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Barcelona's defeat to Valencia raised early doubts about Quique Setien's appointment and gave Real Madrid the chance to move three points clear at the top.
Valencia will provide Barcelona's new manager Quique Setien with his first true test and an opportunity to make his mark.
Toni Kroos scored a sensational goal in Real Madrid's 3-1 win over Valencia in the Spanish Super Cup semi-final.
Real Madrid beat Valencia 3-1 on Wednesday to reach the final of the controversial Spanish Super Cup in Saudi Arabia.
Karim Benzema scored a dramatic injury-time equaliser to salvage a 1-1 draw for Real Madrid against Valencia at Mestalla.
FC Barcelona and RB Leipzig sealed their spots in the round of 16 of the Champions League while Liverpool and Chelsea will have to wait for the final round of group stage matches.
Frank Lampard said Chelsea were taught a "harsh lesson" in Champions League football after Valencia put a week of turmoil behind them to win 1-0 at Stamford Bridge.
In contrast to Chelsea's bright hope for the future, Valencia travel to England mired in an institutional and sporting crisis.
Chasing a record fifth consecutive triumph, Barcelona were undone by a relentless and gutsy Valencia side.
Unai Emery insisted his side's Europa League semi-final against Valencia is still "50-50" despite Arsenal taking a 3-1 first leg lead to Spain.
Alexandre Lacazette's stunning 36th-minute free-kick put Arsenal through to a Europa League final four meeting with Spanish side Valencia.
Barcelona started the day at the top of the pile and then Atletico Madrid enjoyed a couple of hours at the summit after edging past Real Betis.
Jose Mourinho again pointed the finger at his players' failings after a 0-0 draw against Valencia in a Champions League match.
Manchester United again looked devoid of ideas and invention to draw a blank and fall two points behind Group H leaders Juventus.
Ahead of Tuesday's UEFA Champions League clash with Valencia, Jose Mourinho insisted he doesn't fear for his job.
A tearful Cristiano Ronaldo left the pitch in disbelief in the 29th minute, having aimed a petulant, but seemingly harmless, kick at Valencia defender Jeison Murillo.
Holders Barcelona secured a place in the Copa del Rey final for the fifth season running, becoming the first side to achieve such a feat.
Messi was pivotal in Barcelona's 1-0 win where he created something out of nothing for Luis Suarez to head home in the 67th minute.