Deportivo La Coruna have been relegated from La Liga after a 2-0 home loss to Valencia on Saturday.
Their loss meant that Mallorca and Getafe will keep their spot in Spanish football’s top-flight despite their failure to win on the final day of the season.
Elsewhere, Cristiano Ronaldo broke the record for most goals scored in a league season with a double in Real Madrid’s 8-1 humiliation of bottom side Almeria.
But there were tears for Deportivo – a semi-finalist in the Champions League in 2004 and a consistent top-half finished in La Liga in recent seasons – who enter the Segunda Division for the first time since 1991.
Starting the game one spot above the drop zone, things looked bad for the hosts after just four minutes when striker Aritz Aduriz struck.
As Deportivo chased a result and grew ever more desperate, the gaps at the back became bigger, culminating in Roberto Soldado’s match-sealing goal on 96 minutes.
If Deportivo had snatched a draw, they would have stayed up on goal difference after Mallorca lost 4-3 at home to Atletico Madrid.
A Sergio Aguero double and Juanfran’s strike in the first hour had Atletico cruising, but a Jonathan de Guzman penalty and a Pierre Webo header in a 10-minute spell gave Mallorca a chance.
A third to Argentina striker Aguero with nine minutes to play sealed the result, although Cameroon forward Webo got his second in injury time as Mallorca claimed 17th on the table to escape the drop.
Cata Diaz’s ninth-minute goal gave Getafe the point they needed to remain in La Liga with a 1-1 draw at Real Sociedad, who were also battling relegation.
Real Zaragoza, who began the day in the bottom three, won 2-1 at Levante thanks to a double from midfielder Gabi.
In Madrid, Ronaldo’s double allowed him to finish the La Liga campaign with an incredible 40 goals, two better than former record-holders Hugo Sanchez and Telmo Zarra.
The goals came easy in the 8-1 rout, with Portugal forward Ronaldo opening his account after just four minutes and sealing his brace with 13 minutes to play.
Manchester City loanee Emmanuel Adebayor staked a claim for a permanent move to the club with a hat-trick in his final appearance under his current deal, while Karim Benzema snared a double and youth-team player Joselu scored the eighth in the dying stages.
Real finish the season having scored 102 league goals – the second time in succession they have hit three figures in a campaign.
Barcelona had to come from behind to defeat Malaga 3-1, ensuring they held onto their four-point lead at the top of the league.
Sebastian Fernandez’s early goal put the unfancied hosts into the lead, but midfielder Bojan Krkic’s penalty levelled proceedings.
Goals from Ibrahim Afellay and Marc Bartra in the last 15 minutes sealed the result.
In other matches, Osasuna beat fourth-placed Villarreal 1-0 while Sevilla won 3-2 at Espanyol. Former Spain, Lazio and Barcelona midfielder Ivan De La Pena played his last game for the latter before his retirement.
Athletic Bilbao also won away from home with a 2-1 triumph at Racing Santander while already-relegated Hercules could only manage a goalless draw at home to Sporting Gijon.
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