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Barbs can be aggressive in groups smaller than 6. They aren't always, though. I have had a barb that only had two glassfish to school with, and it did not attack anything.
One oddity that can go in a 5g would be a dwarf puffer. The dwarf puffer (which is the only freshwater puffer that would fit) can live in tiny, tiny tanks, but it absolutely, positively must live alone. If it has tank mates, it will hurt them. It may take weeks or months, but eventually it will feel hungry enough to take a bite of a tank mate, no matter how big the other fish is.
Unfortunately, there are very few small fish that don't school. Schooling is the best way for small fish to survive predation, so it's a pretty common trait.
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