Search

The phase relations of Al-bearing magnetite were investigated between 6–22 GPa and 1000–1550 °C using a multi-anvil apparatus. This study demonstrates that the spinel-structured phase persists up to ~9–10 GPa at 1100–1400 °C irrespective of the amount of hercynite (FeAl2O4) component present (20, 40, or 60 mol%). At ~10 GPa, the assemblage Fe2(Al,Fe)2O5 + (Al,Fe)2O3 forms and remains stable up to 16–20 GPa and 1200–1550 °C. Fe2(Al,Fe)2O5 adopts the CaFe3O5-type structure with the Cmcm space group. At 18–22 GPa and T > 1300 °C the assemblage Fe3(Fe,Al)4O9 + (Al,Fe)2O3 becomes stable. Fe3(Fe,Al)4O9 is isostructural with Fe7O9, having the monoclinic structure of the C2/m space group. At T <1300 °C, Fe3(Fe,Al)4O9 + (Al,Fe)2O3 gives way to the assemblage of a hp-Fe(Fe,Al)2O4 + (Al,Fe)2O3. This hp-Fe(Fe,Al)2O4 phase is unquenchable; a defect-bearing spinel-structured phase was recovered instead, and it contained numerous lamellae parallel to {100} or {113} planes and notably less Al than the initial starting composition. While low-pressure spinel can have a complete solid solution between Fe3+-Al, the post-spinel phases have only very limited Al solubility, with a maximum of ~0.1 cpfu Al in hp-Fe(Fe,Al)2O4, ~0.3 cpfu in Fe2(Fe,Al)2O5, and ~0.4 cpfu in Fe3(Fe,Al)4O9, respectively. As a result, the phase relations of Fe(Fe0.8Al0.2)2O4 can also be applied to bulk compositions richer in Al with the only difference being that larger amounts of an (Al,Fe)2O3 phase are present. Coexisting rhombohedral-structured phases demonstrate that the binary miscibility gap established at low pressure between hematite and corundum is still valid up to 20 GPa. Since iron oxides (e.g., magnetite) with variable Al contents are found in extraterrestrial rocks or as inclusions in diamond, constraints on their high-P-T-fO2 stability might help unravel their formation conditions. [ABSTRACT FROM AUTHOR]

Among all possible NMR crystallography approaches for crystal‐structure determination, crystal structure prediction – NMR crystallography (CSP‐NMRX) has recently turned out to be a powerful method. In the latter, the original procedure exploited solid‐state NMR (SSNMR) information during the final steps of the prediction. In particular, it used the comparison of computed and experimental chemical shifts for the selection of the correct crystal packing. Still, the prediction procedure, generally carried out with DFT methods, may require important computational resources and be quite time‐consuming, especially if there are no available constraints to use at the initial stage. Herein, the successful application of this combined prediction method, which exploits NMR information also in the input step to reduce the search space of the predictive algorithm, is presented. Herein, this method was applied on mebendazole, which is characterized by desmotropism. The use of SSNMR data as constraints for the selection of the right tautomer and the determination of the number of independent molecules in the unit cell led to a considerably faster process, reducing the number of calculations to be performed. In this way, the crystal packing was successfully predicted for the three known phases of mebendazole. To evaluate the quality of the predicted structures, these were compared to the experimental ones. The crystal structure of phase B of mebendazole, in particular, was determined de novo by powder diffraction and is presented for the first time in this paper. [ABSTRACT FROM AUTHOR]

The donor-free potassium silanide K[SiPh3] was prepared by the reaction of hexaphenyldisilane, Ph3Si–SiPh3, with potassium metal in benzene at room temperature. The solid-state structure, determined by powder X-ray diffraction consists of {K[SiPh3]}2 units, which interact with adjacent dimers to form an infinite chain along the crystallographic c axis (orthorhombic, space group Cmc21, Z=4). The structure features short contacts between the π system of the phenyl rings and the potassium atoms of neighbouring K[SiPh3] units. [ABSTRACT FROM AUTHOR]

The donor-free potassium silanide K[SiPh3] was prepared by the reaction of hexaphenyldisilane, Ph3Si–SiPh3, with potassium metal in benzene at room temperature. The solid-state structure, determined by powder X-ray diffraction consists of {K[SiPh3]}2 units, which interact with adjacent dimers to form an infinite chain along the crystallographic c axis (orthorhombic, space group Cmc21, Z=4). The structure features short contacts between the π system of the phenyl rings and the potassium atoms of neighbouring K[SiPh3] units. [ABSTRACT FROM AUTHOR]

