Design of Metal-Organic Polymers MIL-53(M3+): Preparation and Characterization of MIL-53(Fe) and Graphene Oxide Composite

This article presents a crystal chemical analysis, generalization, and systematization of structural characteristics of metal-organic polymers MIL-53(M3+) with M = Al, Cr, Ga, and Fe. The division of the MIL-53(M3+) structures into a morphotropic series was performed, which made it possible to predict the formation of new compounds or solid solutions with the corresponding composition and structure. The change in the symmetry of MIL-53(M3+) and the causes of polymorphs formation are explained on the basis of crystal chemical rules. The efficiency of the revealed regularities in the structural characteristics of the MIL-53(M3+) phases were experimentally confirmed for MIL-53(Fe) and composite MIL-53(Fe)/GO (GO-graphene oxide) by several methods (powder X-ray, X-ray absorption, and photoelectron spectroscopy). For the first time, different coordination numbers (CN) (CNFe = 4.9 for MIL-53(Fe)—two types of coordination polyhedra with CNFe = 6 and CNFe = 4; CNFe = 4 for MIL-53 (Fe3+)/GO) and the formal charges (FC) of iron ions (variable FC of Fe (2+δ)+ in MIL-53(Fe3+) and Fe2+ in MIL-53(Fe3+)/GO) were found. These experimental data explain the higher photocatalytic activity of MIL-53(Fe3+)/GO in photo-Fenton reactions—RR195 decomposition.

Features of the conformation of galunisertib molecules in the crystal structures of its solvates

Crystal chemical analysis of 11 solvates of galunisertib (GAL·Q where GAL is C22H19N5O, Q is a solvent molecule) – one of the most prolific compound in the number of structurally...

Synthesis, characterization and morphotropic transitions in a family of M[(UO2)(CH3COO)3](H2O)n (M=Na, K, Rb, Cs; n=0–1.0) compounds

Experimental investigations of crystallization in a family of uranyl triacetate compounds with Na, K, Rb and Cs were performed. The crystal structures of two novel Cs- and Rb-bearing tri(acetato)uranylates were solved, and the content of H2O molecules in the crystal structure of K-bearing uranyl triacetate was refined. Synthesized compounds were analyzed using IR spectroscopy and single-crystal X-ray diffraction. Crystal chemical analysis of the M[(UO2)(CH3COO)3](H2O)n family (M = Na, K, Rb, Cs; n = 0–1.0) reveals the sequence of structural transformations depending on the size of alkali cation resulting in the symmetry reduction from cubic P 213 (for Na), through tetragonal I 41/a (for K and Rb) to triclinic P 1̅ space groups (for Cs), which is in accordance with the principle of morphotropism, suggested by Paul von Groth, founder of the Zeitschrift für Krystallographie journal, in 1870.

Novel K/Mn phosphate hydrates, K2Mn3(H2O)2[P2O7]2 and KMn(H2O)2[Al2(PO4)3]: hydrothermal synthesis and crystal chemistry

Two novel K/Mn phosphate hydrates, namely, dipotassium trimanganese dipyrophosphate dihydrate, K2Mn3(H2O)2[P2O7]2, (I), and potassium manganese dialuminium triphosphate dihydrate, KMn(H2O)2[Al2(PO4)3], (II), were obtained in the form of single crystals during a single hydrothermal synthesis experiment. Their crystal structures were studied by X-ray diffraction. Both new compounds are members of the morphotropic series of phosphates with the following formulae: A 2 M 3(H2O)2[P2O7]2, where A = K, NH4, Rb or Na and M = Mn, Fe, Co or Ni, and AM 2+(H2O)2[M 3+ 2(PO4)3], where A = Cs, Rb, K, NH4 or (H3O); M 2+ = Mn, Fe, Co or Ni; and M 3+ = Al, Ga or Fe. A detailed crystal chemical analysis revealed correlations between the unit-cell parameters of the members of the series, their structural features and the sizes of the cations. It has been shown that a mixed type anionic framework is formed in (II) by aluminophosphate [(AlO2)2(PO4)2]∞ layers, with a cationic topology similar to the Si/Al-topology of the crystal structures of feldspars. A study of the magnetic susceptibility of (II) demonstrates a paramagnetic behaviour of the compound.

Crystallographic Insights into Uranyl Sulfate Minerals Formation: Synthesis and Crystal Structures of Three Novel Cesium Uranyl Sulfates

An alteration of the uranyl oxide hydroxy-hydrate mineral schoepite [(UO2)8O2(OH)12](H2O)12 at mild hydrothermal conditions was studied. As the result, four different crystalline phases Cs[(UO2)(SO4)(OH)](H2O)0.25 (1), Cs3[(UO2)4(SO4)2O3(OH)](H2O)3 (2), Cs6[(UO2)2(SO4)5](H2O)3 (3), and Cs2[(UO2)(SO4)2] (4) were obtained, including three novel compounds. The obtained Cs uranyl sulfate compounds 1, 3, and 4 were analyzed using single-crystal XRD, EDX, as well as topological analysis and information-based structural complexity measures. The crystal structure of 3 was based on the 1D complex, the topology of which was unprecedented for the structural chemistry of inorganic oxysalts. Crystal chemical analysis performed herein suggested that the majority of the uranyl sulfates minerals were grown from heated solutions, and the temperature range could be assumed from the manner of interpolyhedral linkage. The presence of edge-sharing uranyl bipyramids most likely pointed to the temperatures of higher than 100 °C. The linkage of sulfate tetrahedra with uranyl polyhedra through the common edges involved elevated temperatures but of lower values (~70–100 °C). Complexity parameters of the synthetic compounds were generally lower than that of uranyl sulfate minerals, whose structures were based on the complexes with the same or genetically similar topologies. The topological complexity of the uranyl sulfate structural units contributed the major portion to the overall complexity of the synthesized compounds, while the complexity of the respective minerals was largely governed by the interstitial structure and H-bonding system.

