Next Article in Journal
Melt Inclusions in Plagioclase Macrocrysts at Mount Jourdanne, Southwest Indian Ridge (~64° E): Implications for an Enriched Mantle Source and Shallow Magmatic Processes
Next Article in Special Issue
Dmisteinbergite, CaAl2Si2O8, a Metastable Polymorph of Anorthite: Crystal-Structure and Raman Spectroscopic Study of the Holotype Specimen
Previous Article in Journal
Composition of Amphiboles in the Tremolite–Ferro–Actinolite Series by Raman Spectroscopy
Previous Article in Special Issue
Crystal Chemistry and High-Temperature Behaviour of Ammonium Phases NH4MgCl3·6H2O and (NH4)2Fe3+Cl5·H2O from the Burned Dumps of the Chelyabinsk Coal Basin
 
 
Search for Articles:
Title / Keyword
Author / Affiliation / Email
Journal
Article Type
 
 
Advanced Search
 
Section
Special Issue
Volume
Issue
Number
Page
 
Journals
Minerals
Volume 9
Issue 8
10.3390/min9080492
minerals-logo
Submit to this Journal Review for this Journal Propose a Special Issue
► Article Menu

Article Menu

share Share announcement Help format_quote Cite question_answer Discuss in SciProfiles thumb_up
...
Endorse textsms
...
Comment
first_page
settings
Order Article Reprints
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Article

Dritsite, Li2Al4(OH)12Cl2·3H2O, a New Gibbsite-Based Hydrotalcite Supergroup Mineral

by
Elena S. Zhitova
1,2,*,
Igor V. Pekov
3,
Ilya I. Chaikovskiy
4,
Elena P. Chirkova
4,
Vasiliy O. Yapaskurt
3,
Yana V. Bychkova
3,
Dmitry I. Belakovskiy
5,
Nikita V. Chukanov
6,
Natalia V. Zubkova
3,
Sergey V. Krivovichev
1,7 and
Vladimir N. Bocharov
8
1
Department of Crystallography, St. Petersburg State University, Universitetskaya nab. 7/9, St. Petersburg 199034, Russia
2
Laboratory of Mineralogy, Institute of Volcanology and Seismology, Russian Academy of Sciences, Bulvar Piypa 9, Petropavlovsk-Kamchatsky 683006, Russia
3
Faculty of Geology, Moscow State University, Vorobievy Gory, Moscow 119991, Russia
4
Mining Institute, Ural Branch of the Russian Academy of Sciences, Sibirskaya str., 78a, Perm 614007, Russia
5
Fersman Mineralogical Museum, Russian Academy of Sciences, Leninsky Prospekt 18-2, Moscow 119071, Russia
6
Institute of Problems of Chemical Physics, Russian Academy of Sciences, Akad. Semenova 1, Chernogolovka, Moscow Region 142432, Russia
7
Nanomaterials Research Centre, Kola Science Centre, Russian Academy of Sciences, Fersman Street 14, Apatity 184209, Russia
8
Resource Center Geomodel, St. Petersburg State University, Universitetskaya nab. 7/9, St. Petersburg 199034, Russia
*
Author to whom correspondence should be addressed.
Minerals 2019, 9(8), 492; https://doi.org/10.3390/min9080492
Submission received: 2 August 2019 / Revised: 13 August 2019 / Accepted: 14 August 2019 / Published: 17 August 2019
(This article belongs to the Special Issue Selected Papers from the XIX International Meeting on Crystal Chemistry, X-ray Diffraction and Spectroscopy of Minerals)
Browse Figures
Versions Notes

Abstract

:
Dritsite, ideally Li2Al4(OH)12Cl2·3H2O, is a new hydrotalcite supergroup mineral formed as a result of diagenesis in the halite−carnallite rock of the Verkhnekamskoe salt deposit, Perm Krai, Russia. Dritsite forms single lamellar or tabular hexagonal crystals up to 0.25 mm across. The mineral is transparent and colourless, with perfect cleavage on {001}. The chemical composition of dritsite (wt. %; by combination of electron microprobe and ICP−MS; H2O calculated by structure refinement) is: Li2O 6.6, Al2O3 45.42, SiO2 0.11, Cl 14.33, SO3 0.21, H2Ocalc. 34.86, O = Cl − 3.24, total 98.29. The empirical formula based on Li + Al + Si = 6 apfu (atom per formula unit) is Li1.99Al4.00Si0.01[(OH)12.19Cl1.82(SO4)0.01]Σ14.02·2.60(H2O). The Raman spectroscopic data indicate the presence of O–H bonding in the mineral, whereas CO32– groups are absent. The crystal structure has been refined in the space group P63/mcm, a = 5.0960(3), c = 15.3578(13) Å, and V = 345.4(5) Å3, to R1 = 0.088 using single-crystal data. The strongest lines of the powder X-ray diffraction pattern (d, Å (I, %) (hkl)) are: 7.68 (100) (002), 4.422 (61) (010), 3.832 (99) (004, 012), 2.561 (30) (006), 2.283 (25) (113), and 1.445 (26) (032). Dritsite was found as 2H polytype, which is isotypic with synthetic material and shows strong similarity to chlormagalumite-2H. The mineral is named in honour of the Russian crystallographer and mineralogist Prof. Victor Anatol`evich Drits.

1. Introduction

In this paper we provide a description of the new hydrotalcite supergroup mineral dritsite. Hydrotalcite supergroup minerals are commonly known as layered double hydroxides (LDHs), i.e., hydroxides containing two cations, usually di- and trivalent [1,2,3], although a group of synthetic LiAl2-based LDHs is also known [4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19]. Currently, forty-four hydrotalcite supergroup minerals are known, including some that are questionable as mineral species [3]. All of them, excluding mössbauerite, are composed of di- and trivalent cations, whereas mössbauerite contains only Fe3+ [20]. The new monoclinic mineral akopovaite, recently approved by the IMA−CNMNC (International Mineralogical Association, Commission on new minerals, nomenclature and classification) (IMA2018-095, [21]), has the chemical formula Li2Al4(OH)12CO3·3H2O, however, its full description has not yet been published. Thus, here we provide the first description of this natural LiAl2-based LDH. The crystal structures of all currently known hydrotalcite supergroup members are based on brucite-type layers (Figure 1), where some of M2+ cations are replaced by M3+. A strong predominance of M2+ cations over M3+ is observed, with the most common M2+:M3+ ratios being 2:1 and 3:1. The crystal structures of LiAl2-LDHs are based upon gibbsite-derived dioctahedral layers of Al(OH)6 octahedra, with vacant octahedral sites occupied by Li+ cations (Figure 1). The [LiAl2(OH)6]+ octahedral layers alternate, with negatively charged interlayer constituents represented by anions Cl−, CO32−, SO42−, and H2O groups.
The new mineral is named in honour of the Russian crystallographer and mineralogist Victor Anatol`evich Drits (Виктор Анатольевич Дриц) (born 1932) from Geological Institute of the Russian Academy of Sciences, Moscow, Russia. Prof. Drits is an outstanding specialist in mineralogy of sedimentary rocks and crystal chemistry of compounds with layered structures, especially clay minerals. He contributed greatly to the development of new scientific methods and approaches for the studies of crystal chemistry and systematics of layered minerals, including hydrotalcite supergroup members [22,23]. The mineral and its name have been approved by the IMA-CNMNC (IMA2019-017).
The type material is deposited in the collections of the Fersman Mineralogical Museum of the Russian Academy of Sciences, Moscow, Russia, under the registration number 5380/1.

