The answer to this is the same 'ol baking soda. Aside from filling the stained cup with boiling water, you can try rubbing insde the mug (where the stain is) with baking soda. That is if an overnight soaking in hot water or vinegar does not work.
You can also try rubbing a paste of cornstarch and vinegar on the stained part for a few minutes and then scrub away. A lot of times this is enough.
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