35Cl NQR spectra in SnCl4.DME have been observed in the range of 77 K to 420 K. Two NQR lines have been detected at the temperatures above 96 K and a single line at 77 K. Three crystal modifications of SnCl4.DME have been found. A trans geometry is suggested for one of them. The Zeeman effect on a single crystal of SnCl4.DME has been studied at room temperature. It is revealed on the basis of the orientations of the z axes of the electric field gradient that the molecule of SnCl4.DME has a cis geometry at room temperature. The higher-frequency line is assigned to the axial Cl atoms and the lower-frequency one to the equatorial Cl atoms. The asymmetry parameters
for the Cl atoms contributing to the higher- and lower-frequency lines are 0.038 and 0.099, respectively.