Crystalline 1,4-distannabarrelene compounds [(ADC Ar ) 3 Sn 2 ]SnCl 3 ( 3-Ar ) (ADC Ar = {CC(NDipp)CAr}; Dipp = 2,6-iPr 2 C 6 H 3 , Ar = Ph or DMP; DMP = 4-Me 2 NC 6 H 4 ) derived from anionic dicarbenes Li(ADC Ar ) ( 2-Ar ) (Ar = Ph or DMP) have been reported. The cationic moiety of 3-Ar features a barrelene framework with three coordinated Sn(II) atoms at the 1,4-positions, whereas the anionic unit SnCl 3 is formally derived from SnCl 2 and chloride ion. The all carbon substituted bis-stannylenes 3-Ar have been characterized by NMR spectroscopy and X-ray diffraction. DFT calculations reveal that the HOMO of 3-Ph (epsilon = -6.40 eV) is mainly the lone-pair orbital at the Sn(II) atoms of the barrelene unit. 3 - Ar readily react with sulfur and selenium to afford the mixed-valence Sn(II)/Sn(IV) compounds [(ADC Ar ) 3 SnSn(E)](SnCl 6 ) 0.5 (E = S 4-Ar , Ar = Ph or DMP; E = Se 5-Ph ). © 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.