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The crystal structure of balićžunićite, Bi2O(SO4)2, a new natural bismuth oxide sulfate

Published online by Cambridge University Press:  02 January 2018

Daniela Pinto ,
Anna Garavelli  and
Tonci Balić-Žunić
Daniela Pinto*
Affiliation:
Dipartimento di Scienze della Terra e Geoambientali, Università di Bari, via E. Orabona 4, I-70125 Bari, Italy
Anna Garavelli
Affiliation:
Dipartimento di Scienze della Terra e Geoambientali, Università di Bari, via E. Orabona 4, I-70125 Bari, Italy
Tonci Balić-Žunić
Affiliation:
Natural History Museum, University of Copenhagen, Øster Voldgade 5-7, DK-1350 Copenhagen K, Denmark
*
*E-mail: daniela.pinto@uniba.it
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Abstract

The crystal structure of balićžunićite, Bi2O(SO4)2, a new mineral species from the La Fossa crater of Vulcano (Aeolian Islands, Italy), was solved from single-crystal X-ray diffraction data and refined to R = 0.0507. The structure is triclinic, space group P1, with a = 6.7386(3), b = 11.1844(5), c = 14.1754(7) Å, α = 80.082(2), β = 88.462(2)°, γ = 89.517(2)°, V = 1052.01(8) Å3 and Z = 6. The crystal structure consists of six independent Bi sites, six S sites and 27 O sites of which three are oxo oxygen atoms not bonded to sulfur. Bismuth and S atoms are arranged close to a eutectic pattern parallel to the (100) plane. The planes are stacked atom on atom such that Bi always overlays S and vice versa. This structural feature is shared with the known structure of the high-temperature polymorph of the same compound, stable at T >535°C. However, the sequences of Bi and S atoms in the two structures are different and so are the arrangements of oxygen atoms. Characteristic building blocks in the structure of balićžunićite are clusters of five Bi atoms which form nearly planar trapezoidal Bi5 groups with oxo oxygens located in the centres of the three Bi3 triangles, which form the trapezoids. The trapezoidal Bi5O39+ ions are joined along [100] with SO42– groups by means of strong bismuth-sulfate oxygen bonds, forming infinite [100] rods with composition Bi5O3(SO4)5–. One sixth of the Bi atoms do not participate in trapezoids, but form, with additional SO42– groups, rows of composition BiSO4+, also parallel to [100]. [Bi5O3(SO4)5–] rods form infinite layers parallel to (010) with [BiSO4+] rows located on the irregular surface of contact between adjacent layers. Bi atoms occur in four different coordination types, all showing the stereochemical influence of the Bi3+ lone electron pair. In this respect the crystal structure of balićžunićite shows greater variability than its high-temperature polymorph which has only two types of the Bi coordination spheres present in balićžunićite.

Keywords

balićžunićitebismuth oxide sulfatesingle-crystal X-ray diffractioncrystal structurelone electron pair
Type
Research Article
Information
Mineralogical Magazine , Volume 79 , Issue 3 , June 2015 , pp. 597 - 611
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2015

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