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Pinto D, Garavelli A, Bindi L. Fluorite-related one-dimensional units in natural bismuth oxysulfates: the crystal structures of Bi14O16(SO4)5 and Bi30O33(SO4)9(AsO4)2. Acta Crystallogr B Struct Sci Cryst Eng Mater. 2015;71:514-23doi: 10.1107/S205252061501358X.
Pinto, D., Garavelli, A., & Bindi, L. (2015). Fluorite-related one-dimensional units in natural bismuth oxysulfates: the crystal structures of Bi14O16(SO4)5 and Bi30O33(SO4)9(AsO4)2. Acta crystallographica Section B, Structural science, crystal engineering and materials, 71514-23. https://doi.org/10.1107/S205252061501358X
Pinto, Daniela, et al. "Fluorite-related one-dimensional units in natural bismuth oxysulfates: the crystal structures of Bi14O16(SO4)5 and Bi30O33(SO4)9(AsO4)2." Acta crystallographica Section B, Structural science, crystal engineering and materials vol. 71 (2015): 514-23. doi: https://doi.org/10.1107/S205252061501358X
Pinto D, Garavelli A, Bindi L. Fluorite-related one-dimensional units in natural bismuth oxysulfates: the crystal structures of Bi14O16(SO4)5 and Bi30O33(SO4)9(AsO4)2. Acta Crystallogr B Struct Sci Cryst Eng Mater. 2015 Oct;71:514-23. doi: 10.1107/S205252061501358X. Epub 2015 Sep 19. PMID: 26428401.
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Acta Crystallogr B Struct Sci Cryst Eng Mater. 2015 Oct;71:514-23. doi: 10.1107/S205252061501358X. Epub 2015 Sep 19.

Fluorite-related one-dimensional units in natural bismuth oxysulfates: the crystal structures of Bi14O16(SO4)5 and Bi30O33(SO4)9(AsO4)2.

Acta crystallographica Section B, Structural science, crystal engineering and materials

Daniela Pinto, Anna Garavelli, Luca Bindi

Affiliations

  1. Dipartimento di Scienze della Terra e Geoambientali, Università degli Studi di Bari A. Moro, Via E. Orabona, 4, I-70125 Bari, Italy.
  2. Dipartimento di Scienze della Terra, Università degli Studi di Firenze, Via La Pira, 4, I-50121 Firenze, Italy.

PMID: 26428401 DOI: 10.1107/S205252061501358X

Abstract

The crystal structures of two new natural Bi oxysulfates with the formula Bi14O16(SO4)5 [labelled new phase I; monoclinic, space group C2, a = 21.658 (4), b = 5.6648 (9), c = 15.092 (3) Å, β = 119.433 (11)° and Z = 2] and Bi30O33(SO4)9(AsO4)2 [labelled new phase II; triclinic, space group P1, a = 5.670 (3), b = 13.9408 (9), c = 22.7908 (18) Å, α = 80.903 (5), β = 82.854 (14), γ = 78.27 (2)° and Z = 1] from the high-temperature fumarole deposit of the La Fossa crater at Vulcano (Aeolian Islands, Italy) are reported. The structures are built up by a combination of fluorite-related Bi-O units and isolated (SO4)(2-) tetrahedra (new phase I) or both (SO4)(2-) and (AsO4)(3-) tetrahedra (new phase II). Owing to the effect of stereoactive lone pairs of Bi(3+), Bi-O units in both the structures can be suitably described in terms of oxo-centered OBi4 tetrahedra. The structure of Bi14O16(SO4)5 is based upon one-dimensional [O16Bi14](10+) ribbons formed by six chains of edge-sharing OBi4 tetrahedra extending along [010]. In the structure of Bi30O33(SO4)9(AsO4)2 the same ribbon type coexists with another one-dimensional ribbon formed by seven chains of edge-sharing OBi4 tetrahedra and with the composition [O17Bi16](14+). Ribbons of the same type are joined by (SO4)(2-) and (AsO4)(3-) tetrahedra along [010] – if a reduced triclinic unit-cell setting is considered – so forming two different (001) slabs which alternate to each other along [001] and are joined by additional (SO4)(2-) tetrahedra. New phase I represents the natural analogues of synthetic Bi14O16(SO4)5, but with an ordered structure model.

Keywords: Bi oxysulfates; Vulcano; fluorite; oxo-centered tetrahedra; sublimates

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