I cannot tell that from the database, sure, because a database is simply structural information, not functional. Without a list of things that the database is supposed to
do, it might be great or it might suck. Don't know.
But all modern systems have both structure and behavior. For every database there is a MVC model somewhere, for instance. And looking at those controllers, you should absolutely be able to tell whether the database is well-constructed or not.
Now there's another consideration: does the database structure map into some problem domain such that the introduction of new controllers will be supported? That's usually what people mean when they talk about architecture: the mapping of a problem domain over to a solution domain such that changes in the requirements have minimal impact on the solution.
In System-of-Systems work I'd argue yes, such work has some value -- as long as it is continually driving some kind of delivery (and not just "smart guys drawing boxes"). But in regular green-field system development? Not so much. That's because the tendency is to begin focusing on the wrong thing, the model instead of the user. Timeboxes help with this, so much so that I wouldn't advise any stand-alone architectural work in such an environment without team integration and time-boxing.