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Title: Bi{sub 2}O{sub 3}–CuO–P{sub 2}O{sub 5} system: Two novel compounds built from the intergrowths oxocentered polycationic 1D-ribbons

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). Bi{sub 29.4}Cu{sub 9.29}O{sub 32}(PO{sub 4}){sub 16}Cu{sub 2.63} (1) is orthorhombic, space group Pca2{sub 1}, a=33.0549(2)A, b=11.6991(4)A and c=5.2902(2)A, R{sub 1}=0.059 and wR{sub 2}=0.061. Bi{sub 37.2}Cu{sub 18.8}O{sub 44}(PO{sub 4}){sub 24}Cu{sub 5} (2) is orthorhombic, space group Pna2{sub 1}, a=11.6010(3)A, b=47.4384(5)A and c=5.267(2)A, R{sub 1}=0.0940 and wR{sub 2}=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){sub 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-Bi{sub 2}O{sub 3} 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. - Graphical abstract: This paper reports the crystal structure of two new bismuth oxophosphate compounds. Both are built on the association of n=3 and 4more » building unit ribbons surrounded by isolated PO4 tetrahedra and tunnels hosting Cu{sup 2+} 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. - Highlights: • 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){sub 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.« less
Authors:
 [1] ; ;  [1] ;  [2] ; ;  [1]
  1. Universite Lille 1, Universite Lille Nord France, ENSCL, CNRS, UCCS, UMR 8181, F-59652 Villeneuve d' Ascq (France)
  2. Plateforme Imagerie Cellulaire et Tissulaire, 51 Rue Cognacq-Jay, 51100 Reims (France)
Publication Date:
OSTI Identifier:
22309046
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 203; Other Information: Copyright (c) 2013 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; BISMUTH; BISMUTH OXIDES; CATIONS; FLUORITE; MONOCRYSTALS; ORTHORHOMBIC LATTICES; PHOSPHATES; PHOSPHORUS; SPACE GROUPS; X-RAY DIFFRACTION