No. The relationship has to be at a certain point above friend and you still have to have the "Sociable" mood going on. I've done it several times in the last couple of days. Ask to be Roommate comes earlier in a conversation I've noticed. Sometimes you do have to remove options from the friendly section. Don't forget to ask about their day and the game/book. Make sure you know their alma mater, career. It's there though.