This was after Inaki Williams struck in the 90th minute to earn Athletic Bilbao a 1-0 win at the Ramon Sanchez Pizjuan.
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Moments before Bilbao’s momentous triumph was confirmed, Messi threw an arm at Asier Villalibre, who had earlier scored a 90th-minute equaliser in normal time to deny Barca victory.
Athletic Bilbao got off to a dream start in their first match under new coach Marcelino when forward Inaki Williams latched on to a low through ball and raced towards goal.
They only avoided defeat thanks to some outstanding saves by Germany goalkeeper Marc-Andre ter Stegen