Details

Autor(en) / Beteiligte

• Colmont, Marie
• Endara, Diana
• Aliev, Almaz
• Terryn, Christine
• Huvé, Marielle
• Mentré, Olivier

Titel

Bi2O3–CuO–P2O5 system: Two novel compounds built from the intergrowths oxocentered polycationic 1D-ribbons

Ist Teil von

• Journal of solid state chemistry, 2013-07, Vol.203, p.266-272

Ort / Verlag

Amsterdam: Elsevier Inc

Erscheinungsjahr

2013

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• Single crystals of two novel bismuth copper oxyphosphates were grown from a unique melt. They have been structurally characterized by means of single crystal X-Ray Diffraction (XRD). Bi29.4Cu9.29O32(PO4)16Cu2.63 (1) is orthorhombic, space group Pca21, a=33.0549(2)Ǻ, b=11.6991(4)Ǻ and c=5.2902(2)Ǻ, R1=0.059 and wR2=0.061. Bi37.2Cu18.8O44(PO4)24Cu5 (2) is orthorhombic, space group Pna21, a=11.6010(3)Ǻ, b=47.4384(5)Ǻ and c=5.267(2)Ǻ, R1=0.0940 and wR2=0.0981. Both compounds are formed of similar 1D building units (BUs) organized into two different 3D regular intergrowths mediated by phosphate groups. Here, the so-called 1D-BUs are infinite ribbons formed by edge-sharing O(Bi,M)4 tetrahedra with n=4 and n=3 tetrahedra-wide units. Both compounds were analyzed from the viewpoint of their relationship with the parent δ-Bi2O3 fluorite-like structure, where phosphorus atoms substitutes for some Bi sites. A non-exhaustive review of the related structural types is given. We have checked by second harmonic generacy (SHG) microscopy that the two non-centrosymmetric structures (despite polar subunits) lead to SHG before the samples are irreversibly damaged. This paper reports the crystal structure of two new bismuth oxophosphate compounds. Both are built on the association of n=3 and 4 building unit ribbons surrounded by isolated PO4 tetrahedra and tunnels hosting Cu2+ cations. They come in addition to the numerous Bi-based compounds already pointed out. Once more, this is the proof of the richness of this crystal system. [Display omitted] •Two new bismuth oxophosphates were synthesized.•Crystal structure were solved thanks to single crystal X-Ray diffraction.•They show two different associations of n=3 and 4 ribbons built on [O,(Bi,M)4] tetrahedral sharing edges and surrounded by isolated PO4 groups.•SHG microscopy confirm the NCS character of both compounds.•The family of bismuth oxophosphate compounds contained several structures already pointed out but also still to be evidenced.