English Prepositions: In and At

English native speaker here, with a question that came up while tutoring ESL:

What are some (non-obscure) instances/examples in which you cannot use "at" plus a building word, and instead *must* use in?

For example, we have:
at the library
at the museum
at the cafe
at city hall
etc

Some of these have more general/specific meanings (at the library is more general than at the cafe, which refers usually to an already mentioned cafe), and often "in" could be used too... but "at" works in all of these situations. When MUST one use "in"?

Thanks! :D