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The Portuguese side will host the first leg on April 1 against the Premier League team, whose only hope of silverware this season now lies with Europe's secondary club competition.
"We know they are a good team and of course we have played them before in the Champions League," Liverpool coach Rafa Benitez told Liverpool's website.
"They are a massive club with a lot of support from their fans and it will be a tough game.
"They are top of the table and playing really well at the moment. I know a number of their players well - Aimar, Saviola, Garcia - so we know they have a lot of quality."
