I would say because you get more out of an RDBMS than merely relational data structure. You also get:
- High level and powerful query language (OtoDB uses this feature rather extensively)
- Optimized storage and data retrieval engine (data indexes, etc)
- A well-known paradigm
- Additional power at the data server level like views, or clusters
An RDBMS does more than just store and retrieve datasets. It also prepares data based on SQL commands you send it. Maybe I'm wrong, but it seems that memcached is just a storage mechanism. I.e. your code has to handle sorting/filtering. With an RDBMS you can ask the data servers to do this.
There are probably some other reasons too, that I'm not thinking of. I should also point out that you are in fact using one relational feature, that of one-to-one relationships.