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The crystal structure of kraisslite, [4]Zn3(Mn, Mg)25(Fe3+,Al)(As3+O3)2[(Si,As5+)O4]10(OH)16, from the Sterling Hill mine, Ogdensburg, Sussex County, New Jersey, USA

Published online by Cambridge University Press:  05 July 2018

M. A. Cooper  and
F. C. Hawthorne
M. A. Cooper
Affiliation:
Department of Geological Sciences, University of Manitoba, Winnipeg, Manitoba R3T 2N2, Canada
F. C. Hawthorne*
Affiliation:
Department of Geological Sciences, University of Manitoba, Winnipeg, Manitoba R3T 2N2, Canada
*
*E-mail: [email protected]
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Abstract

The crystal structure of kraisslite, orthorhombic (pseudo-hexagonal), a = 8.1821(1), b = 14.1946(3), c = 43.9103(8) Å, V = 5099.8(2) Å3, Z = 4 and dcalc = 4.083 g cm–3, has been solved by direct methods and refined in the space group C2221 to an R1 index of 1.68% for 7432 observed (|Fo| > 4σ|F|) reflections. Electron-microprobe analysis gave the following chemical composition: As2O510.86, As2O36.18, SiO213.39, Al2O30.25, Fe2O32.06, MnO 51.14, ZnO 7.39, MgO 2.13, CaO 0.05, H2Ocalc = 4.50, sum 97.95 wt.%; and empirical formula: Zn2.91(Mn23.07Mg1.69Ca0.03)Σ=24.79(Fe0.833+Al0.16)Σ=0.99(As3+O3)2[(Si0.71As0.305+)O4]10(OH)16 calculated on the basis of 62 anions with (OH) = 16 and As3+/(As3+ + As5+) taken from the refined crystal structure. The general formula, [4]Zn3(Mn,Mg)25(Fe3+,Al)(As3+O3)2[(Si,As5+)O4]10(OH)16, differs from those given previously.

There is one As3+ site with a <As–O> distance of 1.780 Å and a stereochemistry typical of a stereoactive lone-pair of electrons. There are five tetrahedrally coordinated T sites with <T–O> distances from 1.635 to 1.692 Å; the T(1) site is fully occupied by As5+, and the T(2)–T(5) sites are occupied by both Si and As5+. There are two tetrahedrally coordinated Zn sites with <T–O> distances of ∼1.996 Å, both of which are occupied by dominant Zn and minor Mn2+. There are thirteen octahedrally coordinated M sites, twelve of which are occupied by dominant Mn2+ with lesser Mg and minor Zn; <M–O> distances are in the range 2.197–2.284 Å. The <M(13)–O> distance is 2.083 Å and its lower site scattering indicates occupancy by Fe3+, Mn2+, Mg and Al. The structure consists of five crystallographically distinct layers of polyhedra, labelled m = 0 – 4. Layer m = 0 consists of corner-sharing Zn and (Si, As5+) tetrahedra, and layers m = 1–4 each consist of trimers of Mn2+ octahedra linked by (Si, As5+) tetrahedra and intrasheet hydrogen bonds (m = 1, 3) or (Si, As5+) tetrahedra and (Fe3+,Al) octahedra (m = 2) or (As5+) tetrahedra and (As3+O3) triangular pyramids and intrasheet hydrogen bonds (m = 4). The layers stack along [001] with reversals of the sequence m = 1, 2, 3, 4 at z = 0, ¼, ½ and ¾. Kraisslite is a member of the mcgovernite family.

Keywords

crystal structureelectron-microprobe analysismcgovernite family
Type
Research Article
Information
Mineralogical Magazine , Volume 76 , Issue 7 , December 2012 , pp. 2819 - 2836
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2016

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