the degree of preservation of initial OM at the expense of its sulfurization. This process runs first in the lipid and then in the carbohydrate fractions of initial OM.     

Schorlomite: a discussion of the crystal chemistry, formula, and inter-species boundaries

Examination of schorlomite from ijolite at Magnet Cove (USA) and silicocarbonatite at Afrikanda (Russia), using electron-microprobe and hydrogen analyses, X-ray diffraction and Mössbauer spectroscopy, shows the complexity of substitution mechanisms operating in Ti-rich garnets. These substitutions involve incorporation of Na in the eightfold-coordinated X site, Fe²⁺ and Mg in the octahedrally coordinated Y site, and Fe³⁺, Al and Fe²⁺ in the tetrahedrally coordinated Z site. Substitutions Ti⁴⁺Fe³⁺Fe³⁺_–1Si_–1 and Ti⁴⁺Al³⁺Fe³⁺_–1Si_–1 are of major significance to the crystal chemistry of schorlomite, whereas Fe²⁺ enters the Z site in relatively minor quantities (<3% Fe). There is no evidence (either structural or indirect, such as discrepancies between the measured and calculated Fe²⁺ contents) for the presence of ^[6]Ti³⁺ or ^[4]Ti⁴⁺ in schorlomite. The simplified general formula of schorlomite can be written as Ca₃Ti⁴⁺₂[Si_3-x(Fe³⁺,Al,Fe²⁺)_xO₁₂], keeping in mind that the notion of end-member composition is inapplicable to this mineral. In the published analyses of schorlomite with low to moderate Zr contents, x ranges from 0.6 to 1.0, i.e. Ti⁴⁺ in the Y site is <2 and accompanied by appreciable amounts of lower-charged cations (in particular, Fe³⁺, Fe²⁺ and Mg). For classification purposes, the mole percentage of schorlomite can be determined as the amount of ^[6]Ti⁴⁺, balanced by substitutions in the Z site, relative to the total occupancy in the Y site: (^[6]Ti⁴⁺–^[6]Fe²⁺–^[6]Mg²⁺– ^[8]Na⁺)/2. In addition to the predominant schorlomite component, the crystals examined in this work contain significant (>15 mol.%) proportions of andradite (Ca₃Fe³⁺₂Si₃O₁₂), morimotoite (Ca₃Fe²⁺TiSi₃O₁₂), and Ca₃MgTiSi₃O₁₂. The importance of accurate quantitative determination and assignment of Fe, Ti and other cations to the crystallographic sites for petrogenetic studies is discussed.

Lithium-containing Na-Fe-amphibole from cryolite rocks of the Katugin rare-metal deposit (Transbaikalia,Russia): chemical features and crystal structure

Detailed chemical and structural studies were carried out for Li-Na-Fe-amphibole from cryolite rocks of the Katugin deposit, Transbaikalia. The rocks contain 30-70 vol.% cryolite, mafic minerals as Fe-silicates (Li-Na-Fe-amphibole, Li-containing fluorannite, and bafertisite), oxides (magnetite, ilmenite, pyrochlore, cassiterite, and others), and sulfides (sphalerite, pyrite, and chalcopyrite). Quartz, K-feldspar, polylithionite, REE-fluorides, and albite occur as minor or accessory phases. The chemical composition of amphibole (wt.%) varies as follows: SiO₂, 48.5-48.9; TiO2, 0.4-0.8; M2O3, 1.6-2.2; Fe2O3, 15.9-17.1; FeO, 17.6-18.4; MnO, 0.8-0.9; ZnO, 0.3-1.1; MgO, 0.2-0.3; CaO, < 0.1; Na2O, 8.4-8.7; K₂O, 1.4-1.5; Li₂O, 0.6-0.8; H₂O, 0.7-0.8; and F, 2.2-2.5. The amphibole has a specific composition intermediate among the F-Fe members of the Na-amphibole subgroup: 40-45 mol.% ferro-ferri-fluoro-nyb0ite, 40-45 mol.% ferro-ferri-fluoro-leakeite, and 10-20 mol.% fluoro-riebeckite ± fluoro-arfvedsonite. The mineral is monoclinic, space group C2/m, a = 9.7978(2), b = 17.9993(3), c = 5.33232(13) A, P = 103.748(2)°, V = 913.43(3) A³, and Z = 2. The structural formula of Li-Na-Fe-amphibole is (Nao.₄6Ko.₂₄do.₃o)Na₂.oo(Fea95Mgo.o5)₂- (Fe0⁺ 95Ti0.025Mg0.025)2(Li0.37Fea48Mn0.10Zn0.05)[(Si0.91Al <).09)4Si4O22](F0.58(OH)0.42)2. R^amaⁿ and Mossbauer spectroscopy data are given for this amphibole.     