2. Materials and Methods

2.1. Occurrence, Appearance, Physical Properties, and Optical Data

Dritsite was found in the core of the borehole #2001, at a depth of 247.6–248 m, drilled at the Romanovskiy area of the well-known giant Verkhnekamskoe potassium salt deposit, 30-km south of the city of Berezniki, Perm Krai, Western Urals, Russia [26,27,28]. The new mineral was found in a halite−carnallite rock in association with dolomite, magnesite, quartz, Sr-bearing baryte, kaolinite, potassic feldspar, krasnoshteinite, Al8[B2O4(OH)2](OH)16Cl4⋅7H2O (IMA2018-077) [29], congolite, members of the goyazite–woodhouseite series, fluorite, hematite, and anatase. We believe that dritsite was formed as a result of diagenetic or post-diagenetic processes in a halite–carnallite evaporitic rock belonging to Layer E of the Verkhnekamskoe deposit.
Dritsite forms separate lamellar to tabular hexagonal crystals flattened on {001} up to 0.25 mm across and up to 0.02 mm thick and their parallel intergrowths (Figure 2). The pinacoid {0001} is the major crystal form. The hexagonal prism {1100} is the most typical lateral form, whereas the hexagonal prism {10-10} faces are rare and minor; faces of hexagonal dipyramids {hh(-2h)l}, and occasionally {h0il}, were observed but not indexed. Crystals shown in Figure 2 were separated after dissolution of the host halite–carnallite rock in cold water. The mineral is colorless with a white streak and vitreous luster. The Mohs hardness is approximately 2 (by comparison with other hydrotalcite supergroup minerals). The mineral has a perfect mica-like cleavage on {001} and a laminated fracture. The crystals are easily bent but are non-resilient. The mineral is non-fluorescent in the ultraviolet light. The density could not be measured because of the paucity of material; the density calculated using the empirical formula and the unit-cell parameters determined from single-crystal X-ray diffraction data is 2.123 g/cm3. Dritsite is insoluble in water.
The mineral is optically uniaxial (+), ε = 1.583(2), and ω = 1.546(2) (589 nm). Under a microscope it is colorless and non-pleochroic. The Gladstone–Dale compatibility index [30] is 1 − (KP/KC) = –0.001 (superior).

2.2. Chemical Composition

The chemical composition of dritsite was studied using a Jeol JSM-6480LV scanning electron microscope equipped with an INCA-Wave 500 wavelength-dispersive spectrometer (Laboratory of Analytical Techniques of High Spatial Resolution, Department of Petrology, Moscow State University, Moscow, Russia). Electron microprobe analyses (5) were obtained in the wavelength-dispersive spectroscopy mode (20 kV and 20 nA; the electron beam was rastered to a 5 × 5 μm area) and given contents of Al, Si, S, and Cl. The standards used were: Al2O3 (Al), wollastonite (Si), SrSO4 (S), and NaCl (Cl). The content of other elements with atomic numbers higher than 8 is below the detection limit.
The Li content was determined using inductively coupled plasma mass spectrometry (ICP–MS). The measurements were carried out with an Element-2 (Thermo Fisher Scientific, Moscow, Russia) instrument, which had a high resolution (that avoids interference of components) and sensitivity. Several crystals of the mineral were dissolved in 10 cm3 of 3% HNO3 solution (Merck, Suprapur®, Darmstadt, Germany) in deionized water (EasyPure, Moscow, Russia). Since the mass of the sample was too low for accurate weighing, we have determined contents of Li and Al in relative units and further used the average Al content, obtained by electron microprobe, for calculation of the Li content. The obtained value is in good agreement with the Li content determined from the crystal-structure refinement.
The H2O content was not determined because of the paucity of the material but was calculated based on the crystal-structure data (see below) and by considering the charge-balance requirements (for OH groups). The analytical total (98.29 wt. %) was close to 100 wt. %, which demonstrated the agreement between the electron microprobe data for Al, Si, S, and Cl, the ICP−MS data for Li, and the H2O content calculated from the crystal-structure data.

2.3. Raman Spectroscopy

The Raman spectra of dritsite were obtained with a spectrometer Horiba Jobin-Yvon LabRam HR 800 (Geomodel Resource Center, St. Petersburg State University, St. Petersburg, Russia) equipped with an Ar+ laser (λ = 514 nm) at 50 mW output power. The spectra were recorded at room temperature from the cleavage plane and an edge of the plate and were further processed using LabSpec and Origin software.

2.4. Single-Crystal X-ray Diffraction and Crystal Structure Determination

Single-crystal X-ray diffraction data were collected by means of an Xcalibur S charge-coupled device (CCD) diffractometer (Faculty of Geology, Moscow State University, Moscow, Russia) operated at 40 kV and 50 mA using MoKα radiation. The data were integrated and corrected for absorption using a multi-scan model and the CrysAlisPro program [31]. The crystal structure was solved and refined with the ShelX (Version 2016, ShelX, Göttingen, Germany) program package using direct methods [32].

2.5. Powder X-ray Diffraction

Powder X-ray diffraction data (PXRD) were collected by means of a Rigaku R-Axis Rapid II (X-ray Diffraction Resource Center, St. Petersburg State University, St. Petersburg, Russia) diffractometer (Debye-Sсherrer geometry, d = 127.4 mm) equipped with a rotating anode X-ray source (CoKα, λ = 1.79021 Å) and a curved image plate detector. The data were integrated using the software package Osc2Tab/SQRay [33]. The unit-cell parameters were refined from the powder data using the Pawley method and Topas (Topas, Brisbane, Australia) software [34].

3. Results

3.1. Chemical Composition

The chemical composition of dritsite is given in Table 1. The empirical formula was calculated considering crystal-structure data on the basis of (Li + Al + Si) = 6 apfu, with the content of interlayer H2O equal to 2.60 groups pfu. The empirical formula is Li1.99Al4.00Si0.01[(OH)12.19Cl1.82(SO4)0.01]Σ14.02·2.60H2O. The ideal formula is Li2Al4(OH)12Cl2·3H2O, which requires Li2O 6.63, Al2O3 45.23, H2O 35.97, Cl 15.72, –O=Cl − 3.55, total 100 wt. %.

3.2. Raman Spectroscopy

The Raman spectra of dritsite are shown in Figure 3 and the assignment of the bands is provided in Table 2. The spectra contain several bands in the range from 3200 to 3600 cm–1, corresponding to the O–H stretching vibrations. Raman bands observed around 940–980 and 727–745 cm–1 are assigned to Al···O–H and Li···O–H bending vibrations involving OH groups that form stronger (to O atoms) and weaker (to Cl– anions) hydrogen bonds, respectively. The bands in the ranges 560–599 and 461–464 cm–1 are assigned to the Al···O and Li···O, and Al···O stretching vibrations, respectively [35,36,37]. The bands below 400 cm–1 correspond to the lattice modes.
Considering the observed low intensity of the band at 1047 cm−1 (Figure 3a), it was assigned to the combination mode (594 + 461 = 1055 cm−1, which differs from the value of 1047 cm−1 by the magnitude of the anharmonic shift of 8 cm−1). The assignment of this band to carbonate groups seems unlikely due to the absence of the v1 band of the CO32− anion in the spectrum (Table 2). It is worth noting that v1 bands of the CO32− anion are found around 1055–1057 cm−1 for stichtite-3R and stichtite-2H, Mg6Cr2(OH)16CO3(H2O)4 [38,39], and at 1062 cm−1 (stronger) and 1046 (weaker) cm−1 for quintinite-2T, Mg4Al2(OH)12CO3(H2O)3 [40].

