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Yes, I started off using double quotes then tried single. I used SQLite shell version 3.7.9 from SQLite.org and also tried sqlite admin 0.8.3.2...
Update: Whoops, I should have thought of this before. Soon after assigning a different volume letter to my media drive, I instinctively rescanned the folders in question, went off to do something else and forgot about it. Of course now it's obvious the "not unique" error is due to the path already existing. The fact that I added files as a playlists the first time and as folders this time made it less obvious. Sorry, hope I didn't waste too much of your time!
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Happy to hear you have it all sorted out now.