Vanarsite, Packratite, Morrisonite, and Gatewayite: Four New Minerals Containing the [As3+V4+,5+12As5+6O51] Heteropolyanion, A Novel Polyoxometalate Cluster

Kampf, Anthony R.; Hughes, John M.; Nash, Barbara P.; Marty, Joe

doi:10.3749/canmin.1500062

Cited by 16 publications

(12 citation statements)

References 14 publications

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“…Morrisonite, Ca 11 [As 3+ V 4+ 2 V 5+ 10 As 5+ 6 O 51 ] 2 •78H 2 O, has 13558.354 bits of Shannon information per unit cell and, after ewingite, is the second most complex mineral known so far. The vanarsite-group minerals (Kampf et al 2016(Kampf et al , 2020 contain unique and previously unknown type of the V-As POM cluster with the composition [As 3+ V 12 As 5+ 6 O 51 ]. The cluster consists of twelve (VO 6 ) octahedra forming wheel-or corona-shaped unit centered by As 3+ cation in a trigonal-pyramidal coordination (due to the stereoactivity of a lone-electron pair) and surrounded by six (As 5+ O 4 ) tetrahedra (Fig.…”

Section: Most Complex Mineral Structuresmentioning

confidence: 99%

Producing highly complicated materials. Nature does it better

et al. 2020

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Through the years, mineralogical studies have produced a tremendous amount of data on the atomic arrangement and mineral properties. Quite often, structural analysis has led to elucidate the role played by minor components, giving interesting insights into the physicochemical conditions of minerals and allowing the description of unpredictable structures that represented a body of knowledge critical for assessing their technological potentialities. Using such a rich database, containing many basic acquisitions, further steps became appropriate and possible, into the directions of more advanced knowledge frontiers. Some of these frontiers assume the name of modularity, complexity, aperiodicity, and matter organization at not conventional levels, and will be discussed in this review.

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Section: Most Complex Mineral Structuresmentioning

confidence: 99%

Producing highly complicated materials. Nature does it better

et al. 2020

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“…From the viewpoint of structural complexity, kegginite, bicapite and sherwoodite belong to the group of complex or very complex minerals and, in this respect, do not differ much from the pascoite-group minerals. In contrast, the minerals of the vanarsite group (morrisonite, packratite, gatewayite, vanarsite, and lumsdenite; Kampf et al, 2016bKampf et al, , 2020c are the champions in complexity among natural polyoxovanadates (Table 2). In particular, morrisonite has 13558.354 bits of Shannon information per unit cell and, after ewingite (see below), is the second most complex mineral known so far.…”

Section: Polyoxovanadatesmentioning

confidence: 99%

Polyoxometalate clusters in minerals: review and complexity analysis

Krivovichev¹

2020

Acta Crystallogr B Struct Sci Cryst Eng Mater

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Most research on polyoxometalates (POMs) has been devoted to synthetic compounds. However, recent mineralogical discoveries of POMs in mineral structures demonstrate their importance in geochemical systems. In total, 15 different types of POM nanoscale-size clusters in minerals are described herein, which occur in 42 different mineral species. The topological diversity of POM clusters in minerals is rather restricted compared to the multitude of moieties reported for synthetic compounds, but the lists of synthetic and natural POMs do not overlap completely. The metal–oxo clusters in the crystal structures of the vanarsite-group minerals ([As3+V4+ 2V5+ 10As5+ 6O51]7−), bouazzerite and whitecapsite ([M 3+ 3Fe7(AsO4)9O8–;n (OH) n ]), putnisite ([Cr3+ 8(OH)16(CO3)8]8−), and ewingite ([(UO2)24(CO3)30O4(OH)12(H2O)8]32−) contain metal–oxo clusters that have no close chemical or topological analogues in synthetic chemistry. The interesting feature of the POM cluster topologies in minerals is the presence of unusual coordination of metal atoms enforced by the topological restraints imposed upon the cluster geometry (the cubic coordination of Fe3+ and Ti4+ ions in arsmirandite and lehmannite, respectively, and the trigonal prismatic coordination of Fe3+ in bouazzerite and whitecapsite). Complexity analysis indicates that ewingite and morrisonite are the first and the second most structurally complex minerals known so far. The formation of nanoscale clusters can be viewed as one of the leading mechanisms of generating structural complexity in both minerals and synthetic inorganic crystalline compounds. The discovery of POM minerals is one of the specific landmarks of descriptive mineralogy and mineralogical crystallography of our time.

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“…The parameters without H-corrections are v = 972, I G = 7.925 bits per atom, I G, total = 7702.918 bits per cell, which means that hydration is responsible for ca 36% of the total structural complexity. Kampf et al (2016)]. Since both ewingite and morrisonite contain nanoscale clusters, ilmajokite is the most complex with a framework structure, and in terms of its complexity, is very close to paulingite-(Ca), Ca 5 (Al 10 Si 32 O 84 )Á34H 2 O [11 590.532 bits per cell with Hcorrection and 6766.998 bits per cell after H-correction ($42% complexity is due to H atoms); Passaglia et al (2001)].…”

Section: Complexity Analysismentioning

confidence: 99%

“…Recently, a number of highly complex minerals has been characterized with structural features never before seen in synthetic materials. In particular, the crystal structures of charoite and denisovite are based on different kinds of silicate nanotubules (Rozhdestvenskaya et al, 2009(Rozhdestvenskaya et al, , 2010(Rozhdestvenskaya et al, , 2017, and ewingite (Olds et al, 2017) and morrisonite (Kampf et al, 2016) contain novel types of nanoscale heteropolyhedral clusters.…”

Section: Introductionmentioning

confidence: 99%

Extraordinary structural complexity of ilmajokite: a multilevel hierarchical framework structure of natural origin

Zolotarev

Krivovichev

Cámara

et al. 2020

IUCrJ

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The crystal structure of ilmajokite, a rare Na-K-Ba-Ce-titanosilicate from the Khibiny mountains, Kola peninsula, Russia, has been solved using single-crystal X-ray diffraction data. The crystal structure is based on a 3D titanosilicate framework consisting of trigonal prismatic titanosilicate (TPTS) clusters centered by Ce3+ in [9]-coordination. Four adjacent TPTS clusters are linked into four-membered rings within the (010) plane and connected via ribbons parallel to 101. The ribbons are organized into layers parallel to (010) and modulated along the a axis with a modulation wavelength of csinβ = 32.91 Å and an amplitude of ∼b/2 = 13.89 Å. The layers are linked by additional silicate tetrahedra. Na+, K+, Ba2+ and H2O groups occur in the framework cavities and have different occupancies and coordination environments. The crystal structure of ilmajokite can be separated into eight hierarchical levels: atoms, coordination polyhedra, TPTS clusters, rings, ribbons, layers, the framework and the whole structure. The information-based analysis allows estimation of the complexity of the structure as 8.468 bits per atom and 11990.129 bits per cell. According to this analysis, ilmajokite is the third-most complex mineral known to date after ewingite and morrisonite, and is the most complex mineral framework structure, comparable in complexity to paulingite-(Ca) (11 590.532 bits per cell).

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Vanarsite, Packratite, Morrisonite, and Gatewayite: Four New Minerals Containing the [As³⁺V^4+,5+₁₂As⁵⁺₆O₅₁] Heteropolyanion, A Novel Polyoxometalate Cluster

Cited by 16 publications

References 14 publications

Producing highly complicated materials. Nature does it better

Producing highly complicated materials. Nature does it better

Polyoxometalate clusters in minerals: review and complexity analysis

Extraordinary structural complexity of ilmajokite: a multilevel hierarchical framework structure of natural origin

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