Functionality in metal–organic framework minerals: proton conductivity, stability and potential for polymorphism

Huskić, Igor; Novendra, Novendra; Lim, Dae‐Woon; Topić, Filip; Titi, Hatem M.; Pekov, Igor V.; Krivovichev, Sergey V.; Navrotsky, Alexandra; Kitagawa, Hiroshi; Friščić, Tomislav

doi:10.1039/c8sc05088k

Cited by 37 publications

(36 citation statements)

References 48 publications

(41 reference statements)

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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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“…This inverse sorption-symmetry relation is surprising, as according to our survey an increased water content of the pores either increases or preserves the crystal symmetry. For example, the spacegroup symmetry R3 of anhydrate stepanovite polymorph ST1d increases to space group R3c for stepanovite [Mg(H 2 O) 6 ][NaFe(C 2 O 4 ) 3 ]Á3H 2 O; for the polymorph ST2d its anhydrate has space-group symmetry P3 and after hydration the symmetry increases to P3c (Huskić et al, 2019); the space-group symmetries P2 1 /n and P1 of lithium acetate (LiC 2 H 3 O 2 ) polymorphs increase to Cmmm for the dihydrate; and space group P1 of lithium acetate monohydrate, 4(LiC 2 H 3 O 2 )ÁH 2 O, increases to P2 1 /c for the tetrahydrate 4(LiC 2 H 3 O 2 )Á4H 2 O (Martínez-Casado et al, 2011).…”

Section: Resultsmentioning

confidence: 99%

High-pressure preference for reduced water content in porous zinc aspartate hydrates

Roszak

Katrusiak

2020

Acta Crystallogr Sect B

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The zinc aspartate (ZnAsp2) complex, a common dietary supplement, preferentially crystallizes as the dihydrate (ZnAsp2·2H2O) from aqueous solution. Under normal conditions the dihydrate easily transforms into the sesquihydrate (ZnAsp2·1.5H2O). The dihydrate crystal structure is triclinic, space group P 1, and the sesquihydrate is monoclinic, space group C2/c. However, their structures are closely related and similarly consist of zinc aspartate ribbons parallel to pores accommodating water molecules. These porous structures can breathe water molecules in and out depending on the temperature and air humidity. High pressure above 50 MPa favours the sesquihydrate, as shown by recrystallizations under pressure and compressibility measured by single-crystal X-ray diffraction up to 4 GPa. This preference is explained by the reduced volume of the sesquihydrate and water compressed separately, compared with the dihydrate. The sesquihydrate undergoes an isostructural phase transition when the voids collapse at 0.8 GPa, whereas no phase transitions occur in the dihydrate, because its pores are supported by increased water content.

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“…Compared to the nets discussed by Öhrström & Larsson that were all formed from 10-gons as the shortest rings between nodes, the lig-net also forms 8-rings (point symbol 8 2 30 forms the nodnet, see Fig. 3.…”

Section: Tris-oxalates [M′mĳox) 3 ] X−mentioning

confidence: 97%

“…1 But oxalates are also very much present in today's cutting edge science. [2][3][4][5][6][7] Recently, for example, MOFs from tetrakis oxalates with zeolite topologies have been prepared. 3 Tri-potassium trioxalato-rhodium monohydrate was the focus of the first diffraction study of oxalates in 1927 (ZZZVZK) 8 followed by beryllium oxalate trihydrate in 1928 (ZZZQZK), and today the Cambridge Crystallographic Data Centre has collected over 6000 oxalate entries into the CSD.…”

Section: Introductionmentioning

confidence: 99%

Natural and synthetic metal oxalates – a topology approach

et al. 2019

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Functionality in metal–organic framework minerals: proton conductivity, stability and potential for polymorphism

Abstract: Metal–organic framework minerals stepanovite and zhemchuzhnikovite can exhibit high proton conduction and structure retention on dehydration.

Cited by 37 publications

References 48 publications

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

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

High-pressure preference for reduced water content in porous zinc aspartate hydrates

Natural and synthetic metal oxalates – a topology approach

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