Crystal chemistry of natural layered double hydroxides. I. Quintinite-2<i>H</i>-3<i>c</i> from the Kovdor alkaline massif, Kola peninsula, Russia

Krivovichev, Sergey V.; Yakovenchuk, Victor N.; Zhitova, Elena S.; Zolotarev, Andrey A.; Pakhomovsky, Yakov A.; Ivanyuk, Gregory Yu.

doi:10.1180/minmag.2010.074.5.821

Cited by 37 publications

(42 citation statements)

References 38 publications

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“…Thus, the presence of the reflection with d = 4.57 Å in the powder pattern of pure LDHs having M 2+ :M 3+ = 2:1 is a reliable indicator of cation ordering similar to the Li 2 Al LDHs [47][48][49][50]. In contrast to Cl-bearing hydrotalcite-supergroup members, the carbonate species have been structurally characterized in more details including recent single-crystal or Rietveld structure refinements of hydrotalcite [31], pyroaurite [51][52][53], quintinite [34,[53][54][55][56][57][58], takovite [59], and zaccagnaite [60]. It has been found that C atoms of CO 3 groups occupy central parts of the interlayer prisms (Figure 7b), whereas O atoms of CO 3 groups and H 2 O molecules are disordered around the middle points of the prism edges.…”

Section: Discussionmentioning

confidence: 99%

Crystal Chemistry of Chlormagaluminite, Mg4Al2(OH)12Cl2(H2O)2, a Natural Layered Double Hydroxide

et al. 2019

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Chlormagaluminite is the only Cl-dominated hydrotalcite-supergroup mineral species with M2+:M3+ = 2:1. The holotype sample of chlormagaluminite from the Kapaevskaya volcanic pipe (Irkutsk Oblast, Siberia, Russia) has been chemically and structurally characterized. The average chemical composition of the mineral is (electron microprobe, OH content is calculated by stoichiometry and H2O from the crystal-structure data, wt. %): MgO 33.85, FeO 1.09, Al2O3 22.07, Cl 14.72, H2Otot 30.96, Cl=O −3.39, total 99.30. The empirical formula based on Mg + Al + Fe = 6 atoms per formula unit (apfu) is [Mg3.91Fe2+0.07Al2.02(OH)12]Cl2.02(H2O)2.0(2). The crystal structure has been solved from single-crystal X-ray diffraction data in the space group P63/mcm, a = 5.268(3), c = 15.297(8) Å and V = 367.6(4) Å3. The refinement converged to R1 = 0.083 on the basis of 152 unique reﬂections with I > 2σ(I) collected at room conditions. The powder pattern contains standard reflections of a 2H polytype and two additional reflections [(010), d010 = 4.574 Å; (110), d110 = 2.647 Å] indicative of Mg and Al ordering according to the superstructure. The structure is based upon brucite-type octahedral layers with an ordered distribution of Mg and Al over octahedral sites. The Cl− anions and H2O molecules reside in the interlayer, providing a three-dimensional integrity of the structure.

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Section: Discussionmentioning

confidence: 99%

Crystal Chemistry of Chlormagaluminite, Mg4Al2(OH)12Cl2(H2O)2, a Natural Layered Double Hydroxide

et al. 2019

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“…Up to a certain point, the hydrocerussite-related structures bear similarities to other families of layered structures, such as graphite, micas (Brigatti & Guggenheim, 2002), layered double hydroxides (Krivovichev et al, 2010;Mills et al, 2012) or certain transition metal sulfides, to name just a few. The combination of relatively strong bonds within the layers, but weak interlayer coherence, provides all these structures with a variety of certain common characteristics and properties, e.g.…”

Section: Discussionmentioning

confidence: 99%

Hydrocerussite-related minerals and materials: structural principles, chemical variations and infrared spectroscopy

Siidra

Nekrasova

Depmeier

et al. 2018

Acta Crystallogr Sect B

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White lead or basic lead carbonate, 2PbCO·Pb(OH), the synthetic analogue of hydrocerussite Pb(OH)(CO), has been known since antiquity as the most frequently used white paint. A number of different minerals and synthetic materials compositionally and structurally related to hydrocerussite have been described within the last two decades. Herein, a review is given of general structural principles, chemical variations and IR spectra of the rapidly growing family of hydrocerussite-related minerals and synthetic materials. Only structures containing a hydroxo- and/or oxo-component, i.e. which are compositionally directly related with hydrocerussite and `white lead', are reviewed in detail. An essential structural feature of all the considered phases is the presence of electroneutral [PbCO] cerussite-type layers or sheets. Various interleaved sheets can be incorporated between the cerussite-type sheets. Different sheets are stacked into two-dimensional blocks separated by the stereochemically active 6s lone electron pairs on Pb cations. Minerals and synthetic materials described herein, together with a number of still hypothetical members, constitute a family of modular structures. Hydrocerussite, abellaite and grootfonteinite can be considered to constitute a merotype family of structures. The remaining hydrocerussite-related structures discussed are built on similar principles, but are more complex. Structural architectures of somersetite and slag phase from Lavrion, Attica, Greece, are unique for oxysalt mineral structures in general. Thus, the whole family of hydrocerussite-related phases can be denoted as a plesiotype family of modular structures. The crystal structures of hydrocerussite from Merehead quarry, Somerset, England, and of its synthetic analogue, both determined from single crystals, are reported here for the first time. The results of the infrared (IR) spectroscopy show that this method is useful for distinguishing several different minerals related to hydrocerussite and their synthetic analogues.

