Barcelona slumped to a 1-0 home defeat by Rayo Vallecano which pushed leaders Real Madrid a step closer to the La Liga title.
Karim Benzema's last-gasp winner sealed Real Madrid's stunning comeback as they recovered from 2-0 down to beat Sevilla 3-2.
Valencia shook off the late red card for Jose Gaya to hold La Liga title challengers Sevilla to a 1-1 draw.
Real Madrid were crowned Spanish Super Cup champions after goals from Luka Modric and Karim Benzema earned them a 2-0 win over Athletic Bilbao.
La Liga champions Atletico Madrid were stunned by Granada, losing 2-1 on Wednesday, while Napoli slipped to defeat against Spezia in Serie A.
Serie A leaders Napoli lost for the first time this season as Inter Milan reinvigorated their own title bid with a 3-2 win at the San Siro.
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