DogeCoin was the first coin that had random block rewards, and BlackCoin the first PoW/PoS hybrid.
A bit inaccurate

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First random block reward coin was Junkcoin.
First PoW/PoS hybrid was Novacoin
Edit:
First PoW/PoS hybrid was Peercoin for SHA and Novacoin for script.
Blackcoin was the one that started multi-pool for another coin other than btc...If not the first, it was the one that made other coins change the way they think.