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Spain's famed passing game failed against a high-tempo, tenacious Chile team, its era ending in the storied Maracana Stadium filled mostly with Chilean supporters.
Eduardo Vargas tricked goalkeeper Iker Casillas into diving the wrong way, then shot into an unguarded goal in the 20th minute. Charles Aranguiz scored in the 43rd when the ball landed at his feet after Casillas punched out a free kick.
Spain's second loss, after a 5-1 rout by the Netherlands, ended any hope of advancing. Chile and the Netherlands will both advance, regardless of who wins the game between them.
Spain won the European Championship in 2008 and 2012, in addition to the 2010 World Cup.