Villarreal went down 2-0 at El Madrigal against third-tier Mirandes in the second leg of their fourth-round tie to crash out of the Copa del Rey 3-1 on aggregate.
• Villarreal sack Garrido
The defeat, coupled with the team's precarious position of 17th in the Primera Division, prompted the club's board to dispense with coach Juan Carlos Garrido's services.
Pablo Infante scored both of Mirandes' goals, while Villarreal had Mateo Musacchio sent off late on.
Atletico Madrid were knocked out by Segunda Division opposition in the form of Albacete.
Victor Curto scored the only goal in the first minute to seal a 1-0 win and 3-1 aggregate success.
Other shock exits saw Alcoron see off Real Zaragoza and Real Betis go out despite victory over Cordoba.
Alcoron won 2-0, with Oriol Riera and Joaquin Quini both notching in the last three minutes, for a 3-1 aggregate win.
Cordoba lost 2-1 at Betis as Jorge Molina's brace bettered Garcia Borja's effort, but the lower-ranked side progressed on away goals. Cerra saw red for Cordoba two minutes from time.
Away goals also came into play as Rayo Vallecano beat Racing Santander 4-3 at home, only to see their opponents go through after the tie ended 6-6 over the two games.
Two from Christian Stuani and one from Alexis Tziolis provided Racing with the vital three goals, while Medina Piti, Miguel Michu, Andrija Delibasic and Raul Tamudo were on target for Rayo.
Levante won the all-Primera Division clash against Deportivo La Coruna in extra-time with an eventual 4-1 win on the night.
Nabil El Zhar, Sergio Ballesteros and Ruben Suarez all scored in normal time for Levante, while Depor's Pablo Alvarez also netted.
That left the scores matched after 180 minutes, leaving Arouna Kone to seal it 11 minutes into the first period of extra-time. Borj a was sent off for a second yellow in the dying seconds.
Another eye-catching fixture, between Malaga and Getafe was decided when Diego
Buonanotte put the former through five minutes after coming on as an 80th-minute substitute.
The score on the night was 2-2 - Willy Cabellero's own-goal and Mane's effort going in after Ruud van Nistelrooy's strike - handing Malaga the tie following their earlier 1-0 win. Malaga had also coped with Weligton's sending off in the 77th minute.
A 1-1 draw was enough to see Osasuna through 4-2 overall, at the expense of La Liga rivals Almeria. Roland Lamah and Henok Goitom were on target as the game came to life in the last ten minutes.
Athletic Bilbao repeated their first-leg 1-0 win over Real Oviedo, with Ander
Herrera the scorer in the second leg.
A 2-1 win for Granada over Real Sociedad was not enough to prevent a 5-2 defeat in the tie. Guilherme Siqueira's penalty and Alexandre Geijo's follow-up came before Imanol Agirretxe's riposte but, with the visitors' three-goal cushion, it was largely academic.
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