(CH3)3Si-CG SRC="/images/entities/tbd1.gif">C-Cges/entities/tbd1.gif">C-Si(OCH2CH2)3N·2CHCl3 (3·2CHCl3) was analyzed crystallographically. Each chloroform molecule interacts with diacetylene 3 through one C-H···O contactand one C-H···ges/gifchars/pi.gif" BORDER=0 > contact. Based on distances and angles, these interactions are found to beweaker than those encountered in compounds containing only C-H···O interactions orC-H···ges/gifchars/pi.gif" BORDER=0 > interactions. A comparison between the infrared, 13C, and 29Si NMR data of 3obtained in CHCl3 or CDCl3 solutions with data obtained in the solid state for the unsolvatedmaterial gives further evidence that the chloroform molecules are only weakly bonded tothe diacetylenic silatrane. Density functional theory (DFT) calculations have been carriedout at the B3LYP level that confirm these findings.