Carbon<sup>13</sup> chemical shift assignments are reported for <i>Z</i>- and <i>E</i>-dothiepin hydrochloride (N,N-dimethyldibenzo[b,e]thiepin-<i>delta</i>-11(6H)', <i>gamma</i>-propylamine hydrochloride). The commercial product, a mixture of approximately 95% <i>E</i>-isomer, is of clinical importance as an antide-pressant drug. The precursor and degradation product, 6H-dibenzo[b,e]thiepin-11-one, and related model compounds were also studied. Homo- and heteronuclear shift-correlated 2D NMR, selective INEPT, selective and off-resonance decoupling, and inversion-recovery (<i>T</i><sub>1</sub>) experiments as well as model compound comparisons were used in assignments.

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