The previously observed effect that the ³⁵Cl resonance frequency of cyclic a-chloroethers is highly dependant on whether the chlorine atom is in the axial or equatorial position has been investigated theoretically by the CNDO/2 and CNDO/BW methods. The observed effect is reproduced by the CNDO calculations and the results are discussed in an attempt to discern the origin of the interaction. Similar studies were performed for 1,2 dichloroethane, and benzotrichloride where marked orientational effect on the NQR frequencies are not present and again the agreement between theory and experiment is satisfactory.