3.3. Single-Crystal X-ray Diffraction and Crystal Structure Determination

The single-crystal X-ray diffraction data were indexed in the P63/mcm space group with the unit-cell parameters: a = 5.0960(3), c = 15.3578(13) Å, and V = 345.4(5) Å3 (Table 3). Details on data collection and structure refinement are provided in Table 3. The final structure refinement converged to R1 = 0.0885 for 250 unique observed reflections with I > 2σ(I). Site occupancies of the Al, Li, and O atoms of the gibbsite-based layer (Figure 4) were found to be close to 100%, and therefore fixed, while occupancies of the interlayer sites were refined. The position of the H atom in the double hydroxide layer was determined from Fourier electron-density maps and was refined with no imposed restraints on the O–H distances and their geometry. The refined O‒H distances of 0.94 Å are consistent with the O–H distances observed in neutron-diffraction studies [41]. Anisotropic displacement parameters were refined only for Al, Li, and O of the gibbsite-based layer and for the rest of the atoms an isotropic approximation was used. Atom coordinates, site occupancies, and displacement parameters are given in Table 4. Selected interatomic distances are provided in Table 5. A crystallographic information file (CIF) for dritsite is available as Supplementary Materials (see below).

3.4. Powder X-ray Diffraction

The indexed powder X-ray diffraction data are given in Table 6. The obtained data show a good agreement with the Joint Committee on Powder Diffraction-International Centre for Diffraction Data (JCPDS-ICDD), card #01-087-1768, of the synthetic analogue of dritsite obtained in previous work [4] (Table 6). The unit-cell parameters refined from the powder data are as follows: P63/mcm (#193), a = 5.0992(10), c = 15.3644(14) Å, and V = 345.98(12) Å3.
The powder pattern recorded for dritsite contains reflections characteristic of the 2H hexagonal layer stacking sequence. The reflection with d010 = 4.422 Å (Table 6) is the evidence of cation ordering according to the 3 × 3 superstructure in the xy plane, which is typical of LiAl2-based LDHs [5,6,7,8,18,19].

4. Discussion

4.1. Crystal Structure of Dritsite-2H

In general, the crystal structure of dritsite is similar to those of other hydrotalcite supergroup members. It is layered and is composed from alternating positively charged metal-hydroxide layers and negatively charged interlayers (Figure 4a). As the symmetry of dritsite is hexagonal and the unit cell contains two layers, the polytype should be identified as 2H, in accordance with the polytype nomenclature [42]). The specific feature of dritsite is that its alumohydroxide layers are dioctahedral (i.e., gibbsite-based) with octahedral voids occupied by Li atoms (Figure 4b). It is worth noting that the single-crystal structure refinement of dritsite-2H is the first for the family of LiAl2-LDHs, because neither synthetic species nor akopovaite were found in crystals suitable for such a study. In the crystal structure of dritsite the octahedral layers contain two symmetrically independent cation sites occupied by Li with <Li‒O> = 2.101 Å and Al with <Al‒O> = 1.893 Å (Table 5). The structural formula of the octahedral layer can be written as [{Al2(OH)6}Li]+ [18], which reflects that the layer is gibbsite-like with Li occupying octahedral vacancies.
The arrangement of Cl− anions and H2O groups in the interlayer space of dritsite shows statistical disorder (Figure 5). The general architecture of the interlayer arrangement of dritsite is principally different from that of carbonate hydrotalcite supergroup minerals, namely quintinite, hydrotalcite, pyroaurite, stichtite, takovite, and zaccagnaite [38,43,44,45,46,47,48,49,50], as shown in Figure 5c,d. In accordance with the approach by Bookin and Drits [23], the interlayer space can be considered as consisting of trigonal prisms formed by H atoms occupying the H1 site of the metal-hydroxide layers (Figure 5e,f). The interlayer consists of three types of such prisms, namely A1, A2, and A3, hosting Cl atoms at their centers and H2O groups in the vertical edge middle points (Figure 5e). The Cl−H1 distances range from 2.51 to 2.99 Å, while the H2O−H1 distances are much shorter (1.94‒2.03 Å) (Table 5). Similar results with Cl− sitting in a trigonal prismatic environment of 6(OH)− groups have been obtained for LiAl2–Cl LDHs using 35Cl nuclear magnetic resonance (NMR) spectroscopy and molecular dynamic modelling, although a distorted octahedral environment caused by 4(OH)‒ and 2(H2O)0 has also been suggested by other authors [51], however was not observed in our study.

4.2. Comparison to Other Hydrotalcite Supergroup Minerals and Synthetic Compounds

Hydrotalcite supergroup members have been described in various geological settings, but it is important for the present study that naturally occurring LDHs, namely quintinite and two unnamed natural phases (the sulphate and sulphate-carbonate analogues of quintinite), were reported from the saline deposits in the central part of the pre-Caspian depression (West Kazakhstan) by Drits et al. [22]. Recently, another hydrotalcite supergroup mineral—motukoreaite, [Mg6Al3(OH)18][Na(H2O)6][SO4]2·nH2O]; n << 6—was reported from the Kłodawa Salt Dome (Central Poland), where it forms during diagenetic and metamorphic processes [52]. Our finding of dritsite shows that hydrotalcite supergroup minerals may be much more abundant in saline deposits than previously thought.
This study, the results of which are reported herein, is the first single-crystal structure refinement of LiAl2-LDH, though synthetic LiAl2-LDHs are well-known and have been structurally characterized using powder X-ray diffraction or neutron diffraction on fine-grained materials accompanied by Rietveld structure refinements. It has been shown that synthetic LiAl2-LDHs form two polytypic modifications: 1M, space group C2/m, a ~5.10, b ~8.88, c ~7.80 Å, β ~103°, and 2H, space group P63/mcm (or P63/m), a ~5.10, and c ~15.36 Å [5,6,7,8]. Both modifications are characterized by the strong Li–Al ordering, with Li occupying vacancies in the gibbsite-like layered structure and different layer-stacking sequences. As noted above, natural dritsite is found as a 2H polytype. Among natural LDHs, i.e., hydrotalcite supergroup minerals, the LiAl2-members show structural similarities with the quintinite group members (M2+2M3+-LDH) due to the same scheme of cation ordering, i.e., the formation of the 3 × 3 superstructure (Figure 5). In particular, dritsite-2H is isotypic to chlormagaluminite-2H, considering the following substitution scheme: [Mg2Al(OH)6]+ (brucite-type layers) → [Al2Li(OH)6]+ (gibbsite-based layers with Li+ cations filling octahedral voids) (Table 7). Despite the structural isotypism of LiAl2-based and quintinite group members, they demonstrate essential crystal chemical differences. The hydrotalcite supergroup members with di- and trivalent cations have fully occupied M sites (M2+, M3+ or M2+,3+) within brucite-type layers and the layer charge controlled by the number of trivalent cations. For the LiAl2-based members, Li occupies vacancies in the gibbsite-type structure and the charge of the layer is controlled by the Li content. For instance, a hypothetical member with Li:Al = 1:4, i.e., with [Li0.5Al2(OH)6]0.5+ layers with half-occupied Li sites, is quite possible, whereas natural di- and trivalent member samples with the ratio M2+:M3+ = 4:1 have not yet been found. In principle, the formation of new Li-deficient members is possible due to Li+ leaching from gibbsite-based layers [18], which is a specific feature of synthetic LiAl2-LDHs. The strong crystal-chemical difference of natural LiAl2-LDHs from LDHs with di- and trivalent cations suggests their separation into a separate group within the hydrotalcite supergroup.
It is important to note that synthetic LiAl2-LDHs have always been considered under the term “layered double hydroxides” [4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19], because in terms of both their chemistry and crystal structure they satisfy the criteria of LDHs. Therefore, we suggest that dritsite should be included into the hydrotalcite supergroup [3] as the first representative of a new group. At the same time, LiAl2-LDHs, [LiAl2(OH)12]2+[Ax2-/x(H2O)n] (where A—anion; x—anion apfu, 2-/x—anion charge), are structurally closely related to the chalcoalumite group minerals, [M2+Al4(OH)12][(TO3/SO4)m(H2O)n], where species-defining M = Ni, Zn or Cu2+; T = N3+ or V5+; m = 1, 2; 2 < n < 12 (Table 8). The crystal structures of both types of compounds consist of gibbsite-based dioctahedral layers, with Li+ filling all octahedral voids or M2+ filling one half of octahedral voids. The chalcoalumite group minerals have not been considered as a part of the hydrotalcite supergroup, mainly due to the vacancies in the octahedral layers [3]. However, the addition of LiAl2-LDHs to the hydrotalcite supergroup could change the approach to vacancies in the octahedral layer from the viewpoint of mineral nomenclature. This is because the hypothetical occupancy of the Li site of 80% in dritsite does not lead to the formation of a new mineral species, but results in the formation of 20% vacancies in the metal-hydroxide layers. The structural similarity between dritsite and chalcoalumite group minerals indicates that the place of the chalcoalumite group members in mineral nomenclature may be reconsidered with their insertion into the hydrotalcite supergroup, i.e., recognized as LDHs [54]).

