- 1. FC Köln
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.
Two penalties helped Real register a healthy victory in the first leg of their cup tie.
Just a second slip up from Barcelona this La Liga season allowed Real Madrid and Atletico Madrid to close to within eight points of the leaders.
Valencia withstood a late onslaught from Real Betis to move up to second with an enthralling 6-3 win at the Benito Villamarin on Sunday.
Barcelona and Real Madrid remain locked together on 81 points at the top of La Liga after seeing off Espanyol and Valencia respectively on Saturday.
Antoine Griezmann scored a brace to help Atletico Madrid win their La Liga encounter 3-0 against Valencia on Sunday.
Real Madrid currently top La Liga with two wins from two games. They are still missing Cristiano Ronaldo due to the knee ligament injury that forced him off during Portugal's Euro 2016 final victory over France
Villareal guaranteed a spot in the Champions League qualifiers after four years after sealing fourth spot in the La Liga with a 2-0 win over Valencia.
Lionel Messi suffered renal colic, a problem commonly caused by kidney stones, at the Club World Cup in Japan in December forcing him to miss Barcelona's semi-final against China's Guangzhou Evergrande.