Hmm, kinda new to me. Never encountered this, though weather this will help.
I once had to talk to an NPC but it wouldent let me since NPC was stuck in combat, all i did was attack the npc till they went to ground since it was an essential NPC which i'm sure serana is. Could give it a try might let you talk to her afterward if you try that? :S cant guarantee it'll work though.