5. Conclusions

Herein we reported on the new mineral species dritsite, the representative of natural Li2Al-LDHs. Its discovery essentially extends the current knowledge on natural LDHs, which until now included only di- and trivalent cations. It is also important that we report on the first single-crystal refinement performed on Li2Al-LDHs, since all previous studies were focused on synthetic fine-grained powdered material. The crystal–chemical uniqueness of Li2Al-LDH minerals suggests that they should be placed into a separate group within the hydrotalcite supergroup.
The study also points to the need for detailed and careful crystal–chemical comparison of the chalcoalumite group of minerals with members of hydrotalcite supergroup, considering the new crystal chemistry introduced by the approval of a new LiAl2-LDH mineral-dritsite.

Supplementary Materials

The crystallographic information file (cif) is available online at https://www.mdpi.com/2075-163X/9/8/492/s1.

Author Contributions

Conceptualization, E.S.Z., I.V.P., I.I.C.; methodology, E.S.Z., I.V.P.; investigation, E.S.Z., I.V.P., I.I.C., E.P.C., V.O.Y., Y.V.B., D.I.B., N.V.C., N.V.Z., V.N.B.; writing—original draft preparation, E.S.Z., I.V.P., N.V.C., V.N.B.; writing—review and editing, E.S.Z., I.V.P., N.V.C., N.V.Z., S.V.K.; visualization, E.S.Z.

Funding

This research was funded by grants of the President of the Russian Federation for leading scientific schools, NSh-3079.2018.5 for E.S.Z. and S.V.K. (structural study), and Russian Fund for Basic Research, 18-05-00046 for I.I.C., E.P.C. (field work).

Acknowledgments

The research has been carried out using facilities of XRD and Geomodel Research Centers of Saint Petersburg State University. We would like to thank three anonymous reviewers and Stuart Mills for valuable comments that improved the quality of the manuscript.

Conflicts of Interest

The authors declare no conflict of interest.

