I just tried it and it worked fine for me. And I added several to newly-created collections during the recent Open Road freebie bonanza. I just click the button next to the book, select "Add to Collection" and either create a new one or add it to an existing one.
If it's not working for you, it may just be a temporary glitch. If you continue to have issues, maybe try logging out and back in, or contact Amazon support.
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