Luis Muriel, Alejandro Gomez, Mario Pasalic, Duvan Zapata and Sam Lammers shared the goals in another hugely-entertaining Atalanta performance.
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Luis Muriel became the first Colombian to score two goals against Brazil when he netted twice in the first half.
Barca, who played an hour without the benched Messi, could see their lead at the top of the table reduced to nine points if Atletico Madrid beat relegation-threatened Deportivo La Coruna on Sunday night
Despite a confidence-boosting victory over Liverpool on Saturday, the hosts reverted to the cautious approach, which restricted them to a goalless draw in Spain last month
Clear chances were few and far between for both sides despite Sevilla registering 25 shots to United’s six, but the only one which looked like going in came when Luis Muriel’s header was spectacularly tipped over by De Gea