References

  1. Rives, V. Layered Double Hydroxides: Present and Future; Nova Science Publishers: New York, NY, USA, 2001. [Google Scholar]
  2. Evans, D.G.; Slade, R.C.T. Structural aspects of layered double hydroxides. In Layered Double Hydroxides; Duan, X., Evans, D.G., Eds.; Springer: Berlin, Germany, 2006; Volume 119, pp. 1–87. [Google Scholar]
  3. Mills, S.J.; Christy, A.G.; Génin, J.-M.R.; Kameda, T.; Colombo, F. Nomenclature of the hydrotalcite supergroup: natural layered double hydroxides. Miner. Mag. 2012, 76, 1289–1336. [Google Scholar] [CrossRef]
  4. Besserguenev, A.V.; Fogg, AM.; Francis, R.J.; Price, S.J.; O’Hare, D.; Isupov, V.P.; Tolochko, B.P. Synthesis and structure of the gibbsite intercalation compounds [LiAl2(OH)6]X {X = Cl, Br, NO3} and [LiAl2(OH)6]Cl·H2O using synchrotron X-ray and neutron powder diffraction. Chem. Mater. 1997, 9, 241–247. [Google Scholar] [CrossRef]
  5. Britto, S.; Kamath, P.V. Structure of Bayerite-Based Lithium–Aluminum Layered Double Hydroxides (LDHs): Observation of Monoclinic Symmetry. Inorg. Chem. 2009, 48, 11646–11654. [Google Scholar] [CrossRef] [PubMed]
  6. Britto, S.; Kamath, P.V. Polytypism in the lithium–aluminum layered double hydroxides: the [LiAl2(OH)6]+ layer as a structural synthon. Inorg. Chem. 2011, 50, 5619–5627. [Google Scholar] [CrossRef] [PubMed]
  7. Britto, S.; Thomas, G.S.; Kamath, P.V.; Kannan, S. Polymorphism and structural disorder in the carbonate containing layered double hydroxide of Li with Al. J. Phys. Chem. 2008, 112, 9510–9515. [Google Scholar] [CrossRef]
  8. Nagendran, S.; Kamath, P.V. Structure of the chloride- and bromide-intercalated Layered Double Hydroxides of Li and Al–interplay of coulombic and hydrogen-bonding interactions in the interlayer gallery. Eur. J. Inorg. Chem. 2013, 26, 4686–4693. [Google Scholar] [CrossRef]
  9. Niksch, A.; Pöllmannm, H. Synthesis and characterization of a [Li0+xMg2−2xAl1+x(OH)6][Cl·mH2O] Solid solution with X= 0–1 at different temperatures. Nat. Resour. J. 2017, 8, 445–459. [Google Scholar]
  10. Devyatkina, E.T.; Kotsupalo, N.P.; Tomilov, N.P.; Berger, A.S. On the lithium carbonate-hydroxyl-aluminate. Zhurnal Neorg. Khimii. 1983, 28, 1420–1425. (In Russian) [Google Scholar]
  11. Drewien, C.A.; Eatough, M.O.; Tallant, D.R.; Hills, C.R.; Buchheit, R.G. Lithium-aluminum-carbonate-hydroxide hydrate coatings on aluminum alloys: composition, structure, and processing bath chemistry. J. Mater. Res. 1996, 11, 1507–1513. [Google Scholar] [CrossRef]
  12. Hou, X.; Kirkpatrick, R.J. Thermal Evolution of the Cl-–LiAl2 Layered Double Hydroxide: A Multinuclear MAS NMR and XRD Perspective. Inorg. Chem. 2001, 40, 6397–6404. [Google Scholar] [CrossRef]
  13. Huang, L.; Wang, J.; Gao, Y.; Qiao, Y.; Zheng, Q.; Guo, Z.; Zhao, Y.; O'Hare, D.; Wang, Q. Synthesis of LiAl2-layered double hydroxides for CO2 capture over a wide temperature range. J. Mater. Chem. 2014, 2, 18454–18462. [Google Scholar] [CrossRef]
  14. Isupov, V.P. Intercalation compounds of aluminium hydroxide. J. Struct. Chem. 1999, 40, 672–685. [Google Scholar] [CrossRef]
  15. Isupov, V.P.; Chupakina, L.E.; Tarasov, K.A.; Shestakova, N.Yu. Synthesis of superfine carbonate form of Li–Al double hydroxide from sodium hydroaluminocarbonate. Chem. Sustain. Dev. 2007, 15, 63–69. [Google Scholar]
  16. Serna, C.J.; White, J.L.; Hem, S.L. Hydrolysis of aluminium-tri-(sec-butoxide) in ionic and nonionic media. Clay Clay Miner. 1977, 25, 384–391. [Google Scholar] [CrossRef]
  17. Serna, C.J.; Rendon, J.L.; Iglesias, J.E. Crystal-chemical study of layered [Al2Li(OH)6]+·nH2O. Clay Clay Miner. 1982, 30, 180–184. [Google Scholar] [CrossRef]
  18. Sissoko, I.; Iyagba, E.T.; Sahai, I.; Biloen, P. Anion intercalation and exchange in Al(OH)3− derived compounds. J. Solid State Chem. 1985, 60, 283–288. [Google Scholar] [CrossRef]
  19. Thiel, J.P.; Chiang, C.K.; Poeppelmeier, K.R. Structure of LiAl2(OH)7·H2O. Chem. Mater. 1993, 5, 297–304. [Google Scholar] [CrossRef]
  20. Génin, J.-M.R.; Mills, S.J.; Christy, A.G.; Guérin, O.; Herbillon, A.J.; Kuzmann, E.; Ona-Nguema, G.; Ruby, C.; Upadhyay, C. Mössbauerite, Fe3+6O4(OH)8[CO3]·3H2O, the fully oxidized ‘green rust’ mineral from Mont Saint-Michel Bay, France. Miner. Mag. 2014, 78, 447–465. [Google Scholar] [CrossRef]
  21. Karpenko, V.Yu.; Pautov, L.A.; Zhitova, E.S.; Agakhanov, A.A.; Krzhizhanovskaya, M.G.; Siidra, O.I.; Rassulov, V.A. Akopovaite, IMA 2018-095. CNMNC Newsletter No. 46, December 2018, page 1186. Eur. J. Miner. 2018, 30, 1181–1189. [Google Scholar]
  22. Drits, V.A.; Sokolova, T.N.; Sokolova, G.V.; Cherkashin, V.I. New members of hydrotalcite-manasseite group. Clay Clay Min. 1987, 35, 401–417. [Google Scholar] [CrossRef]
  23. Bookin, A.S.; Drits, V.A. Polytype diversity of the hydrotalcite-like minerals. I. Possible polytypes and their diffraction patterns. Clay Clay Min. 1993, 41, 551–557. [Google Scholar] [CrossRef]
  24. Saalfeld, H.; Wedde, M. Refinement of the crystal structure of gibbsite, Al(OH)3. Z. für Krist. 1974, 139, 129–135. [Google Scholar] [CrossRef]
  25. Zigan, F.; Rothbauer, R. Neutronenbeugungsmeeungen am Brucit. Neues JB Miner. Mon 1967, 1967, 137–143. [Google Scholar]
  26. Kudryashov, A.I. Verkhnekamskoe Salt Depos., 2nd ed.; Epsilon Plus: Moscow, Russia, 2013; pp. 1–368. (In Rusian) [Google Scholar]
  27. Chaikovskiy, I.I.; Chaikovskaya, E.V.; Korotchenkova, O.V.; Chirkova, E.P.; Utkina, T.A. Autogenic titanium and zirconium minerals at the Verkhnekamskoe salt deposit. Geochem. Int. 2019, 57, 184–196. [Google Scholar] [CrossRef]
  28. Ivanov, A.A.; Voronova, M.L. Verkhnekamskoe Potash Salt Depos.; Nedra: Leningrad, Russian, 1975; pp. 1–219. [Google Scholar]
  29. Pekov, I.V.; Zubkova, N.V.; Chaikovskiy, I.I.; Chirkova, E.P.; Belakovskiy, D.I.; Yapaskurt, V.O.; Bychkova, Y.V.; Lykova, I.S.; Britvin, S.N.; Pushcharovsky, D.Y. Krasnoshteinite, IMA 2018-077. CNMNC Newsletter No. 46, December 2018, page 1182. Eur. J. Miner. 2018, 30, 1181–1189. [Google Scholar]
  30. Mandarino, J.A. The Gladstone–Dale compatibility of minerals and its use in selecting mineral species for further study. Can. Miner. 2007, 45, 1307–1324. [Google Scholar] [CrossRef]
  31. CrysAlisPro, version 1.171.37.35; Data Collection and Processing Software for Agilent X-ray Diffractometers; Agilent Technologies UK Ltd.: Oxford, UK, 2014.
  32. Sheldrick, G.M. Crystal structure refinement with SHELXL. Acta Cryst. 2015, C71, 3–8. [Google Scholar]
  33. Britvin, S.N.; Dolivo-Dobrovolsky, D.V.; Krzhizhanovskaya, M.G. Software for processing of X-ray powder diffraction data obtained from the curved image plate detector of Rigaku RAXIS Rapid II diffractometer. Zap. Ross. Miner. Obs. 2017, 146, 104–107, (In Russian with English abs.). [Google Scholar]
  34. Topas, version 4.2; General Profile and Structure Analysis Software for Powder Diffraction Data. Bruker-AXS: Karlsruhe, Germany, 2009.
  35. Brabers, V.A.M. Infrared spectra and ionic ordering of the lithium ferrite–aluminate and chromite systems. Spectrochim. Acta. A 1976, 32, 1709–1711. [Google Scholar] [CrossRef]
  36. Khosravi, I.; Yazdanbakhsh, M.; Eftekhar, M.; Haddadi, Z. Fabrication of nano delafossite LiCo0.5Fe0.5O2 as the new adsorbent in efficient removal of reactive blue from aqueous solutions. Mater. Res. Bull. 2013, 48, 2213–2219. [Google Scholar] [CrossRef]
  37. Ruan, H.D.; Frost, R.L.; Kloprogge, J.T. Comparison of Raman spectra in characterizing gibbsite, bayerite, diaspore and boehmite. J. Raman Spectrosc. 2001, 32, 745–750. [Google Scholar] [CrossRef] [Green Version]
  38. Mills, S.J.; Whitfield, P.S.; Wilson, S.A.; Woodhouse, J.N.; Dipple, G.M.; Raudsepp, M.; Francis, C.A. The crystal structure of stichtite, re-examination of barbertonite, and the nature of polytypism in MgCr hydrotalcites. Am. Miner. 2011, 96, 179–187. [Google Scholar] [CrossRef]
  39. Zhitova, E.S.; Pekov, I.V.; Chukanov, N.V.; Yapaskurt, V.O.; Bocharov, V.N. Minerals of the stichtite-pyroaurite-iowaite-woodallite system from serpentinites of Terektinsky range, Altay Mountains, Russia. Russ. Geol. Geoph 2019, in press. [Google Scholar]
