ABSTRACT
The title compound, hexapotassium octairon(II,III) dodecaphosphonate, exhibiting a two-dimensional structure, is a new mixed alkali/3d metal phosphite. It crystallizes in the space group R3m, with two crystallographically independent Fe atoms occupying sites of 3m (Fe1) and 3m (Fe2) symmetry. The Fe2 site is fully occupied, whereas the Fe1 site presents an occupancy factor of 0.757â (3). The three independent O atoms, one of which is disordered, are situated on a mirror and all other atoms are located on special positions with 3m symmetry. Layers of formula [Fe3(HPO3)4](2-) are observed in the structure, formed by linear Fe3O12 trimer units, which contain face-sharing FeO6 octahedra interconnected by (HPO3)(2-) phosphite oxoanions. The partial occupancy of the Fe1 site might be described by the formation of two [Fe(HPO3)2](-) layers derived from the [Fe3(HPO3)4](2-) layer when the Fe1 atom is absent. Fe(2+) is localized at the Fe1 and Fe2 sites of the [Fe3(HPO3)4](2-) sheets, whereas Fe(3+) is found at the Fe2 sites of the [Fe(HPO3)2](-) sheets, according to bond-valence calculations. The K(+) cations are located in the interlayer spaces, between the [Fe3(HPO3)4](2-) layers, and between the [Fe3(HPO3)4](2-) and [Fe(HPO3)2](-) layers.
ABSTRACT
The title compound is a new mixed alkali/3d metal phosphite. It exhibits a layered structure formed by linear Mn(3)O(12) trimer units which contain face-sharing MnO(6) octahedra interconnected by (HPO(3))(2-) phosphite oxoanions. The K(+) cations located between the anionic [Mn(3)(HPO(3))(4)](2-) sheets are ninefold coordinated. The presence of the alkaline ion leads to the highest symmetry and shortest interlayer distance compared with two previous compounds showing the same anionic framework and having ammonium salts as cations. The compound crystallizes in the space group R3m, with two crystallographically independent Mn atoms occupying sites of 3m and 3m symmetry. All the other atoms, except for the phosphite O atoms, are located on special positions with 3m symmetry.
ABSTRACT
The title synthesized hypophosphite has the formula V(H(2)PO(2))(3). Its structure is based on VO(6) octahedra and (H(2)PO(2))(-) pseudo-tetrahedra. The asymmetric unit contains two crystallographically distinct V atoms and six independent (H(2)PO(2))(-) groups. The connection of the polyhedra generates [VPO(6)H(2)](6-) chains extended along a, b and c, leading to the first three-dimensional network of an anhydrous transition metal hypophosphite.
ABSTRACT
This article presents results of first-principles calculations of quadrupolar parameters measured by solid-state nuclear magnetic measurement (NMR) spectroscopy. Different computational methods based on density functional theory were used to calculate the quadrupolar parameters. Through a series of illustrations from different areas of solid state inorganic chemistry, it is shown how quadrupolar solid-state NMR properties can be tackled by a theoretical approach and can yield structural information.
ABSTRACT
The remediation of chromated copper arsenate or CCA-treated wood is a challenging problem in many countries. In a wet remediation, the recycling of the washing solutions is the key step for a successful process. Within this goal, owing to its solubility and its toxicity, the removal of arsenic from washing solution is the most difficult process. The efficiency of arsenic removal from As(III) solutions by electrolysis was investigated in view of the recycling of acidic washing solutions usable in the remediation of CCA-treated wood. Electrochemical reduction of As(III) is irreversible and thus difficult to perform at carbon electrodes. However the electrolytic extraction of arsenic can be performed by the concomitant reduction of the cupric cation and arsenite anion. The cathodic deposits obtained by controlled potential electrolysis were analyzed by X-ray diffraction (XRD) and energy dispersive X-ray microanalysis. XRD diffraction data indicated that these deposits were mixtures of copper and copper arsenides Cu(3)As and Cu(5)As(2). Electrolysis was carried out in an undivided cell with graphite cathode and copper anode, under a controlled nitrogen atmosphere. The evolution of arsine gas AsH(3) was not observed under these conditions.
