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The 3,3-disubstitued 3-silaheterocyclohexane with an electronegative substituent at silicon, 3-fluoro-3-methyl-3-silatetrahydropyran 1, was synthesized, and its molecular structure and conformational properties studied by gas-phase electron diffraction (GED) and low temperature C-13 and F-19 NMR spectroscopy. Quantum-chemical calculations were carried out both for the isolated species and Hcomplexes in gas and in polar medium. The predominance of the 1-FeqMeax conformer (1-F-eq:1-F-ax ratio of 65:35, Delta G degrees = 0.37 kcal/mol) determined from GED is close to the theoretically estimated conformational equilibrium, especially at the DFT level. In solution, low temperature NMR spectroscopy showed no decoalescence of the signals in C-13 (down to 95 K) and F-19 NMR spectra (down to 123 K). However, the calculated F-19 chemical shift of -173.6 ppm for the 1-FeqMeax conformer practically coincides with the experimentally observed value (-173 to -175 ppm) as distinct from that for the 1-FaxMeeq conformer (-188.8 ppm), suggesting compound 1 to be anancomeric in solution, in compliance with its theoretical and experimental preference in the gas phase.