  40. Theiss, F.; López, A.; Frost, R.L.; Scholz, R. Spectroscopic characterisation of the LDH mineral quintinite Mg4Al2(OH)12CO3 × 3H2O. Spectrochim. Acta, A 2015, 150, 758–764. [Google Scholar] [CrossRef]
  41. Jeffrey, G.A. An Introduction to Hydrogen Bonding; Oxford University Press: New York, NY, USA, 1997. [Google Scholar]
  42. Guinier, A.; Bokij, G.B.; Boll-Dornberger, K.; Cowley, J.M.; Durovic, S.; Jagodzinski, H.; Krishna, P.; DeWolff, P.M.; Zvyagin, B.B.; Cox, D.E.; et al. Nomenclature of polytype structures. Report of the International Union of Crystallography ad-hoc committee on the Nomenclature of discordered, modulated and polytype structures. Acta Cryst. 1984, A40, 399–404. [Google Scholar] [CrossRef]
  43. Krivovichev, S.V.; Yakovenchuk, V.N.; Zhitova, E.S.; Zolotarev, A.A.; Pakhomovsky, Y.A.; Ivanyuk, G.Y. Crystal chemistry of natural layered double hydroxides. 1. Quintinite-2H-3c from the Kovdor alkaline massif, Kola peninsula, Russia. Miner. Mag. 2010, 74, 821–832. [Google Scholar]
  44. Krivovichev, S.V.; Yakovenchuk, V.N.; Zhitova, E.S.; Zolotarev, A.A.; Pakhomovsky, Y.A.; Ivanyuk, G.Y. Crystal chemistry of natural layered double hydroxides. 2. Quintinite-1M: First evidence of a monoclinic polytype in M2+–M3+ layered double hydroxides. Miner. Mag. 2010, 74, 833–840. [Google Scholar]
  45. Zhitova, E.S.; Yakovenchuk, V.N.; Krivovichev, S.V.; Zolotarev, A.A.; Pakhomovsky, Y.A.; Ivanyuk, G.Y. Crystal chemistry of natural layered double hydroxides. 3. The crystal structure of Mg, Al-disordered quintinite-2H. Miner. Mag. 2010, 74, 841–848. [Google Scholar]
  46. Zhitova, E.S.; Ivanyuk, G.Y.; Krivovichev, S.V.; Yakovenchuk, V.N.; Pakhomovsky, Y.A.; Mikhailova, Y.A. Crystal Chemistry of Pyroaurite from the Kovdor Pluton, Kola Peninsula, Russia, and the Långban Fe–Mn deposit, Värmland, Sweden. Geol Ore Depos. 2017, 59, 652–661. [Google Scholar] [CrossRef]
  47. Zhitova, E.S.; Krivovichev, S.V.; Yakovenchuk, V.N.; Ivanyuk, G.Y.; Pakhomovsky, Y.A.; Mikhailova, J.A. Crystal chemistry of natural layered double hydroxides. 4. Crystal structures and evolution of structural complexity of quintinite polytypes from the Kovdor alkaline massif, Kola peninsula, Russia. Miner. Mag. 2018, 82, 329–346. [Google Scholar]
  48. Zhitova, E.S.; Krivovichev, S.V.; Pekov, I.V.; Greenwell, H.C. Crystal chemistry of natural layered double hydroxides. 5. Single-crystal structure refinement of hydrotalcite, [Mg6Al2(OH)16](CO3)(H2O)4. Miner. Mag. 2019, 83, 269–280. [Google Scholar]
  49. Mills, S.J.; Whitfield, P.S.; Kampf, A.R.; Wilson, S.A.; Dipple, G.M.; Raudsepp, M.; Favreau, G. Contribution to the crystallography of hydrotalcites: The crystal structures of woodallite and takovite. J. Geosci. 2012, 58, 273–279. [Google Scholar] [CrossRef]
  50. Lozano, R.P.; Rossi, C.; La Iglesia, A.; Matesanz, E. Zaccagnaite-3R, a new Zn–Al hydrotalcite polytype from El Soplao cave (Cantabria, Spain). Am. Miner. 2012, 97, 513–523. [Google Scholar] [CrossRef]
  51. Hou, X.; Kalinichev, A.G.; Kirkpatrick, R.J. Interlayer structure and dynamics of Cl–LiAl2-Layered Double Hydroxides: 35Cl NMR observation and molecular dynamic simulation. Chem. Mater. 2002, 14, 2078–2085. [Google Scholar] [CrossRef]
  52. Wachowiak, J.; Pieczk, A. Motukoreaite from the Kłodawa Salt Dome, Central Poland. Miner. Mag. 2016, 80, 277–289. [Google Scholar] [CrossRef]
  53. Zhitova, E.S.; Krivovichev, S.V.; Pekov, I.V.; Yapaskurt, V.O. Crystal Chemistry of Chlormagaluminite, Mg4Al2(OH)12Cl2(H2O)2, a Natural Layered Double Hydroxide. Minerals 2019, 9, 221. [Google Scholar] [CrossRef]
  54. Jensen, N.D.; Duong, N.T.; Bolanz, R.; Nishiyama, Y.; Rasmussen, C.A.; Gottlicher, J.; Steininger, R.; Prevot, V.; Nielsen, U.G. Synthesis and structural characterization of a pure ZnAl4(OH)12(SO4)·2.6H2O Layered Double Hydroxide. Inorg. Chem 2019, in press. [Google Scholar] [CrossRef]
  55. Hawthorne, F.C.; Cooper, M.A. The crystal structure of chalcoalumite: mechanisms of Jahn-Teller-driven distortion in [6]Cu2+-containing oxysalts. Miner. Mag. 2013, 77, 2901–2912. [Google Scholar] [CrossRef]
  56. Uvarova, Yu. A.; Sokolova, E.; Hawthorne, F.C.; Karpenko, V.V.; Agakhanov, A.A.; Pautov, L.A. The crystal chemistry of the “nickelalumite”-group minerals. Can. Miner. 2005, 43, 1511–1519. [Google Scholar] [CrossRef]
  57. Karpenko, V.V.; Agakhanov, A.A.; Pautov, L.A.; Dikaya, T.V.; Bekenova, G.K. New occurrence of nickelalumite on Kara-Chagyr, South Kirgizia. New Data Miner. 2004, 39, 32–39. [Google Scholar]
  58. Agakhanov, A.A.; Karpenko, V.Y.; Pautov, L.A.; Uvarova, Y.A.; Sokolova, E.; Hawthorne, F.C.; Bekenova, G.K. Kyrgyzstanite, ZnAl4(SO4)(OH)12(H2O)3—A new mineral from the Kara-Tangi, Kyrgyzstan. New Data Miner. 2005, 40, 23–28. [Google Scholar]
  59. Williams, S.; Khin, B.S. Chalcoalumite from Bisbee, Arizona. Miner. Rec. 1971, 2, 126–127. [Google Scholar]
  60. Larsen, E.S.; Vassar, H.E. Chalcoalumite, a new mineral from Bisbee, Arizona. Am. Miner. 1925, 10, 79–83. [Google Scholar]
  61. Pertlik, F.; Dunn, P.J. Crystal structure of alvanite, (Zn,Ni)Al4(VO3)2(OH)12·2H2O, the first example of an unbranched zweier-single chain vanadate in nature. Neues JB Miner. Mon. 1990, 9, 385–392. [Google Scholar]
  62. Karpenko, V.V.; Pautov, L.A.; Sokolova, E.; Hawthorne, F.C.; Agakhanov, A.A.; Dikaya, T.V.; Bekenova, G.K. Ankinovichite, nickel analogue of alvanite, a new mineral from Kurunsak (Kazakhstan) and Kara-Chagyr (Kirgizia). Zap. RMO 2004, 133, 59–70. [Google Scholar]
  63. Martini, J.E.J. Mbobomkulite, hydrombobomkulite, and nickelalumite, new minerals from Mbobo Mkulu cave, eastern Transvaal. Ann. Geol. Surv. S. Afr. 1980, 14, 1–10. [Google Scholar]
Minerals 09 00492 g001 550
Figure 1. (a) The dioctahedral layer in the crystal structure of gibbsite [24] composed of Al(OH)6 octahedra and containing vacancies. (b) The trioctahedral layer in the crystal structure of brucite [25] composed of Mg(OH)6 octahedra as a main structural unit of LDHs composed of di- and trivalent cations (all currently known hydrotalcite supergroup members).
Figure 1. (a) The dioctahedral layer in the crystal structure of gibbsite [24] composed of Al(OH)6 octahedra and containing vacancies. (b) The trioctahedral layer in the crystal structure of brucite [25] composed of Mg(OH)6 octahedra as a main structural unit of LDHs composed of di- and trivalent cations (all currently known hydrotalcite supergroup members).
Minerals 09 00492 g001
Minerals 09 00492 g002 550
Figure 2. Crystals of dritsite: (a) secondary electron image; (b) photomicrograph in unpolarized visible light.
Figure 2. Crystals of dritsite: (a) secondary electron image; (b) photomicrograph in unpolarized visible light.
Minerals 09 00492 g002
Minerals 09 00492 g003 550
Figure 3. Raman spectra of dritsite recorded from the (a) basal face {001} and (b) lateral face of tabular crystal.
Figure 3. Raman spectra of dritsite recorded from the (a) basal face {001} and (b) lateral face of tabular crystal.
Minerals 09 00492 g003
Minerals 09 00492 g004 550
Figure 4. The crystal structure of dritsite-2H (a) and gibbsite-based layer as its part (b); the unit cell is outlined.
Figure 4. The crystal structure of dritsite-2H (a) and gibbsite-based layer as its part (b); the unit cell is outlined.
Minerals 09 00492 g004
Minerals 09 00492 g005 550
Figure 5. Electron density maps at the interlayer level for dritsite-2H (a) and quintinite-2T, [Mg4Al2(OH)12][(CO3)(H2O)3] (b); the architecture of the interlayer space superimposed upon metal-hydroxide layers for dritsite-2H (c) and quintinite-2T (d); the arrangement of interlayer species in trigonal prisms built by H atoms of the upper and lower metal-hydroxide layers for dritsite-2H (e) and quintinite-2T (f).
Figure 5. Electron density maps at the interlayer level for dritsite-2H (a) and quintinite-2T, [Mg4Al2(OH)12][(CO3)(H2O)3] (b); the architecture of the interlayer space superimposed upon metal-hydroxide layers for dritsite-2H (c) and quintinite-2T (d); the arrangement of interlayer species in trigonal prisms built by H atoms of the upper and lower metal-hydroxide layers for dritsite-2H (e) and quintinite-2T (f).
