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- Title
Crystal structure of the high-temperature form of the trisulfide Cs<sub>2</sub>S<sub>3</sub> and the (3+1)D modulated structure of the telluride K<sub>37</sub>Te<sub>28</sub>.
- Authors
Stüble, Pirmin; Berroth, Angela; Wortelkamp, Fritz; Röhr, Caroline
- 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 S 3 2 − ${\rm{S}}_3^{2 - }$ 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).
- Subjects
STOICHIOMETRIC combustion; GENETIC polymorphisms; TETRAGONAL crystal system; CRYSTAL structure; X-ray diffraction
- Publication
Zeitschrift für Naturforschung B: A Journal of Chemical Sciences, 2019, Vol 74, Issue 1, p33
- ISSN
0932-0776
- Publication type
Article
- DOI
10.1515/znb-2018-0168