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“…The OÀH bonds are not necessarily aligned parallel to c (cf. Krivovichev et al, 2010a). This arrangement presumably optimizes hydrogen bonding to the interlayer species.…”

Section: Crystal Chemistry Of the Hydrotalcite Supergroupmentioning

confidence: 96%

Nomenclature of the hydrotalcite supergroup: natural layered double hydroxides

Mills¹,

Christy²,

Génin³

et al. 2012

Mineral. mag.

354

319

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Layered double hydroxide (LDH) compounds are characterized by structures in which layers with a brucite-like structure carry a net positive charge, usually due to the partial substitution of trivalent octahedrally coordinated cations for divalent cations, giving a general layer formula [(M1–x2+M3+x)(OH)2]x+. This positive charge is balanced by anions which are intercalated between the layers. Intercalated molecular water typically provides hydrogen bonding between the brucite layers. In addition to synthetic compounds, some of which have significant industrial applications, more than 40 mineral species conform to this description. Hydrotalcite, Mg6Al2(OH)16[CO3]·4H2O, as the longest-known example, is the archetype of this supergroup of minerals. We review the history, chemistry, crystal structure, polytypic variation and status of all hydrotalcite-supergroup species reported to date. The dominant divalent cations,M2+, that have been reported in hydrotalcite supergroup minerals are Mg, Ca, Mn, Fe, Ni, Cu and Zn; the dominant trivalent cations,M3+, are Al, Mn, Fe, Co and Ni. The most common intercalated anions are (CO3)2–, (SO4)2–and Cl–; and OH–, S2–and [Sb(OH)6]– have also been reported. Some species contain intercalated cationic or neutral complexes such as [Na(H2O)6]+or [MgSO4]0. We define eight groups within the supergroup on the basis of a combination of criteria. These are (1) the hydrotalcite group, withM2+:M3+= 3:1 (layer spacing ∼7.8 Å); (2) the quintinite group, withM2+:M3+= 2:1 (layer spacing ∼7.8 Å); (3) the fougèrite group, withM2+= Fe2+,M3+= Fe3+in a range of ratios, and with O2– replacing OH– in the brucite module to maintain charge balance (layer spacing ∼7.8 Å); (4) the woodwardite group, with variableM2+:M3+and interlayer [SO4]2 –, leading to an expanded layer spacing of ∼8.9 Å; (5) the cualstibite group, with interlayer [Sb(OH)6]– and a layer spacing of ∼9.7 Å; (6) the glaucocerinite group, with interlayer [SO4]2– as in the woodwardite group, and with additional interlayer H2O molecules that further expand the layer spacing to ∼11 Å; (7) the wermlandite group, with a layer spacing of ∼11 Å, in which cationic complexes occur with anions between the brucite-like layers; and (8) the hydrocalumite group, withM2+= Ca2+andM3+= Al, which contains brucite-like layers in which the Ca:Al ratio is 2:1 and the large cation, Ca2+, is coordinated to a seventh ligand of 'interlayer' water.The principal mineral status changes are as follows. (1) The names manasseite, sjögrenite and barbertonite are discredited; these minerals are the 2H polytypes of hydrotalcite, pyroaurite and stichtite, respectively. Cyanophyllite is discredited as it is the 1M polytype of cualstibite. (2) The mineral formerly described as fougèrite has been found to be an intimate intergrowth of two phases with distinct Fe2+:Fe3+ratios. The phase with Fe2+:Fe3+= 2:1 retains the name fougèrite; that with Fe2+:Fe3+= 1:2 is defined as the new species trébeurdenite. (3) The new minerals omsite (IMA2012-025), Ni2Fe3+(OH)6[Sb(OH)6], and mössbauerite (IMA2012-049), Fe3+6O4(OH)8[CO3]·3H2O, which are both in the hydrotalcite supergroup are included in the discussion. (4) Jamborite, carrboydite, zincaluminite, motukoreaite, natroglaucocerinite, brugnatellite and muskoxite are identified as questionable species which need further investigation in order to verify their structure and composition. (5) The ranges of compositions currently ascribed to motukoreaite and muskoxite may each represent more than one species. The same applies to the approved species hydrowoodwardite and hydrocalumite. (6) Several unnamed minerals have been reported which are likely to represent additional species within the supergroup.This report has been approved by the Commission on New Minerals, Nomenclature and Classification (CNMNC) of the International Mineralogical Association, voting proposal 12-B.We also propose a compact notation for identifying synthetic LDH phases, for use by chemists as a preferred alternative to the current widespread misuse of mineral names.

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Crystal chemistry of natural layered double hydroxides. I. Quintinite-2H-3c from the Kovdor alkaline massif, Kola peninsula, Russia

Cited by 37 publications

References 38 publications

Crystal Chemistry of Chlormagaluminite, Mg4Al2(OH)12Cl2(H2O)2, a Natural Layered Double Hydroxide

Crystal Chemistry of Chlormagaluminite, Mg4Al2(OH)12Cl2(H2O)2, a Natural Layered Double Hydroxide

Hydrocerussite-related minerals and materials: structural principles, chemical variations and infrared spectroscopy

Nomenclature of the hydrotalcite supergroup: natural layered double hydroxides

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