Lucchesiite, CaFe2+3Al6(Si6O18)(BO3)3(OH)3O, a new mineral species of the tourmaline supergroup

Lucchesiite, CaFe32+Al6(Si6O18)(BO3)3(OH)3O, is a new mineral of the tourmaline supergroup. It occurs in the Ratnapura District, Sri Lanka (6°35'N, 80°35'E), most probably from pegmatites and in Mirošov near Strážek, western Moravia, Czech Republic, (49°27'49.38"N, 16°9'54.34"E) in anatectic pegmatite contaminated by host calc-silicate rock. Crystals are black with a vitreous lustre, conchoidal fracture and grey streak. Lucchesiite has a Mohs hardnessof ∼7 and a calculated density of 3.209 g/cm3(Sri Lanka) to 3.243 g/cm3(Czech Republic). In plane-polarized light, lucchesiite is pleochroic (O = very dark brown and E = light brown) and uniaxial (–). Lucchesiite is rhombohedral, space groupR3m,a≈ 16.00 Å,c≈ 7.21 Å,V≈ 1599.9 Å3,Z= 3. The crystal structure of lucchesiite was refined toR1 ≈ 1.5% using ∼2000 unique reflections collected with MoKα X-ray intensity data. Crystal-chemical analysis for the Sri Lanka (holotype) and Czech Republic (cotype) samples resulted in the empirical formulae, respectively:X(Ca0.69Na0.30K0.02)∑1.01Y(Fe1.442+Mg0.72Al0.48Ti0.334+V0.023+Mn0.013+Zn0.01)∑3.00Z(Al4.74Mg1.01Fe0.253+)∑6.00[T(Si5.85Al0.15)∑6.00O18](BO3)3V(OH)3W[O0.69F0.24(OH)0.07]∑1.00andX(Ca0.49Na0.45□0.05K0.01)∑1.00Y(Fe1.142+Fe0.953+Mg0.42Al0.37Mn0.03Ti0.084+Zn0.01)∑3.00Z(Al5.11Fe0.383+Mg0.52)∑6.00[T(Si5.88Al0.12)∑6.00O18](BO3)3V[(OH)2.66O0.34]∑3.00W(O0.94F0.06)∑1.00.Lucchesiite is an oxy-species belonging to the calcic group of the tourmaline supergroup. The closest end-member composition of a valid tourmaline species is that of feruvite, to which lucchesiite is ideally related by the heterovalent coupled substitutionZAl3++O1O2–↔ZMg2++O1(OH)1–. The new mineral was approved by the International Mineralogical Association Commission on New Minerals, Nomenclature and Classification (IMA 2015-043).

Fluor-tsilaisite, NaMn3Al6(Si6O18)(BO3)3(OH)3F, a new tourmaline from San Piero in Campo (Elba, Italy) and new data on tsilaisitic tourmaline from the holotype specimen locality

Fluor-tsilaisite, NaMn3Al6(Si6O18)(BO3)3(OH)3F, is a new mineral of the tourmaline supergroup. It occurs in an aplitic dyke of a LCT-type pegmatite body from Grotta d'Oggi, San Piero in Campo, Elba Island, Italy, in association with quartz, K-feldspar, plagioclase, elbaite, schorl, fluor-elbaite and tsilaisite. Crystals are greenish yellow with a vitreous lustre, sub-conchoidal fracture and white streak. Fluor-tsilaisite has a Mohs hardness of ∼7 and a calculated density of 3.134 g/cm3. In plane-polarized light, fluor-tsilaisite is pleochroic (O = pale greenish yellow and E = very pale greenish yellow), uniaxial negative. Fluor-tsilaisite is rhombohedral, space group R3m, a = 15.9398(6), c = 7.1363(3) Å, V = 1570.25(11) Å3, Z = 3. The crystal structure of fluor-tsilaisite was refined to R1 = 3.36% using 3496 unique reflections collected with MoKα X-ray intensity data. Crystal-chemical analysis resulted in the empirical formula: X(Na0.69〈0.29Ca0.02)Σ1.00Y(Mn2+1.29Al1.21Li0.56Ti0.03)Σ6.00ZAl6T(Si5.98Al0.03)Σ6.00B2.92O27V(OH)3W[F0.39(OH)0.25O0.36]Σ1.00.Comparisons were performed between fluor-tsilaisite and a tsilaisitic tourmaline from the same locality as the holotype specimen. This latter tourmaline sample was selected for this study due to its remarkable composition (MnO = 11.63 wt.%), the largest Mn content found in tourmaline so far.Fluor-tsilaisite is related to tsilaisite through the substitution WF ↔ W(OH) and with fluor-elbaite through the substitution Y(Al + Li) ↔ 2YMn2+, and appears to be a stepwise intermediate during tourmaline evolution from tsilaisite to fluor-elbaite.