Abstract
Novel copper phosphate chloride has been obtained under middle-temperature hydrothermal conditions. Its crystal structure was established based on the low-temperature X-ray diffraction data: Na2Li0.75(Cs,K)0.5[Cu5(PO4)4Cl]·3.5(H2O,OH), sp. gr. C2/m, a = 19.3951(8) Å, b = 9.7627(3) Å, c = 9.7383(4) Å, β = 99.329(4)°, T = 150 K, MoKα (λ = 0.71073 Å), R = 0.049. The crystal structure includes tetrameric copper clusters as the main building blocks, which are built of four CuO4Cl pyramids sharing apical Cl vertices. The clusters are combined through phosphate groups and additional copper-centered polyhedra to form two mostly ordered periodic layers. Between the layers and inside the framework channels, alkali ions, H2O molecules, or OH groups are statistically distributed. Na2Li0.75(Cs,K)0.5[Cu5(PO4)4Cl]·3.5(H2O,OH) is a synthetic modification of a sampleite-polymorph of the lavendulan mineral group and represents a new member in a mero-plesiotype series of copper phosphates and arsenates, for which the crystal structures contain two-periodic [Cu4X(TO4)4]∞ modules (T = As, P; X = Cl, O). Magnetically, this phase exhibits the phase transition at TC = 6.5 K, below which it possesses a weak ferromagnetic moment.
Highlights
Quantum Functional Materials Laboratory, National University of Science and Technology “MISiS”, Faculty of Physics, Lomonosov Moscow State University, 119991 Moscow, Russia
We report the hydrothermal synthesis, crystal structure, and physical properties of new complex copper phosphate chloride, Na2 Li0.75 (Cs,K)0.5 [Cu5 (PO4 )4 Cl]·3.5(H2 O,OH), which is a new member of the polysomatic series of the lavendulan mineral group
To obtain mineral-like phases with open framework structures, we provided our exploratory synthesis in a system enriched with alkali metal salts
Summary
Quantum Functional Materials Laboratory, National University of Science and Technology “MISiS”, Faculty of Physics, Lomonosov Moscow State University, 119991 Moscow, Russia. The clusters are combined through phosphate groups and additional copper-centered polyhedra to form two mostly ordered periodic layers. Na2 Li0.75 (Cs,K)0.5 [Cu5 (PO4 ) Cl]·3.5(H2 O,OH) is a synthetic modification of a sampleite-polymorph of the lavendulan mineral group and represents a new member in a mero-plesiotype series of copper phosphates and arsenates, for which the crystal structures contain two-periodic [Cu4 X(TO4 )4 ]∞. Inorganic framework materials, the inorganic metal phosphates, oxyfluorides, nitrides, and sulphides with three-periodic porous structures are well known [4,5]. The interest in these materials is due to their multiple applications in catalysis, gas and ion separations, ion exchange, gas adsorption and storage, waste treatment, anion recognition, etc. The amazing variety of such properties is related to their structure peculiarities: robust 3D framework structures enclose pores of different sizes that may comprise extra-framework molecules and atoms
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