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Zeitschrift für Naturforschung B

A Journal of Chemical Sciences

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1865-7117
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Crystal structure of the high-temperature form of the trisulfide Cs2S3 and the (3+1)D modulated structure of the telluride K37Te28

Pirmin Stüble
  • Institut für Anorganische und Analytische Chemie, Universität Freiburg, Albertstrasse 21, D-79104 Freiburg, Germany
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/ Angela Berroth
  • Institut für Anorganische und Analytische Chemie, Universität Freiburg, Albertstrasse 21, D-79104 Freiburg, Germany
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/ Fritz Wortelkamp
  • Institut für Anorganische und Analytische Chemie, Universität Freiburg, Albertstrasse 21, D-79104 Freiburg, Germany
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/ Caroline Röhr
  • Corresponding author
  • Institut für Anorganische und Analytische Chemie, Universität Freiburg, Albertstrasse 21, D-79104 Freiburg, Germany
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Published Online: 2018-11-16 | DOI: https://doi.org/10.1515/znb-2018-0168

Abstract

The high-temperature polymorph of the trisulfide Cs2S3, which has been synthesized from Cs2S2 and elemental sulfur, crystallizes in a new structure type (monoclinic, space group P21/c, a=999.97(4), b=1029.30(5), c=2642.07(12) pm, β=90.083(2)°, Z=16, R1=0.0324). The structure contains four crystallographically independent angled S32 trisulfide ions with S–S distances of 205.7–208.3 pm. The distorted b.c.c. packing of the anions and their insertion in the five-membered rings of 3.53+3.5.3.5. (1:1) Cs nets are similarly found in the r.t. form (Cmc21, K2S3-type structure) and the two polymorphs differ mainly in the orientation of the S3 groups. The second title compound, K37Te28, was synthesized from stoichiometric melts of the elements. It forms a complex (3+1)D modulated tetragonal structure (space group I41/amd (00σ3)s0s0, q=(0, 0, 0.5143), a=1923.22(2), c=2626.66(4) pm, Z=4, R1all=0.0837). According to K37Te28=K37[Te(1X)]8[Te(2X)2]6[Te(3X)8] the structure contains three different types of Te anions: The two crystallographically different isolated telluride anions [Te(1X)]2− are coordinated by 9/10 K+ cations. Three [Te(2X)2]2− dumbbells (dTe-Te=277.9/286.4 pm) are arranged to ‘hexamers’. The Te(31) and Te(32) atoms are located in columns of face-sharing K square antiprisms. Their z position modulation, which is accompanied by a smaller shift of the surrounding K+ cations, results in the decomposition of the [Te(3X)8]2 chain in a sequence |:Te3–Te2–Te2–Te3–Te2–Te2–Te2:| of dumbbells Te22− (dTe–Te=304 pm) and hypervalent linear trimers Te34− (dTe–Te=325 pm).

Keywords: (3+1)D modulated structure; cesium; potassium; sulfides; tellurides

Dedicated to: Professor Wolfgang Bensch on the occasion of his 65th birthday.

References

About the article

Received: 2018-08-15

Accepted: 2018-10-20

Published Online: 2018-11-16


Citation Information: Zeitschrift für Naturforschung B, 20180168, ISSN (Online) 1865-7117, ISSN (Print) 0932-0776, DOI: https://doi.org/10.1515/znb-2018-0168.

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