Low-temperature single crystal X-ray diffraction and high-pressure Raman studies on [(CH{sub 3}){sub 2}NH{sub 2}]{sub 2}[SbCl{sub 5}]
- Crystallography Laboratory, Department of Geosciences, Virginia Tech, Blacksburg, VA 24061 (United States)
The structure of bis(dimethylammonium) pentachloroantimonate(III), [(CH{sub 3}){sub 2}NH{sub 2}]{sub 2}[SbCl{sub 5}], BDP, was studied at 15 K and ambient pressure by single-crystal X-ray diffraction as well as at ambient temperature and high pressures up to 4.87(5) GPa by Raman spectroscopy. BDP crystallizes in the orthorhombic Pnma space group with a=8.4069(4), b=11.7973(7), c=14.8496(7) A, and Z=4; R{sub 1}=0.0381, wR{sub 2}=0.0764. The structure consists of distorted [SbCl{sub 6}]{sup 3-} octahedra forming zig-zag [{l_brace}SbCl{sub 5}{r_brace}{sub n}]{sup 2n-} chains that are cross-linked by dimethylammonium [(CH{sub 3}){sub 2}NH{sub 2}]{sup +} cations. The organic and inorganic substructures are bound together by the N-H...Cl hydrogen bonds. The distortions of [SbCl{sub 6}]{sup 3-} units increase, partly due to the influence of the hydrogen bonds which became stronger, with decreasing temperature. The preliminary room temperature, high-pressure X-ray diffraction experiments suggest that BDP undergoes a first-order phase transition below ca. 0.44(5) GPa that destroys single-crystal samples. The transition is accompanied by changes in the intensities and positions of the Raman lines below 400 cm{sup -1}. - Graphical abstract: On cooling to 15 K [(CH{sub 3}){sub 2}NH{sub 2}]{sub 2}[SbCl{sub 5}] shows significant changes in the geometries of the longest Sb-Cl bonds that are correlated with the changes in the geometry of the N-H...Cl hydrogen bonds. Applying of quite modest pressures far exceed observed temperature-induced changes-[(CH{sub 3}){sub 2}NH{sub 2}]{sub 2}[SbCl{sub 5}] undergoes a first-order phase transition below ca. 0.44(5) GPa that destroys single-crystal samples.
- OSTI ID:
- 21043722
- Journal Information:
- Journal of Solid State Chemistry, Vol. 180, Issue 11; Other Information: DOI: 10.1016/j.jssc.2007.08.025; PII: S0022-4596(07)00351-9; Copyright (c) 2007 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved; Country of input: International Atomic Energy Agency (IAEA); ISSN 0022-4596
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
AMBIENT TEMPERATURE
ANTIMONY CHLORIDES
ANTIMONY COMPLEXES
CHEMICAL BONDS
MONOCRYSTALS
ORTHORHOMBIC LATTICES
PHASE TRANSFORMATIONS
PRESSURE RANGE MEGA PA 100-1000
RAMAN SPECTROSCOPY
SPACE GROUPS
TEMPERATURE RANGE 0013-0065 K
TEMPERATURE RANGE 0273-0400 K
X-RAY DIFFRACTION