(C 6 F 5 )Te(CH 2 ) 3 NMe 2 ( 1 ), a perfluoro-phe-nyltellurium deriva-tive capable of forming intra-molecular N∙∙∙Te interactions, was prepared and charac-terized. The donor-free reference substance (C 6 F 5 )TeMe( 2 ) and the unsupported adduct (C 6 F 5 )(Me)Te∙NMe 2 Et ( 2b ) were studied in parallel. Mole-cular structures of 1 , 2 and 2b were determined by single crystal X-ray diffraction and for 1 and 2 by gas-phase electron diffraction. The structure of 1 shows N∙∙∙Te distan-ces of 2.639(1) A (solid) and 2.694(53) A (gas). Ab initio plus NBO and QTAIM calculations show significant charge transfer effects within the N∙∙∙Te interactions and indicate sigma-hole interactions. © 2020 Wiley-VCH GmbH.
