The crystal structure of Na4Ni7(PO4)6
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Peculiarities of structure formation of layered chalcogenides with mixed tetrahedral and octahedral cation coodination are considered. The criterion for purposive search of new layered compounds was proposed. New layered compounds as Cu(Ag)Ga 2.5 In 2.5 S 8 , Mg 0.5 Ga 2 InS 5 , CuIn 5 S 3 Se 5 and others were obtained and studied.
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Orthorhombic, space group Pnma with a = 10.132, b = 12.537 and c = 7.775Aa (all + or -0.001Aa). There are four formula units in the unit cell. The two types of octahedra share an edge and/or corners among themselves. The sulfate tetrahedron shares corners with both types of octahedra and these three units form crude sheets centered about the mirror planes. The sheets are jointed by the boron tetrahedra into a three-dimensional structure.--Modified journal abstract.
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A room-temperature structural model of titanium pyrophosphate, TiP2O7, has been determined from synchrotron X-ray data. The structure consists of TiO6 octahedra and PO4 tetrahedra sharing corners in a three-dimensional network. The PO4 tetrahedra form P2O7 groups connecting the TiO6 octahedra. The 3 × 3 × 3 superstructure differs substantially from the parent AB2O7 structure. The P—O—P bonding angles of the pyrophosphate group are between 141.21 (12) and 144.51 (13)° for those groups not located on the threefold axis. The individual TiO6 octahedra and PO4 tetrahedra are somewhat distorted.
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A hypothetical ideal wollastonite with regular octahedra and T3 tetrahedron is presented and used to compare and contrast the pyroxenes and pyroxenoids. While clinopyroxenes have close-packed arrangements of oxygen anions, several lines of evidence demonstrate that pyroxenoids do not. One such line is the number of tetrahedra in a single tetrahedral chain per octahedra in a single associated octahedral chain (interior to the octahedral band), referred to as the "single-chain T:O ratio," which is 1:1 in pyroxenes but 3:2 in wollastonite and always greater than 1:1 in other MSiO3 pyroxenoids. Because the Si-tetrahedron is extremely resistant to distortion, this forces marked distortion in at least one pyroxenoid octahedral site.
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Designing and building unique cage assemblies attract increasing interest from supramolecular chemists but remain synthetically challenging. Herein, we propose the use of a flexible vertex with adjustable angles to selectively form highly distorted tetrahedral and octahedral cages, for the first time, in which the flexible vertex forms from the synergistic effect of coordination and covalent interactions. The inherent interligand angle of the vertex can be modulated by guest anions present, which allows for the fine-tuning of different cage geometries. Furthermore, the reversible structural transformation between tetrahedral and octahedral cages was achieved by anion exchange monitored by mass spectrometric technique, the smaller anions favoring tetrahedral cages, while the larger anions supporting octahedral cages. Additionally, the KBr-based cage thin films exhibited prominent enhancement of their third-order NLO responses in two or three orders of magnitude compared to those obtained for their corresponding solutions. This work not only provides a new methodology to build irregular polyhedral structures in a controlled and tunable way but also provides access to new kinds of promising functional optical materials.
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β-Ga2O3 contains two crystallographically different Ga atoms in the asymmetric unit, one with tetrahedral and the other with octahedral coordination geometry. The Ga-O distances are in the range 1.833 (1)–1.863 (2) Å within the tetrahedra, but are longer within the octahedra [1.935 (2)–2.074 (1) Å]. The O atoms have a distorted cubic close packing. The crystal structure of β-gallium oxide has been determined previously by Geller [J. Chem. Phys. (1960). 33, 676–684].
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