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Charge density of 4-methyl-3-[(tetra­hydro-2H-pyran-2-yl)­­oxy]thia­zole-2(3H)-thione : A comprehensive multipole refinement, maximum entropy method and density functional theory study

Title data

Vénosová, Barbora ; Koziskova, Julia ; Kožíšek, Jozef ; Herich, Peter ; Lušpai, Karol ; Petricek, Vaclav ; Hartung, Jens ; Müller, Mike ; Hübschle, Christian B. ; van Smaalen, Sander ; Bucinsky, Lukas:
Charge density of 4-methyl-3-[(tetra­hydro-2H-pyran-2-yl)­­oxy]thia­zole-2(3H)-thione : A comprehensive multipole refinement, maximum entropy method and density functional theory study.
In: Acta Crystallographica Section B. Vol. 76 (June 2020) Issue 3 . - pp. 450-468.
ISSN 2052-5206
DOI: https://doi.org/10.1107/S2052520620005533

Official URL: Volltext

Project information

Project financing: APVV
VEGA

Abstract in another language

The structure of 4-methyl-3-(tetra{\-}hydro-2{\it H}-pyran-2-yl)oxythia{\-}zole-2(3{\it H})-thione ({\bf MTTOTHP}) was investigated using X-ray diffraction and computational chemistry methods for determining properties of the nitro{\-}gen{---}oxygen bond, which is the least stable entity upon photochemical excitation. Experimentally measured structure factors have been used to determine and characterize charge density via the multipole model (MM) and the maximum entropy method (MEM). Theoretical investigation of the electron density and the electronic structure has been performed in the finite basis set density functional theory (DFT) framework. Quantum Theory of Atoms In Molecules (QTAIM), deformation densities and Laplacians maps have been used to compare theoretical and experimental results. MM experimental results and predictions from theory differ with respect to the sign and/or magnitude of the Laplacian at the N{---}O bond critical point (BCP), depending on the treatment of {\it n} values of the MM radial functions. Such Laplacian differences in the N{---}O bond case are discussed with respect to a lack of flexibility in the MM radial functions also reported by Rykounov {\it et al.} {\it Acta Cryst.} (2011), B{\bf 67}, 425{--}436. BCP Hessian eigenvalues show qualitatively matching results between MM and DFT. In addition, the theoretical analysis used domain-averaged fermi holes (DAFH), natural bond orbital (NBO) analysis and localized (LOC) orbitals to characterize the N{---}O bond as a single {$\sigma$} bond with marginal {$\pi$} character. Hirshfeld atom refinement (HAR) has been employed to compare to the MM refinement results and/or neutron dataset C{---}H bond lengths and to crystal or single molecule geometry optimizations, including considerations of anisotropy of H atoms. Our findings help to understand properties of molecules like {\bf MTTOTHP} as progenitors of free oxygen radicals.

Further data

Item Type: Article in a journal
Refereed: Yes
Keywords: Quantum crystallography; Maximum entropy method; Multipole model; Charge density; Homolytic cleavage; Quantum information crystallography; O-alkyl thiohydroxamate; N,O-bond order; Hydroxylamine derivative
Institutions of the University: Faculties > Faculty of Mathematics, Physics und Computer Science > Group Material Sciences > Chair Crystallography
Faculties > Faculty of Mathematics, Physics und Computer Science > Group Material Sciences > Chair Crystallography > Chair Crystallography - Univ.-Prof. Dr. Sander van Smaalen
Result of work at the UBT: Yes
DDC Subjects: 500 Science > 530 Physics
Date Deposited: 02 Sep 2020 08:42
Last Modified: 02 Sep 2020 08:42
URI: https://eref.uni-bayreuth.de/id/eprint/56712