Flask is great if you're going to do a complex app. All the interface will be custom designed (so the Django admin is of no use). You have a database heavy app, SQLAlchemy is more flexible than Django ORM and allows greater SQL expression, Unit of Work etc. Jinja2 is more flexible then Django templates (and faster). Flatland is more flexible than Django forms (supports nested forms for example).
That being said, Django is also great for some large apps and just for example it's great for news sites where new types of content is added each day and the admin interface saves a ton of time. For simple apps it's also brilliant because everything that's in Django works well together and you don't need the extra features of the aforementioned libraries.
So to sum up, both great frameworks and I use both every day :)