Bi{sub {approx}}{sub 3.785}Cd{sub {approx}}{sub 3.575}Cu{sub {approx}}{sub 1.5}(PO{sub 4}){sub 3.5}O{sub 5}= {sub .5}, a new arrangement of double (n=2) and triple (n=3) [M{sub 4}Bi{sub 2n-2}O{sub 2n}]{sup x+} polycationic ribbons in the bismuth-transition metal oxy-phosphate series

Journal Article · Mon Nov 01 00:00:00 EST 2004 · Journal of Solid State Chemistry

DOI:https://doi.org/10.1016/j.jssc.2004.06.057· OSTI ID:20655405

Colmont, Marie ^[1]; Huve, Marielle ^[1]; Abraham, Francis ^[1]; Mentre, Olivier ^[1]

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1. Laboratoire de Cristallochimie et Physicochimie du Solide, CNRS UMR 8012, ENSCL, Universite des Sciences et Technologies de Lille, BP.108, F-59652 Villeneuve d'Ascq Cedex (France)

This work is dedicated to investigation of new disordered bismuth-containing oxy-phosphates compounds with an original structure type. As previously observed in this series, they are formed of [M{sub 4}Bi{sub 2n-2}O{sub 2n}]{sup x+} polycationic ribbons of width n O(Bi,M){sub 4} tetrahedra, surrounded by PO{sub 4} groups. In the new crystal structure type, double (=D), triple (=T) and tunnels (=t) alternate along a common axis obeying the TtDtTtDt/TTtTTt sequence in respect to a nomenclature previously described and recalled in this work. The existence this new polymorph has first been detected by electron diffraction in a multi-phased sample. Then, the crystal structure type, i.e., the TtDtTtDt/TTtTTt sequence, has been deduced from HREM images help to a contrast-interpreting code available for these series of polycations-formed compounds. The subsequent compounds formulation leads to a number of new materials that verify the general formula: [Bi{sub 2}(Bi,M){sub 4}O{sub 4}]{sub 2} [Bi{sub 4}(Bi,M){sub 4}O{sub 6}]{sub 6} (PO{sub 4}){sub 28} M{sub x}, with x=<12 and M=Cu{sup 2+}, Cd{sup 2+} cations. Single crystals of the nominal [O6Bi{sub 4.57}Cd{sub 3.43}]{sub 4}{sup +8.57} [O{sub 6}Bi{sub 4}Cd{sub 4}]{sub 2}{sup +8} [O{sub 4}Bi{sub 2}Cd{sub 3.56}Cu{sub 0.44}]{sub 2}{sup +6} (PO{sub 4}){sub 28} Cu{sub 10.86} have been prepared in a further stage and confirms the predicted crystal structure, Bi{sub {approx}}{sub 3.785}Cd{sub {approx}}{sub 3.575}Cu{sub {approx}}{sub 1.5}(PO{sub 4}){sub 3.5}O{sub 5.5}= , a=11.506(8)A, b=5.416(4)A, c=53.94 (4)A, {beta}=90.10(1){sup o}, RF=0.0835, RwF=0.0993, SG=A2/m, Z=8. As already observed for other elements of this family such as Bi{sub {approx}}{sub 1.2}M{sub {approx}}{sub 1.2}O{sub 1.5}(PO{sub 4}), Bi{sub {approx}}{sub 6.2}Cu{sub {approx}}{sub 6.2}O{sub 8}(PO{sub 4}){sub 5} or Bi{sub {approx}}{sub 3}Cd{sub {approx}}{sub 3.72}M{sub {approx}}{sub 1.28}O{sub 5}(PO{sub 4}){sub 3} (M=Cu, Co, Zn), this compound shows an additional example of PO{sub 4} disorder due to the presence of mixed Bi{sup 3+}/M{sup 2+} sites at the edges of ribbons. The origin and consequence of this so-called disorder mostly occurring on PO{sub 4} configurations is intensively discussed and has been characterized by infrared spectroscopy and by neutron diffraction on similar compounds. It is noticeable that the great number of antagonist PO{sub 4} configurations may order along the b-axis within a large periodicity which involves incommensurate lattice.

• OSTI ID: 20655405
• Journal Information: Journal of Solid State Chemistry, Vol. 177, Issue 11; Other Information: DOI: 10.1016/j.jssc.2004.06.057; PII: S0022-4596(04)00370-6; Copyright (c) 2004 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved; Country of input: International Atomic Energy Agency (IAEA); ISSN 0022-4596
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ABSORPTION SPECTROSCOPY
BISMUTH COMPOUNDS
BISMUTH IONS
BISMUTH OXIDES
COPPER IONS
CRYSTAL STRUCTURE
ELECTRON DIFFRACTION
INFRARED SPECTRA
NEUTRON DIFFRACTION
PHOSPHATES
TRANSITION ELEMENT COMPOUNDS
TRANSMISSION ELECTRON MICROSCOPY
X-RAY DIFFRACTION