What you could do is create a table solely for reservations.
Assuming that one room can never be occupied by two different entities at any time, you could add a unique key to the "room_id" field.
Alternatively, you could lock the table for writing (see this page in the MySQL manual), insert the reservation, and then unlock the table. I'm no SQL guru, and this might actually be the preferred method, so... perahps someone with more DB experience can comment on these two methods.