Hydrogen bonding and structural complexity of the Cu3(AsO4)(OH)3 polymorphs (clinoclase, gilmarite): a theoretical study

Krivovichev, Sergey V.

doi:10.3190/jgeosci.231

Cited by 15 publications

(6 citation statements)

References 25 publications

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“…The calculations of the structural complexity parameters for different anorthite polymorphs were performed using the TOPOSPro software package [58] and the values are given in Table 6. It can be seen that the crystal structures of the metastable CaAl2Si2O8 polymorphs dmisteinbergite and svyatoslavite are much simpler than that of anorthite, in good agreement with Goldsmith's principle and similar previous observations [22][23][24][25][26][27][28]59,60].…”

Section: Discussionsupporting

confidence: 87%

“…Their formation can be explained using Goldsmith's principle of simplexity [21], which states that metastable kinetic mineral phases are structurally simpler than their stable thermodynamic counterparts. This principle, first formulated in 1953, was recently verified using information-based structural complexity measures and checked against mineral systems with different chemical compositions [22][23][24][25][26][27][28].…”

Section: Introductionmentioning

confidence: 99%

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Dmisteinbergite, CaAl2Si2O8, a Metastable Polymorph of Anorthite: Crystal-Structure and Raman Spectroscopic Study of the Holotype Specimen

et al. 2019

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The crystal structure of dmisteinbergite has been determined using crystals from the type locality in Kopeisk city, Chelyabinsk area, Southern Urals, Russia. The mineral is trigonal, with the following structure: P312, a = 5.1123(2), c = 14.7420(7) Å, V = 333.67(3) Å3, R1 = 0.045, for 762 unique observed reflections. The most intense bands of the Raman spectra at 327s, 439s, 892s, and 912s cm −1 correspond to different types of tetrahedral stretching vibrations: Si–O, Al–O, O–Si–O, and O–Al–O. The weak bands at 487w, 503w, and 801w cm−1 can be attributed to the valence and deformation modes of Si–O and Al–O bond vibrations in tetrahedra. The weak bands in the range of 70–200 cm−1 can be attributed to Ca–O bond vibrations or lattice modes. The crystal structure of dmisteinbergite is based upon double layers of six-membered rings of corner-sharing AlO4 and SiO4 tetrahedra. The obtained model shows an ordering of Al and Si over four distinct crystallographic sites with tetrahedral coordination, which is evident from the average <T–O> bond lengths (T = Al, Si), equal to 1.666, 1.713, 1.611, and 1.748 Å for T1, T2, T3, and T4, respectively. One of the oxygen sites (O4) is split, suggesting the existence of two possible conformations of the [Al2Si2O8]2− layers, with different systems of ditrigonal distortions in the adjacent single layers. The observed disorder has a direct influence upon the geometry of the interlayer space and the coordination of the Ca2 site. Whereas the coordination of the Ca1 site is not influenced by the disorder and is trigonal antiprismatic (distorted octahedral), the coordination environment of the Ca2 site includes disordered O atoms and is either trigonal prismatic or trigonal antiprismatic. The observed structural features suggest the possible existence of different varieties of dmisteinbergite that may differ in: (i) degree of disorder of the Al/Si tetrahedral sites, with completely disordered structure having the P63/mcm symmetry; (ii) degree of disorder of the O sites, which may have a direct influence on the coordination features of the Ca2+ cations; (iii) polytypic variations (different stacking sequences and layer shifts). The formation of dmisteinbergite is usually associated with metastable crystallization in both natural and synthetic systems, indicating the kinetic nature of this phase. Information-based complexity calculations indicate that the crystal structures of metastable CaAl2Si2O8 polymorphs dmisteinbergite and svyatoslavite are structurally and topologically simpler than that of their stable counterpart, anorthite, which is in good agreement with Goldsmith’s simplexity principle and similar previous observations.

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Section: Discussionsupporting

confidence: 87%

Section: Introductionmentioning

confidence: 99%

Dmisteinbergite, CaAl2Si2O8, a Metastable Polymorph of Anorthite: Crystal-Structure and Raman Spectroscopic Study of the Holotype Specimen

et al. 2019

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“…Krivovichev (2013) provided an overview of relations between structural complexity and metastable crystallisation based upon the Goldsmith's simplexity principle that states that simple structures crystallise more easily. This idea was supported by many subsequent observations, including metastable feldspar polymorphs (Zolotarev et al , 2019; Krivovichev, 2020, and references therein), perovskite-group minerals (Zaitsev et al , 2017), uranyl minerals (Plášil et al , 2018b, 2018c), sulfates (Plášil et al , 2017; Majzlan et al , 2018), phosphates and arsenates (Krivovichev et al , 2016; Krivovichev, 2017; Kolitsch et al , 2020), Cu 2 (OH) 3 Cl polymorphs (Krivovichev et al , 2017), borates (Grew et al , 2016), borosilicates (Cempírek et al , 2016), oxalates (Huskić et al , 2019), etc. In his review on metastable-mineral formation in oxidation zones and mine wastes, Majzlan (2020) recently noted that “a quantitative link…” between structural complexity and metastability “…is missing”.…”

Section: Further Directionsmentioning

confidence: 68%

Structural and chemical complexity of minerals: an update

Krivovichev

Кривовичев

Hazen

et al. 2022

MinMag

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The complexities of chemical composition and crystal structure are fundamental characteristics of minerals that have high relevance to the understanding of their stability, occurrence and evolution. This review summarises recent developments in the field of mineral complexity and outlines possible directions for its future elaboration. The database of structural and chemical complexity parameters of minerals is updated by H-correction of structures with unknown H positions and the inclusion of new data. The revised average complexity values (arithmetic means) for all minerals are 3.54(2) bits/atom and 345(10) bits/cell (based upon 4443 structure reports). The distributions of atomic information amounts, chemIG and strIG, versus the number of mineral species fit the normal modes, whereas the distributions of total complexities, chemIG,total and strIG,total, along with numbers of atoms per formula and per unit cell are log normal. The three most complex mineral species known today are ewingite, morrisonite and ilmajokite, all either discovered or structurally characterised within the last five years. The most important complexity-generating mechanisms in minerals are: (1) the presence of isolated large clusters; (2) the presence of large clusters linked together to form three-dimensional frameworks; (3) formation of complex three-dimensional modular frameworks; (4) formation of complex modular layers; (5) high hydration state in salts with complex heteropolyhedral units; and (6) formation of ordered superstructures of relatively simple structure types. The relations between symmetry and complexity are considered. The analysis of temporal dynamics of mineralogical discoveries since 1875 with the step of 25 years show the increasing chemical and structural complexities of human knowledge of the mineral kingdom in the history of mineralogy. In the Earth's history, both diversity and complexity of minerals experience dramatic increases associated with the formation of Earth's continental crust, initiation of plate tectonics and the Great Oxidation event.

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“…The 'Get Locality Counts' feature was used to extract the number of localities associated with each species from the MED. The structural complexity parameters were calculated using the published crystallographic information files (CIFs) input into the ToposPro software package (Blatov et al, 2000), using methods developed by Dr. Sergey Krivovichev (Krivovichev, 2013(Krivovichev, , 2016(Krivovichev, , 2017. Many of the other parameters, such as hardness, colour, lustre, space group and density, were manually extracted from the Handbook of Mineralogy (HoM; Anthony et al, 1990Anthony et al, -2003.…”

Section: Mineral Properties Databasementioning

confidence: 99%