Influence of intermolecular interactions on the Mössbauer quadrupole splitting of organotin(IV) compounds as studied by DFT calculations

Szilvia Kárpáti, Roland Szalay, A. Császár, Károly Siivegh, Sándor Nagy

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Abstract

The influence of intermolecular interactions on the Mössbauer quadrupole splitting (Δ) of 119Sn was investigated in detail by density functional theory (DFT) calculations. Six organotin(IV) complexes [Me2Sn(acac)2 (1), Ph3SnCl (2), Me 3Sn-succinimide (3), Me3Sn-phthalimide (4), Me 3SnCl (5), and cHex3SnCl (6)] of known solid-state structures and quadrupole splittings were selected. Theoretical A values were calculated for both fully optimized geometries and experimental solid-state structures of different size, and the results were compared to the experimental A values. Compared to a synthetic procedure described in the literature for compound 4, a more convenient synthesis is reported here. The experimental A of this compound has also been redetermined at 80 K. For compounds with negligible intermolecular interactions in the solid state, calculated A values obtained did not vary significantly. In contrast, the calculated A values turned out to be very sensitive to the size of the supramolecular moiety considered in the crystal lattice. The crystal structure of compound 2 shows no significant intermolecular interactions; however, the calculated and the experimental A values remained very different, even when the supramolecular moiety considered was extended. Distortion of the coordination sphere of tin in the molecule of 2 toward a trigonal bipyramidal geometry was considered, and a possible weak intermolecular Sn⋯Cl interaction was included in the model. Steps of the distortion followed the new structure correlation function, which was found for the R3SnCl (R = alkyl, aryl) compounds. The experimental A value could be approached by this method. These results suggest that compound 2 is involved in some unexpected intermolecular interaction at 80 K.

Original languageEnglish
Pages (from-to)13172-13181
Number of pages10
JournalJournal of Physical Chemistry A
Volume111
Issue number50
DOIs
Publication statusPublished - Dec 20 2007

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Density functional theory
quadrupoles
density functional theory
solid state
Geometry
Tin
interactions
Crystal lattices
succinimides
phthalimides
Crystal structure
aromatic compounds
geometry
Molecules
crystal lattices
tin
crystal structure
synthesis
molecules
phthalimide

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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Influence of intermolecular interactions on the Mössbauer quadrupole splitting of organotin(IV) compounds as studied by DFT calculations. / Kárpáti, Szilvia; Szalay, Roland; Császár, A.; Siivegh, Károly; Nagy, Sándor.

In: Journal of Physical Chemistry A, Vol. 111, No. 50, 20.12.2007, p. 13172-13181.

Research output: Contribution to journalArticle

Kárpáti, Szilvia ; Szalay, Roland ; Császár, A. ; Siivegh, Károly ; Nagy, Sándor. / Influence of intermolecular interactions on the Mössbauer quadrupole splitting of organotin(IV) compounds as studied by DFT calculations. In: Journal of Physical Chemistry A. 2007 ; Vol. 111, No. 50. pp. 13172-13181.
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AB - The influence of intermolecular interactions on the Mössbauer quadrupole splitting (Δ) of 119Sn was investigated in detail by density functional theory (DFT) calculations. Six organotin(IV) complexes [Me2Sn(acac)2 (1), Ph3SnCl (2), Me 3Sn-succinimide (3), Me3Sn-phthalimide (4), Me 3SnCl (5), and cHex3SnCl (6)] of known solid-state structures and quadrupole splittings were selected. Theoretical A values were calculated for both fully optimized geometries and experimental solid-state structures of different size, and the results were compared to the experimental A values. Compared to a synthetic procedure described in the literature for compound 4, a more convenient synthesis is reported here. The experimental A of this compound has also been redetermined at 80 K. For compounds with negligible intermolecular interactions in the solid state, calculated A values obtained did not vary significantly. In contrast, the calculated A values turned out to be very sensitive to the size of the supramolecular moiety considered in the crystal lattice. The crystal structure of compound 2 shows no significant intermolecular interactions; however, the calculated and the experimental A values remained very different, even when the supramolecular moiety considered was extended. Distortion of the coordination sphere of tin in the molecule of 2 toward a trigonal bipyramidal geometry was considered, and a possible weak intermolecular Sn⋯Cl interaction was included in the model. Steps of the distortion followed the new structure correlation function, which was found for the R3SnCl (R = alkyl, aryl) compounds. The experimental A value could be approached by this method. These results suggest that compound 2 is involved in some unexpected intermolecular interaction at 80 K.

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