Vulcanite, CuTe: hydrothermal synthesis and crystal structure refinement

Summary The crystal structure of the mineral vulcanite, CuTe [a = 3.155(1), b = 4.092(1), c = 6.956(1) ?; Z = 2; space group: Pmmn, No. 59] exhibits a pronounced layer structure with Te-Te distances between the CuTe layers of 4.019(1) ?. Within a range up to 4.2 ? the individual Cu atom is [4Te+4Cu+2Cu], the individual Te atom [4Cu+2Te+4Te] coordinated. Crystals of vulcanite suitable for the present structure investigation were synthesized under hydrothermal conditions.

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Zusammenfassung Vulkanit, CuTe: Hydrothermalsynthese und Verfeinerung der Kristallstruktur Die Kristallstruktur des Minerals Vulkanit, CuTe [a = 3,155(1), b = 4,092(1), c =  6,956(1) ?; Z = 2; Raumgruppe: Pmmn, No. 59] stellt eine ausgepr?gte Schichtstruktur mit Te-Te-Abst?nden zwischen den Cu-Te-Schichten von 4,019(1) ? dar. Im Bereich bis 4,2 ? wird jedes individuelle Cu-Atom von [4Te+4Cu+2Cu], jedes Te-Atom von [4Cu+2Te+4Te] koordiniert. Für die vorliegende Strukturbestimmung geeignete Kristalle von Vulkanit wurden unter hydrothermalen Bedingungen synthetisiert.

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Received December 17, 1999; revised version accepted August 30, 2000     

The crystal structure of sarcolite

Summary The crystal structure of sarcolite from Monte Somma (Vesuvius), Na(Na, K, Fe, Mg)<1 Ca₆[Al₄Si₆O₂₃](OH, H₂O)<2 [(Si,P)O₄]_0.5[(CO₃, Cl)]_0.5, space groupI4/m witha=12,343(5)Å,c=15,463(5)Å andZ=4, has been determined from X-ray data collected on an automatic diffractometer. The 1637 independent reflections withI>2 (I) converged to a conventionalR value of 0.054 with partially anisotropic factors.The tetrahedral framework in sarcolite has a sharing coefficient of 1.85. Mean Si–O and Al–O distances are 1.616 and 1.763 Å, respectively. Isolated (Si, P)O₄, CO₃, OH, H₂O and Cl species occupy cavities in the tetrahedral framework in a partially disordered way. The two crystallographically different Ca atoms coordinate respectively with 5 and 6 framework oxygens; further contacts occur with available anions. Ca–O distances range from 2.34 to 2.69 Å. Na atoms coordinate with 4 oxygens of the tetrahedral frame and one from the CO₃ groups.A structure analysis of a sarcolite crystal baked out at 1100°C confirmed some structural details involving atoms occupying cavities in the tetrahedral framework.