Minerals 09 00492 g005
Table
Table 1. Chemical data (in wt. %) for dritsite.
Table 1. Chemical data (in wt. %) for dritsite.
ConstituentMeanRangeStandart Deviation
Li2O6.6
Al2O345.4245.20–45.670.23
SiO20.110.05–0.250.08
SO30.210.00–0.470.18
Cl14.3314.14–14.460.13
H2Ocalc. *34.86
–O=Cl–3.24
Total98.29
Note: * Calculated taking into account the OH content required by electroneutrality and the amount of H2O groups determined from the crystal-structure study.
Table
Table 2. Raman bands of the dritsite spectra.
Table 2. Raman bands of the dritsite spectra.
DritsiteTentative Assignment
a *b *
3576, 3520 sh, 34583574, 3532, 3478O–H stretching of OH groups forming hydrogen bonds with Cl− (above 3500 cm−1) and O (below 3500 cm−1)
3373 sh, 3288 sh3416O–H stretching of H2O groups
1047-Combination mode
956938Al···O–H and Li···O–H bending vibrations involving OH groups forming strong hydrogen bonds with O atoms
745727Al···O–H and/or Li···O–H bending vibrations involving OH groups forming weak hydrogen bonds (with Cl−(?))
594599, 560Al···O stretching
461464Li···O, Al···O stretching
389, 351, 303, 220354, 247, 145Lattice modes
* The spectrum recorded from the (a) {001} basal face and (b) the lateral face of a tabular crystal;.sh: shoulder; (?): uncertain.
Table
Table 3. Crystal data, data collection information, and structure refinement parameters for dritsite.
Table 3. Crystal data, data collection information, and structure refinement parameters for dritsite.
Crystal Data
Crystal systemHexagonal
Space groupP63/mcm
Unit-cell dimensions a, c (Å)5.0960(3),15.3578(13)
Unit-cell volume (Å3)345.4(5)
Structural formula, ZLi2Al4(OH)12Cl2(H2O)2.6, Z = 1
Absorption coefficient (mm−1)0.762
Data Collection
DiffractometerXcalibur S CCD
Temperature (K)293
Radiation, wavelength (Å)MoKα, 0.71073
θ range for data collection (°)2.65-32.71
h, k, l ranges–7→7, –7→7, –22→23
Axis, frame width (°), time per frame (s)ω, 1, 30
Reflections collected6039
Unique reflections (Rint)257 (0.1035)
Unique reflections F > 2σ(F)250
Data completeness to θmax (%)98.8
Structure Refinement
Refinement methodFull-matrix least-squares on F2
Weighting coefficients, a, b0.199700, 1.606800
Data/restrains/parameters257/1/43
R1 [F > 4σ(F)], wR2 [F > 4σ(F)]0.0885, 0.2606
R1 all, wR2 all0.0910, 0.2648
Goodness-of-fit on F21.053
Largest diff. peak and hole (ēÅ−3)0.82, –0.67
Table
Table 4. Atom coordinates, equivalent isotropic displacement parameters (Å2), and site occupancies for dritsite-2H.
Table 4. Atom coordinates, equivalent isotropic displacement parameters (Å2), and site occupancies for dritsite-2H.
AtomW.P.xyzUeqs.o.fs.s. ref (ē)Assigned Site Populations
Octahedral (gibbsite-based) layer
Al4d1/3 2/300.0128(3)1 *48Al4.0
Li2b0000.034(6)1 *6Li2.0
O112k00.3653(4)0.0635(1)0.0143(9)1 *96(OH)12.0
H112k00.368(12)0.125(2)0.015(17)1 *12
Interlayer components
O26g00.416(14)¼ 0.04(2)0.12(4)5.8(H2O)2.6
O312j−0.220(10)0.687(9)¼ 0.042(13)0.16(3)15.4
Cl116g00.11(3)¼ 0.04(3)0.04(3)4.1Cl2
Cl122a00¼ 0.02(5)0.04(6)1.4
Cl224c−1/3 1/3¼ 0.02(4)0.03(3)2.0
Cl2312j−0.311(9)0.456(17)¼ 0.038(14)0.046(16)9.4
Cl316g00.68(3)¼ 0.00(5)0.01(3)1.0
Cl326g00.77(3)¼ 0.05(3)0.06(3)6.1
Cl3312j−0.094(13)0.566(14)¼ 0.034(12)0.045(13)9.2
Note: * Fixed during refinement in accordance with chemical composition. W.P. = Wyckoff position; x, y, z: coordinates; Ueq: isotropic displacement parameter; s.o.f.: site of occupancy; s.s. ref (ē) = refined site-scattering value.
Table
Table 5. Selected bond lengths (Å) and angles (°) in the crystal structure of dritsite-2H.
Table 5. Selected bond lengths (Å) and angles (°) in the crystal structure of dritsite-2H.
Octahedral (Gibbsite-Like) Layer
Al–O1 × 61.8934(19) Li–O1 × 62.101(3)
Hydrogen Bonding Scheme
D–H d(D–H) d(H···A) <DHA d(D···A) A
O1–H1 0.94(4) 2.34(9) 144(7) 3.15(5) Cl11
O1–H1 0.94(4) 2.92(9) 130(7) 3.60(5) Cl11
O1–H1 0.94(4) 2.69(6) 134(6) 3.417(3) Cl12
O1–H1 0.94(4) 2.51(4) 140(3) 3.293(3) Cl22
O1–H1 0.94(4) 2.66(6) 136(4) 3.41(3) Cl23
O1–H1 0.94(4) 2.21(6) 151(4)3.06(3) Cl23
O1–H1 0.94(4) 2.82(6) 133(4) 3.53(3) Cl23
O1–H1 0.94(4) 2.51(11) 141(7)3.30(7) Cl31
O1–H1 0.94(4) 2.60(11) 137(7) 3.36(7) Cl31
O1–H1 0.94(4) 2.83(12) 134(6) 3.55(8) Cl32
O1–H1 0.94(4) 2.53(12) 139(6) 3.29(8) Cl32
O1–H1 0.94(4) 2.33(6) 146(6) 3.159(19) Cl33
O1–H1 0.94(4) 2.50(6) 140(6) 3.274(19) Cl33
O1–H1 0.94(4) 2.99(6) 130(6) 3.660(19) Cl33
O1–H1 0.94(4) 1.94(4) 173(8) 2.877(7) O2
O1–H1 0.94(4) 2.03(7) 160(6) 2.94(2) O3
Cl—H Distances
Interlayer prism A1Interlayer prism A2Interlayer prism A3
Cl12–H1 × 62.69(4)Cl22–H1 × 62.51(3)Cl31–H1 × 2 2.51(5)Cl33–H1× 22.33(4)
<Cl12–H1>2.69<Cl22–H1>2.51Cl31–H1 × 42.60(3)Cl33–H1× 22.50(3)
Cl11–H1 × 42.92(5)Cl21–H1 × 22.67(4)<Cl31–H1>2.57Cl33–H1× 22.99(3)
Cl11–H1 × 22.34(4)Cl21–H1 × 22.20(3)Cl32–H1 × 42.53(3)<Cl33–H1>2.61
<Cl11–H1>2.73Cl21–H1 × 22.82(3)Cl32–H1 × 22.83(5)
<Cl21–H1>2.56<Cl32–H1>2.63
Table
Table 6. Powder X-ray diffraction data for dritsite-2H.
Table 6. Powder X-ray diffraction data for dritsite-2H.
Dritsite-2H (This Study)Synthetic Analogue of Dritsite-2H* [4]
Imeasdmeas (Å)Icalcdcalc (Å)hkLImeasdmeas (Å)
1007.681007.680021007.65
614.422154.417010114.413
993.832343.840004603.823
203.829012
42.89932.89801442.890
302.56152.56000652.549
82.51682.515111102.513
22.42142.42011242.417
252.283232.283113252.279
32.21612.21501622.207
142.124122.124114142.120
>12.122022
191.963101.962115131.958
71.920>11.92000821.911
1.91421.914024
201.807141.807116161.802
71.67221.67202621.668
21.63211.63121211.630
11.58711.587213<11.585
131.534121.534118121.529
191.47281.47203091.471
261.445101.446032121.445
Note: * JCPDS-ICDD, #01-087-1768. The strongest lines are given in bold.
Table
Table 7. Comparative data of dritsite, its synthetic analogue, and structurally studied, related hydrotalcite supergroup minerals chlormagaluminite and quintinite.
Table 7. Comparative data of dritsite, its synthetic analogue, and structurally studied, related hydrotalcite supergroup minerals chlormagaluminite and quintinite.
Cl-LDHsCO3-LDHs
PhaseDritsiteSynthetic analogue of dritsiteChlormag-aluminite Quintinite *
SymbolLiAl2-ClMg2Al-ClMg2Al-CO3
Polytype2H2H2H2T2H
Crystal chemical formula[Al4Li2(OH)12][Mg4Al2(OH)12][Mg4Al2(OH)12]
[Cl2(H2O)3] [Cl2(H2O)3][(CO3)(H2O)3]
Crystal systemHexagonalTrigonalHexagonal
Space groupP63/mcm**P-3c1P63/mmc
a, Å5.0960(3)5.0963(3)5.268(3)5.2720(6)3.0455(10)
c, Å15.3578(13)15.2919(9)15.297(8)15.113(3)15.125(7)
β, °9090909090
V, Å3345.4(5)344.0367.6(4)363.8121.5
The strongest lines in the PXRD pattern: d, Å (I, %)7.68 (100)7.65 (100)7.72 (100)7.56 (100)7.57 (100)
4.422 (61)3.823 (60)3.856 (38) 3.778 (58) 3.785 (57)
3.832 (99)2.279 (25)2.350 (38) 2.600 (14) 2.600 (11)
2.561 (30)2.210 (14)2.179 (34) 2.519 (10) 2.524 (10)
2.283 (25)1.958 (13)1.843 (29) 2.489 (9) 2.492 (8)
1.445 (26)1.802 (16)1.558 (16)1.987 (7)1.824 (6)
ReferenceThis study[4][53][47][47]
Note: * Powder X-ray diffraction patterns were calculated using crystal structure data. ** The crystal structure of synthetic analogue of dritsite has been solved in P63/m and P63/mcm space groups, with better agreement in the latter [4].
Table
Table 8. The chemical formula and crystallographic parameters of the chalcoalumite group minerals, [M2+Al4(OH)12][(TO3/SO4)m(H2O)n], where M2+ - species-defining cation; T = N3+ or V5+; m = 1, 2; 2 < n < 12 [55].
Table 8. The chemical formula and crystallographic parameters of the chalcoalumite group minerals, [M2+Al4(OH)12][(TO3/SO4)m(H2O)n], where M2+ - species-defining cation; T = N3+ or V5+; m = 1, 2; 2 < n < 12 [55].
TitleM2+AnSpace Groupa, Åb, Åc, Åβ, ºReference
“Nickelalumite”NiSO43P21/n10.25678.881517.098995.548[56,57]
KyrgyzstaniteZnSO43P21/n10.246 8.87317.22096.41[58]
ChalcoalumiteCuSO43P21/n10.2288.92917.09895.800[55,59,60]
AlvaniteZnVO32P21/n17.8085.1328.88192.11[61]
AnkinovichiteNiVO32P21/n17.80985.12288.866592.141[62]
MbobomkuliteNiNO33unknown10.171 8.86517.14595.37[63]
Hydro-MbobomkuliteNiNO312unknown10.145 17.15520.87090.55[63]

