Villarreal continued their unbeaten start after beating struggling Elche 4-0 in La Liga on Sunday, two points behind Real Madrid.
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Gerard Moreno and Giovanni Lo Celso scored in the first half before Francis Coquelin and Jose Luis Morales scored in the closing minutes.
Unai Emery’s team is the only team to have conceded a goal in the Spanish top flight and are level with Barcelona on 10 points.
Athletic Bilbao’s unbeaten run ended in a 1–0 home loss to Espanyol as Martin Braithwaite scored in his debut days after his contract with Barcelona expired.
Osasuna pulled off a 2–1 win over Rio Vallecano for the third time in four games courtesy of a late goal from Rubén García.
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