The structure of monochlorodimethyl ether has been reinvestigated by means of electron diffraction of the vapour. The rotation of both the chloromethyl group and the methyl group is restricted; the chlorine atom is approximately in the gauche position with respect to the O‐C bond. The carbon‐chlorine bond length is 1.813 Å, significantly larger than in chloroalkanes. The bond between the chloromethyl carbon atom and the oxygen atom is shorter than the carbonoxygen bond in aliphatic ethers.
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Planje et al. (1965) studied this question.