Share and Cite

MDPI and ACS Style

Zhitova, E.S.; Pekov, I.V.; Chaikovskiy, I.I.; Chirkova, E.P.; Yapaskurt, V.O.; Bychkova, Y.V.; Belakovskiy, D.I.; Chukanov, N.V.; Zubkova, N.V.; Krivovichev, S.V.; et al. Dritsite, Li2Al4(OH)12Cl2·3H2O, a New Gibbsite-Based Hydrotalcite Supergroup Mineral. Minerals 2019, 9, 492. https://doi.org/10.3390/min9080492

AMA Style

Zhitova ES, Pekov IV, Chaikovskiy II, Chirkova EP, Yapaskurt VO, Bychkova YV, Belakovskiy DI, Chukanov NV, Zubkova NV, Krivovichev SV, et al. Dritsite, Li2Al4(OH)12Cl2·3H2O, a New Gibbsite-Based Hydrotalcite Supergroup Mineral. Minerals. 2019; 9(8):492. https://doi.org/10.3390/min9080492

Chicago/Turabian Style

Zhitova, Elena S., Igor V. Pekov, Ilya I. Chaikovskiy, Elena P. Chirkova, Vasiliy O. Yapaskurt, Yana V. Bychkova, Dmitry I. Belakovskiy, Nikita V. Chukanov, Natalia V. Zubkova, Sergey V. Krivovichev, and et al. 2019. "Dritsite, Li2Al4(OH)12Cl2·3H2O, a New Gibbsite-Based Hydrotalcite Supergroup Mineral" Minerals 9, no. 8: 492. https://doi.org/10.3390/min9080492

Note that from the first issue of 2016, this journal uses article numbers instead of page numbers. See further details here.

Article Metrics

Back to TopTop