Real Madrid was relegated to the second place in La Liga after being held to a 1-1 draw at home by Osasuna on Sunday evening. While Karim Benzema was back in the starting 11, Andriy Lunin replaced Thibaut Courtois in goal.
Earlier on Saturday, Barcelona defeated Mallorca 1-0, helped by Robert Lewandowski's goal. The victory helped them edge out Real Madrid from the top of the table. Barcelona now sits atop with 19 points from seven games.
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Madrid took the lead with a stroke of fortune and a dose of controversy in the 42nd minute when Vinicius Jr's cross went in at the far post. Osasuna players claimed offside as VAR rejected the visitors' appeals.
Kike Garcia's second-half header gave Osasuna a deserved equalizer but Madrid should have won when they were given a 78th-minute penalty after David Garcia's push on Benzema, reports Xinhua.
Benzema sent the spot kick against the bar and Osasuna clung on bravely until the end to take a point and end Madrid's 100 percent start to the season.
Real Betis suffered their second defeat of the season when they lost 1-0 away to Celta Vigo, who took all three points after Gabri Veiga's excellent ninth-minute shot from outside of area.
Betis' options were severely reduced after 20 minutes when Luis Felipe was sent off for a professional foul.
Valencia saved a point in the 96th minute after Espanyol keeper Alvaro Fernandez made a huge error to allow Eray Comert's speculative lob to loop into the net.
Gabriel Paulista's header had put Valencia ahead, before excellent goals from Joselu and Sergi Darder seemed as if they would give Espanyol only their second win of the campaign.
Real Sociedad won a thrilling and chaotic game 5-3 away to Girona with Alexander Sorloth, Martin Zubimendi, Brais Mendes and Takefusa Kubo scoring for the visitors, who took the lead and then had to come back from behind after Rodrigo Riquelme, Arnau Martinez and Valentin Castellano netted for the home side.
On Saturday, Robert Lewandowski's goal after 20 minutes was enough to give Barcelona a 1-0 win away to Mallorca, which takes them top of the table.
Mallorca had chances to level through Jaume Costa, Vedat Muriqi and Lee Kang-in, but Barca keeper Marc-Andre Ter Stegen, who has now gone 534 minutes without conceding a goal, saw Barca cling on for the win.
Marcos Llorente and Alvaro Morata gave Atletico Madrid a comfortable 2-0 win away to Sevilla, whose coach Julen Lopetegui is in danger of the sack after his side have taken just five points from a possible 21.
Cadiz defended stoutly to draw 0-0 at home to Villarreal, with the help of some excellent saves from keeper Jeremias Ledesma.
Cadiz had defender Iza Carcelan sent off in the last minute for a professional foul as Arnaut Danjuma went through on goal, but Dani Parejo hit the resulting free kick into the defensive wall.
Valladolid won an entertaining game 3-2 win away to Getafe.
Sergio Leon's penalty put Valladolid ahead in the 19th minute, before Borja Mayoral (28 minutes) and Damien Sanchez (30 minutes) reacted to put Getafe in front.
Leon's second of the game made it 2-2 in the 36th minute and Oscar Plano put the visitors ahead with a powerful shot in the 48th minute.
Enes Unal then saw Valladolid keeper Jordi Masip save a penalty that would have meant a share of the points.
Athletic Bilbao continued their best start to a season since 1956 with a 4-0 win at home to Almeria.
Inaki Williams opened the scoring after nine minutes following a cross from his brother Nico, and Oihan Sancet doubled the lead in the 17th minute.
Inaki then set up Nico for the third goal and Mikel Vesga rounded off the win from the penalty spot as Athletic move third.