RESUMO
Single crystals of Rb2CaCu6(PO4)4O2 were synthesized by a hydrothermal method in the multicomponent system CuCl2-Ca(OH)2-RbCl-B2O3-Rb3PO4. The synthesis was carried out in the temperature range from 690 to 700â K and at the general pressure of 480-500â atm [1â atm = 101.325â kPa] from the mixture in the molar ratio 2CuO:CaO:Rb2O:B2O3:P2O5. The crystals studied by single-crystal X-ray analysis were found to be monoclinic, space group C2, a = 16.8913â (4), b = 5.6406â (1), c = 8.3591â (3)â Å, ß = 93.919â (3)°, V = 794.57â (4)â Å3. The crystal structure of Rb2CaCu6(PO4)4O2 is similar to that of shchurovskyite and dmisokolovite and is based upon a heteropolyhedral open framework formed by polar layers of copper polyhedra linked via isolated PO4 tetrahedra. The presence of well-isolated 2D heteropolyhedral layers in the title compound suggests low-dimensional magnetic behavior which is masked, however, by the fierce competition between multiple ferromagnetic and antiferromagnetic exchange interactions. At TC = 25â K, Rb2CaCu6(PO4)4O2 reaches a magnetically ordered state with large residual magnetization.
RESUMO
The bismuth(III) oxophosphate Bi3(PO4)O3 was obtained by hydrothermal synthesis. The unit cell has a = 5.6840(6) Å, b = 7.0334(7) Å, c = 9.1578(9) Å, α = 78.958(2)°, ß = 77.858(2)°, γ = 68.992(2)°, V = 331.41(6) Å3, space group P1Ì , and Z = 2. The crystal chemical formula that reflects the presence of oxo-centered tetrahedra and triangles is 2D[OIIIOIV2Bi3](PO4). The crystal structure contains [O3Bi3]3+∞∞-heteropolyhedral corrugated layers parallel to (001), which alternate along [001] with isolated (PO4) tetrahedra. The structural complexity parameters are v = 22 atoms, IG = 3.459 bits/atoms, and IG,total = 76.107 bits/unit cell, and thus Bi3(PO4)O3 is the simplest pure bismuth(III) oxophosphate.