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Die Kristallstruktur des Sarkoliths

Zusammenfassung Die Kristallstruktur des Sarkoliths vom Monte Somma (Vesuv), Na(Na, K, Fe, Mg)<1 Ca₆[Al₄Si₆O₂₃](OH, H₂O)<2[(Si, P)O₄]_0,5[(CO₃, Cl)]_0,5, RaumgruppeI4/m,a ₀=12,343(5)Å,c ₀=15,463(5)Å,Z=4, wurde aus Röntgendaten, die auf einem automatischen Diffraktometer gesammelt worden waren, bestimmt. Der konventionelleR-Wert für 1637 kristallographisch unabhängige Reflexe mitI>2 (I) konvergierte mit partiell anisotropen Temperaturfaktoren auf 0.054.Der Verknüpfungskoeffizient des Tetraedergerüstes in Sarkolith ist 1,85. Die mittleren Si–O-bzw. Al–O-Abstände sind 1,616Å und 1,763 Å. Isolierte Strukturbestandteile (Si, P)O₄, CO₃, OH, H₂O und Cl besetzen zum Teil ungeordnet die Hohlräume des Tetraedergerüstes. Die beiden kristallographisch verschiedenen Ca-Atome werden von funf bzw. sechs Sauerstoffen des Gerüstes koordiniert, weitere Kontakte bestehen zu verfügbaren Anionen. Die Ca–O-Abstände variieren von 2,34 bis 2,69 Å. Die Na–Atome sind von vier Sauerstoffen des Tetraedergerüstes und von einem weiteren der CO₃-Gruppen koordiniert. Die Strukturanalyse eines bei 1100°C getemperten Sarkolithkristalls bestätigte einige Details über die Atome, welche die Hohlräume des Tetraedergerüstes besetzen.

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With 4 Figures     

The crystal structure of stringhamite

Summary The crystal structure of stringhamite, Ca[Cu(SiO₄)](H₂O),a=5.030(2),b=16.135(3),c=5.343(1) Å, =102.96(1)^o,V=422.7(2) ų,Z=4, space groupP2₁/c, has been solved by direct methods and refined by a full-matrix least-squares procedure to anR index of 3.7% for 1009 observed (3 ) reflections measured on a twinned crystal. The structure has one H₂O molecule in its unit formula, rather than two as reported by previous study. As suggested by its formula, stringhamite is a neosilicate with Cu²⁺ in square planar coordination and Ca in [7]-coordination that approximates a diminished square antiprism.The fundametal building block of the stringhamite structure is a [Cu(SiO₄)O₃]^8– heteropolyhedral cluster that polymerizes in two dimensions by corner-sharing between the squares and tetrahedra to form the structure module, a [Cu(SiO₄)]^2– heteropolyhedral sheet parallel to (010). These sheets are linked together by Ca atoms and hydrogen-bonding involving the H₂O anioris in the structure.

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Die Kristallstruktur des Stringhamits

Zusammenfassung Die Kristallstruktur des Stringhamits, Ca[Cu(SiO₄)](H₂O),a=5,030(2),b=16,135(3),c=5,343(1) Å, =102,96(1)^o,V=422,7(2) ų,Z=4, RaumgruppeP2₁/c, wurde mit direkten Methoden gelöst und für 1009 beobachtete (3 ) Reflexe, die an einem verzwillingten Kristall gemessen worden waren, aufR=3,7 verfeinert. Die Struktur enthält nur ein H₂O-Molekül pro Formeleinheit und nicht zwei, wie in einer früheren Arbeit angegeben wurde. In Übereinstimmung mit seiner Formel ist Stringhamit ein Nesosilikat, Cu²⁺ hat eine planare 4-Koordination und Ca eine 7-Koordination, die einem tetragonalen Antiprisma mit einer unbesetzten Ecke ähnelt.Der fundamentale Baublock in der Struktur des Stringhamits ist eine heteropolyedrische [Cu(SiO₄)O₃]^8–-Gruppe. Diese polymerisieren über gemeinsame Ecken zwischen den Quadraten und den Tetraedern in zwei Richtungen zur Baueinheit, einer heteropolyedrischen [Cu(SiO₄)]^2–-Schicht parallel (010). Diese Schichten werden durch Ca-Atome und Wasserstoffbrücken, welche die H₂O-Anionen einbeziehen, miteinander verknüpft.

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With 3 Figures