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Hydrothermal synthesis and crystal structure of Na(Na,Mn) (sub 7) Mn (sub 22) (PO (sub 4) ) (sub 18) .0.5H (sub 2) O, a new compound of fillowite structure type

Paul Keller, Frederic Hatert, Falk Lissner, Thomas Schleid and Andre-Mathieu Fransolet
Hydrothermal synthesis and crystal structure of Na(Na,Mn) (sub 7) Mn (sub 22) (PO (sub 4) ) (sub 18) .0.5H (sub 2) O, a new compound of fillowite structure type
European Journal of Mineralogy (December 2006) 18 (6): 765-774

Abstract

The chemical compound Na(Na,Mn) (sub 7) Mn (sub 22) (PO (sub 4) ) (sub 18) .0.5H (sub 2) O was synthesized with a Tuttle pressure vessel at 800 degrees C and 1 kbar during experimental investigations on the conditions of fillowite formation. The crystal structure of a single-crystal, space group R3 (No. 148), a = 15.2741(9), c = 43.334(3) A, Z = 6, was determined from X-ray intensity data and refined up to R (sub 1) = 0.0728 and R (sub 1{FO >4sigma (FO)}) = 0.0546. The crystal structure of Na(Na,Mn) (sub 7) Mn (sub 22) (PO (sub 4) ) (sub 18) .0.5H (sub 2) O is similar to the structure of fillowite, Na (sub 6) Ca (sub 3) (Mn,Fe) (sub 21) (PO (sub 4) ) (sub 18) , but a significant difference between the synthetic H (sub 2) O containing compound and fillowite is the replacement of (Na12)O (sub 8) - by Mn(H (sub 2) O) (sub 2) O (sub 5) - polyhedra, which form characteristic six-member rings. The coordination polyhedra around Na12 and Mn12 are so different that simple isomorphous substitution of Na12 by Mn12 is very unlikely, but whole six-member rings either of (Na12)O (sub 8) - or (Mn12)(H (sub 2) O) (sub 2) O (sub 5) polyhedra seem to be distributed statistically over the crystal structure. No indication for ordering, e.g. sheet by sheet, has been observed. Na(Na,Mn) (sub 7) Mn (sub 22) (PO (sub 4) ) (sub 18) .0.5H (sub 2) O is the first fillowite-like compound for which water is located in the structure from single-crystal study. This result is proved by infrared spectral data and indicates that water can play an essential role in the fillowite structure-type. Structural features of the synthetic compounds Na(Na,Mn) (sub 7) Mn (sub 22) (PO (sub 4) ) (sub 18) .0.5H (sub 2) O, Na (sub 4) Ca (sub 4) Mg (sub 21) (PO (sub 4) ) (sub 18) and fillowite are compared.


ISSN: 0935-1221
EISSN: 1617-4011
Serial Title: European Journal of Mineralogy
Serial Volume: 18
Serial Issue: 6
Title: Hydrothermal synthesis and crystal structure of Na(Na,Mn) (sub 7) Mn (sub 22) (PO (sub 4) ) (sub 18) .0.5H (sub 2) O, a new compound of fillowite structure type
Affiliation: Universitaet Stuttgart, Institut fuer Mineralogie und Kristallchemie, Stuttgart, Federal Republic of Germany
Pages: 765-774
Published: 200612
Text Language: English
Publisher: Schweizerbart'sche Verlagsbuchhandlung (Naegele u. Obermiller), Stuttgart, Federal Republic of Germany
References: 31
Accession Number: 2007-017129
Categories: Mineralogy of non-silicates
Document Type: Serial
Bibliographic Level: Analytic
Illustration Description: illus. incl. 5 tables
Secondary Affiliation: Universite de Liege, BEL, BelgiumRuhr-Universitaet Bochum, DEU, Federal Republic of Germany
Country of Publication: Germany
Secondary Affiliation: GeoRef, Copyright 2017, American Geosciences Institute.
Update Code: 200710
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