A novel Mg-bearing iron oxide Mg 0.87 (1) Fe 4.13 (1) 2 + Fe 4 3 + O 11 $ \begin{array} {} {\rm{M}}{{\rm{g}}_{0.87(1)}}{\rm{Fe}}_{4.13(1)}^{2 + }{\rm{Fe}}_4^{3 + }{{\rm{O}}_{11}}\end{array} $ was synthesized at 12 GPa and 1300 °C using a large volume press. Rietveld structural analysis was conducted with a laboratory X‑ray diffraction pattern obtained at ambient conditions. The crystal structure, which has one oxygen trigonal prism site and four octahedral sites for the cations, was found to be isostructural with Ca2Fe7O11. The unit-cell lattice parameters are a = 9.8441(5) Å, b = 2.8920(1) Å, c = 14.1760(6) Å, β = 99.956(4)°, V = 397.50(3) Å3, and Z = 2 (monoclinic, C2/m). Mg and Fe cations are disordered on the trigonal prism site and on two of the four octahedral sites, and the remaining Fe is accommodated at the other two octahedral sites. The present structure is closely related to the other recently discovered Fe oxide structures, e.g., Fe4O5 and Fe5O6, by distortion derived either from incorporation (Fe4O5) or removal (Fe5O6) of an edge-shared FeO6 single octahedral chain in their structures. The present synthesis at deep upper mantle conditions and the structural relationships observed between various novel Mg-Fe oxides indicate that a series of different phases become stable above 10 GPa and that their relative stabilities (Fe2+/Fe3+) must be controlled by oxygen fugacity. [ABSTRACT FROM AUTHOR]

A series of adducts of LiCN, namely [Li(Me2CO3)CN], [Li(Et2CO3)CN], and [Li(NMP)CN] (NMP = N-methyl-2-pyrrolidone) were prepared by treatment of solvent-free LiCN with the appropriate donor. The starting material for these approaches, donor-free LiCN, was quantitatively prepared from Me3SiCN and Li[Me] in diethyl ether at 0 °C. Alternatively, [Li(NMP)CN] was synthesized by metathesis reaction of LiCl with NaCN in the presence of stoichiometric amounts of NMP. Although [Li(Me2CO3)CN] and [Li(Et2CO3)CN] are water-sensitive compounds and decompose at the exposure to air, [Li(NMP)CN] is stable in air, even at elevated temperatures. The thermal stability of [Li(NMP)CN] was proven by differential thermal analysis (DTA). [Li(NMP)CN] shows thermal stability up to temperatures of about 132 °C. To evaluate the cyanation ability the reactions of 1-bromooctane and 3-bromocyclohexene with unsupported LiCN, [Li(NMP)CN], and a mixture of NaCN/LiCl/NMP were investigated. We found that [Li(NMP)CN] as well as LiCl/NaCN/NMP are efficient cyanation reagents comparable to the expensive and air-sensitive, donor-free LiCN. A product of the chloride-cyanide-bromide exchange could be isolated and structurally characterized by X-ray diffraction. [ABSTRACT FROM AUTHOR]

The crystal structures of two thiolato complexes of the type [Au(SR)(PPh3)] with SR=2-mercaptobenzoxazol-2-yl (MBOx) and SR=2-mercaptoanthraceneoxazol-2-yl (MAOx) were determined from X-ray powder diffraction data. Both complexes include η1-S-monodentate ligands with the nitrogen atom preferably oriented towards the gold atom. [Au(MBOx)(PPh3)] ( 1a) represents a new triclinic polymorph of [Au(MBOx)(PPh3)], whereas [Au(MAOx)(PPh3)] ( 2) is hitherto unknown and yields information about the molecular structure of the ligand MAOx as well as the coordination geometry in 2. The structure determinations were validated by low temperature XRPD measurements. DTA-TG and in-situ XRPD measurements revealed a monotropic phase transition of 1a at 443 K to a monoclinic phase. Additionally, solid-state DFT-D calculations using CASTEP were carried out to evaluate the experimental results. [ABSTRACT FROM AUTHOR]