[C 6H 21N 4][Sb 9S 14O]: Solvothermal synthesis, crystal structure and characterization of the first non-centrosymmetric open Sb–S–O framework containing the new [SbS 2O] building unit

• Published in: Journal of solid state chemistry Vol. 179; no. 10; pp. 3082 - 3086
• Main Authors: Kiebach, Ragnar, Näther, Christian, Peter Sebastian, C., Mosel, Bernd D., Pöttgen, Rainer, Bensch, Wolfgang
• Format: Journal Article
• Language: English
• Published: San Diego, CA Elsevier Inc 2006; Elsevier
• Subjects: ANTIMONATES; ANTIMONY OXIDES; ANTIMONY SULFIDES; BOND LENGTHS; Condensed matter: electronic structure, electrical, magnetic, and optical properties; Cross-disciplinary physics: materials science; rheology; Crystal structure; Exact sciences and technology; Growth from solutions; HYDROTHERMAL SYNTHESIS; Magnetic resonances and relaxations in condensed matter, mössbauer effect; MATERIALS SCIENCE; Methods of crystal growth; physics of crystal growth; MOESSBAUER EFFECT; Mössbauer effect; other γ-ray spectroscopy; Mössbauer spectroscopy; ORTHORHOMBIC LATTICES; Oxo-thioantimonates; Physics; SPACE GROUPS; SPECTRA; Hydrothermal synthesis; Oxo-thioantimonates; Mössbauer spectroscopy; Crystal structure; Non centrosymmetric crystals; Moessbauer effect; Inorganic compounds; Semiconductor materials; Hybrid material; Solvothermal synthesis; Thermogravimetry; Line widths; Differential thermal analysis; Experimental study; Heat treatments; Antimony sulfides; Open framework; Aqueous solutions; Orthorhombic lattices; Crystal growth from solutions; Ultraviolet visible spectrum; Optical materials; Tetradentate ligand; Organic compounds
• ISSN: 0022-4596; 1095-726X
• DOI: 10.1016/j.jssc.2006.05.041

[C
6H
21N
4][Sb
9S
14O] represents the first known oxo-thioantimonate with an organic ion acting as structure director. The compound crystallizes in the non-centrosymmetric space group
Cmc2
1 with
a
=
29.679
(
2
)
,
b
=
9.9798
(
6
)
,
c
=
11.7155
(
7
)
Å
,
V
=
3470.1
(
4
)
Å
3
,
Z
=
4
. The structure contains the hitherto unknown [SbS
2O] unit as a structural motif. The [SbS
3] trigonal pyramids and [SbS
2O] units are joined to form a 10-membered ring with large pores having a diameter of 7.7
Å×8.3
Å. The organic template molecule acts like a tetra-dentate ligand around the O atom of the [SbS
2O] group. Depending on the value chosen for the Sb–S bond lengths, the material contains a 1-, 2- or 3-dimensional anion. The optical band gap of 2.03
eV demonstrates that the material is an optical semi-conductor. Upon heating, the compound decomposes in two steps yielding finally a mixture of Sb and Sb
2S
3. The
121Sb Mössbauer spectrum shows a relative large line width in accordance with the superposition of the five signals.
The [Sb
9S
14O]
3− chain in [C
6H
21N
4][Sb
9S
14O] directed along the
b-axis with the organic template molecule acting like a tetra-dentate ligand around the O atom of the [SbS
2O] group.