One case is where you have fairly ragged entities that may have several of many attributes but result in very sparse rows.
Another case is when users are effectively designing their own schemas but you want to keep them, for example I have a database for a CMS where users can define nested hierarchies of keys with translations that would be impossible to fit into a schema. You could just toss this data into a JSON column, but its an example of nonrelational data.
What's an example of data that's not relational?