There were big wins for Sevilla and Malaga on a busy day of La Liga action Saturday.
Champions Barcelona suffered their second La Liga defeat of the season as they went down to a 2-1 loss at Sevilla.
Without the injured Lionel Messi, Luis Enrique's side - who lost 4-1 to Celta Vigo in their last away league match - hit the post through a Neymar free-kick midway through the first half.
The woodwork denied Barca again as Luis Suarez's curling effort came close and Unai Emery's men took advantage of those escapes after the interval.
Sevilla moved in front when Kevin Gameiro's dangerous ball across the face of goal found Michael Krohn-Dehli, who smashed past Claudio Bravo. Within six minutes it was two when Vicente Iborra beat the offside trap to head home a Krohn-Dehli delivery.
Barca had a lifeline when Neymar converted a penalty 16 minutes from time after substitute Sandro Ramirez's shot had been blocked by the hand of Benoit Tremoulinas.
The visitors then hit the frame of the goal for a third time through Sandro as Sevilla held on for a famous victory.
The result means Barcelona remain behind top two Villarreal and Celta Vigo, while title rivals Atletico Madrid and Real Madrid have the opportunity to move above the champions when they play each other on Sunday.
Elsewhere, a brilliant hat-trick from Charles gave Malaga their first win of the league season as their 10 men beat David Moyes' Real Sociedad 3-1 at home.
The former Celta striker scored twice in the opening seven minutes, including a spectacular opener before Imanol Agirretxe got a goal back for the visitors.
Moyes' hopes of a much-needed result were boosted when Fernando Tissone received a second yellow card, but were then dashed by Charles' 89th-minute strike. The defeat leaves struggling Real with just six points from their opening seven fixtures.
Eibar's impressive start to the campaign continued with a 2-0 win at relegation candidates Las Palmas, with the goals coming from Saul Berjon and Borja Baston.
On-loan Barcelona youngster Alen Halilovic scored in Sporting Gijon's 2-1 victory away to Espanyol.
Alex Menendez's last-gasp goal sealed the points after Felipe Caicedo had cancelled out Halilovic's opener.
In Saturday's other game, Deportivo La Coruna were held to a 1-1 draw at Granada. The away side had taken the lead through Faycal Fajr, but Piti's equaliser stalled their positive run of form.