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1. Account was already created with that cd-key and maybe you don't remeber that you created it or you don't know it that it has been already used.
2. You use wrong cd-key (right on game- View CD-Key)
There isn't other options, because is almost imposible for steam fault that he gave you wrong cd-key.
Now you can only try contact to Steam or ubisoft support.
BTW "I bought it through STEAM thus it was showing in my library." To be sure you bought game from here
http://store.steampowered.com/app/232910/
Or from other place you just bought code for steam??
But i don't get it how to underdstand that what you wrote. You bought one copy of game as a gift and you sent it to your brother OR you bought game because your brother already have it and you wanted it too but after buy you still have demo?
If number one then I already explained to you. The only way is to download non steam version and play with your brother on this one account.
If second then use CD-Key to already existed account (it should automatic add to account after log-in to first account after first time playing) or create new one with this account (if you didn't already use this cd key).